На задната корица:
This Laboratory Manual contains detailed descriptions for the synthesis and characterization of macromolecules. 110 elaborated examples (descriptions of experiments) plus sufficient theoretical explanations enable the reader to learn about the syntheses, modification, characterization and properties of polymers including recent developments. All experiments can be conducted with adequate laboratory equipment. Suitable for students in organic and polymer chemistry as well as for chemists in industry who want to acquaint themselves with the theoretical and practical aspects of macro-molecular chemistry.
*
Contents
1 Introduction 1
1.1 Definitions 1
1.2 Structure and Nomenclature of Macromolecular Substances 2
1.3 Properties of Macromolecular Substances 10
1.3.1 Macromolecules in Solution 11
1.3.2 Macromolecules in the Molten State 12
1.3.3 Macromolecules in the Solid State 14
1.3.3.1 Macromolecules in the Amorphous State 14
1.3.3.2 Macromolecules in the Crystalline State 15
1.3.3.3 Macromolecules in the Elastomeric State 20
1.3.4 Liquid Crystal Polymers (LCP) 21
1.4 General Literature on Macromolecules 23
1.4.1 Textbooks 23
1.4.2 Monographs and Handbooks 23
1.4.3 Laboratory Manuals 24
1.4.4 Nomenclature 24
1.4.5 Journals and Periodicals 25
1.5 List of General Abbreviations 29
1.6 Abbreviations for Technically Important Polymers 30
1.7 Relevant SI Units and Conversions 32
2 Methods and Techniques for Synthesis, Characterization, Processing, and Modification of Polymers 35
2.1 Methods for Synthesis of Macromolecules 35
2.2 Processes for Manufacturing Macromolecular Materials 47
2.2.1 Particularities in the Preparation of Polymers 47
2.2.2 Polyreactions in Bulk 49
2.2.2.1 Homogeneous Polyreactions in Bulk 49
2.2.2.2 Heterogeneous Polyreactions in Bulk 50
2.2.3 Polyreactions in Solution 50
2.2.4 Polyreactions in Dispersion 52
2.2.4.1 Polyreactions in Suspension 53
2.2.4.2 Polyreactions in Emulsion 53
2.2.5 General Techniques for Preparation of Macromolecular Substances in the Laboratory 57
2.2.5.1 Safety in the Laboratory 57
2.2.5.2 Working with Exclusion of Oxygen and Moisture 57
2.2.5.3 Purification and Storage of Monomers 58
2.2.5.4 Reaction Vessels for Polymerization Reactions 60
2.2.5.5 Control and Termination of Polymerization Reactions 62
2.2.5.6 Isolation of Polymers 64
2.2.5.7 Purification and Drying of Polymers 65
2.3 Characterization of Macromolecules 66
2.3.1 Solvents and Solubility 67
2.3.2 Determination of Molecular Weight of Polymers 71
2.3.2.1 Determination of Solution Viscosity of Polymers 73
2.3.2.2 Determination of the End Groups of Polymers 80
2.3.3 Fractionation of Polymers 81
2.3.3.1 Analysis of Fractionation Data 84
2.3.3.2 Fractionation According to the Chemical Composition 86
2.3.4 Determination of Glass Transition Temperature, Softening Point, Melting Range, and Crystallite Melting Point 87
2.3.4.1 Determination of the Glass Transition Temperature 87
2.3.4.2 Determination of the Softening Point 88
2.3.4.3 Determination of the Melting Range and the Crystallite Melting Point. . . 89
2.3.5 Determination of the Melt Viscosity (Melt Index) of Polymers 91
2.3.6 Determination of the Crystallinity of Polymers 92
2.3.7 Determination of the Density of Polymers 92
2.3.8 Degradation of Polymers 93
2.3.8.1 Thermal Degradation of Polymers 93
2.3.8.2 Chemical Degradation of Polymers 95
2.3.9 Optical Investigations on Polymers 96
2.3.10 Determination of Important Groups and Elements 97
2.3.11 Characterization of Copolymers 97
2.3.12 Mechanical Measurements on Polymers 982.
2.3.12.1 Stress-Strain Measurements 100
2.3.12.2 Dynamic-Mechanical Measurements 102
2.3.12.3 Determination of Impact Strength and Notched Impact Strength 104
2.3.12.4 Determination of Hardness 105
2.4 Processing of Polymers 105
2.4.1 Size Reduction of Polymers 106
2.4.2 Melt Processing of Polymers 106
2.4.2.1 Preparation of Polymer Films from the Melt 107
2.4.2.2 Melt-Spinning 107
2.4.3 Processing of Polymers from Solution 108
2.4.3.1 Preparation of Films from Solution 108
2.4.3.2 Solution-Spinning 109
2.4.4 Processing of Aqueous Polymer Dispersions 109
2.5 References for Chapter 2 110
3 Synthesis of Macromolecular Substances by Addition Polymerization 111
3.1 Radical Homopolymerization 112
3.1.1 Polymerization with Peroxo Compounds as Initiators 119
Example 3-1 Thermal Polymerization of Styrene in Bulk (Effect of Temperature) 121
Example 3-2 Emulsion Polymerization of Styrene with Potassium Peroxodisulfate 121
Example 3-3 Bulk Polymerization of Vinyl Acetate with Dibenzoyl Peroxide 122
Example 3-4 Polymerization of Vinyl Acetate with Ammonium Peroxodisulfate in Emulsion 122
Example 3-5 Polymerization of Acrylonitrile with Ammonium Peroxodisulfate in Organic Solution 123
Example 3-6 Bead Polymerization of Vinyl Acetate 124
Example 3-7 Polymerization of Methacrylic Acid with Potassium Peroxodisulfate in Aqueous Solution 124
3.1.2 Polymerization with Azo Compounds as Initiator 125
Example 3-8 Bulk Polymerization of Styrene with 2,2'-Azo- bisisobutyronitrile (Effect of Initiator Concentration) 126
Example 3-9 Bulk Polymerization of Styrene with 2,2'-Azo- bisisobutyronitrile in a Dilatometer 126
Example 3-10 Polymerization of Styrene with 2,2'-Azobisisobutyronitrile in Solution 128
Example 3-11 Bulk Polymerization of Methyl Methacrylate with 2,2'-Azo- bisisobutyronitrile 129
3.1.3 Polymerization with Redox Systems as Initiators 130
Example 3-12 Polymerization of Acrylamide with aRedox System in Aqueous Solution 131
Example 3-13 Fractionation of Polyacrylamide by Gel Permeation Chromatography in Water 132
Example 3-14 Polymerization of Acrylonitrile with a Redox System in Aqueous Solution (Precipitation Polymerization) 133
Example 3-15 Emulsion Polymerization of Isoprene with a Redox System . . 134
Example 3-16 Polymerization of Styrene with Redox Systems in an Organic Solvent 135
3.1.4 Polymerization Using Photolabile Compounds as Initiators 136
Example 3-17 Photopolymerization of Hexamethylene Bisacrylate 136
3.1.5 Polymerization of Cyclodextrin Host-Guest Complexes in Water 137
Example 3-18 Free Radical Polymerization of Cyclodextrin Host-Guest Complexes of Butyl Acrylate from Homogeneous Aqueous Solution (Precipitation Polymerization) 138
3.2 Ionic Homopolymerization 138
3.2.1 Ionic Polymerization via C=C Bonds 139
3.2.1.1 Cationic Polymerization with Lewis Acids as Initiators 143
Example 3-19 Cationic Polymerization of Isobutylene with Gaseous BF3 at Low Temperatures 145
Example 3-20 Cationic Polymerization of Isobutyl Vinyl Ether with BFj-Etherate at Low Temperatures 145
Example 3-21 Cationic Polymerization of oc-Methylstyrene in Solution. . . . 146
3.2.1.2 Anionic Polymerization with Organometallic Compounds as Initiators . . 147
Example 3-22 Anionic Polymerization of oc-Methylstyrene with Sodium Naphthalene in Solution ("Living Polymerization") 147
Example 3-23 Stereospecific Polymerization of Styrene with Pentylsodium . 150
Example 3-24 Preparation of Isotactic and Syndiotactic Poly(methyl Methacrylate) with Butyllithium in Solution 152
Example 3-25 Stereospecific Polymerization of Isoprene with Butyllithium. . 153
3.2.2 Ionic Polymerization via C=0 Bonds 156
Example 3-26 Anionic Polymerization of Formaldehyde in Solution (Precipitation Polymerization) 157
3.2.3 Ring-Opening Polymerization 158
3.2.3.1 Ring-Opening Polymerization of Cyclic Ethers 158
Example 3-27 Bulk Polymerization of THF with Antimony Pentachloride ... 159
3.2.3.2 Ring-Opening Polymerization of Cyclic Acetals 160
Example 3-28 Polymerization of Trioxane with BF3-Etherate as Initiator 162
3.2.3.3 Ring-Opening Polymerization of Cyclic Esters (Lactones) 163
Example 3-29 Ring-Opening Polymerization of Dilactide with Cationic Initiators in Solution 164
3.2.3.4 Ring-Opening Polymerization of Cyclic Amides (Lactams) 164
Example 3-30 Bulk Polymerization of e-Caprolactam with Anionic Initiators (Flash Polymerization) 166
3.2.3.5 Ring-Opening Polymerization of Oxazolines 166
Example 3-31 Synthesis of a Linear, N-Acylated Polyethylenimine Through Cationic Polymerization of an Oxazoline Prepared from Octanoic Acid and 2-Aminoethanol 167
3.3 Metal Catalyzed Polymerization 168
3.3.1 Polymerization with Ziegler-Natta Catalysts 169
Example 3-32 Polymerization of Ethylene with Ziegler-Natta-Catalysts ... 171
Example 3-33 Polymerization of Ethylene on a Supported Catalyst 173
Example 3-34 Stereospecific Polymerization of Propylene with Ziegler-Natta-Catalysts 174
Example 3-35 Stereospecific Polymerization of Styrene with Ziegler-Natta-Catalysts 175
Example 3-36 Stereospecific Polymerization of Butadiene with Ziegler-Natta-Catalysts: Preparation of cis-l,4-Polybutadiene 176
3.3.1.1 Metathesis Polymerization 178
Example 3-37 PolyO -Pentenylene) by Metathesis Polymerization of Cyclopentene with a Ziegler-Natta-Catalyst in Solution .. 179
3.3.2 Polymerization with Metallocene Catalysts 180
Example 3-38 Metallocene-Catalyzed Polymerization of Propylene to Highly Isotactic Polypropylene 181
3.4 Copolymerization 182
3.4.1 Random and Alternating Copolymerization 182
Example 3-39 Radical Copolymerization of Methacrylic Acid with n-Butyl Acrylate in Emulsion 191
Example 3-40 Copolymerization of Styrene with Methyl Methacrylate. . . . 192
Example 3-41 Radical Copolymerization of Styrene with 4-Chlorostyrene (Determination of the Reactivity Ratios) 194
Example 3-42 Cationic Copolymerization of Styrene with 4-Chlorostyrene (Determination of the Reactivity Ratios) 194
Example 3-43 Radical Copolymerization of Styrene with Acrylonitrile (Determination of the Reactivity Ratios) 196
Example 3-44 Radical Copolymerization of Styrene with Butadiene in Emulsion 197
Example 3-45 Radical Copolymerization of Butadiene with Acrylonitrile in Emulsion 198
Example 3-46 Radical Copolymerization of Vinyl Chloride with Vinyl Acetate (Internal Plasticization) 198
Example 3-47 Copolymerization of Styrene with Methyl Acrylate (Internal Plasticization) 200
Example 3-48 Preparation of a Styrene/Butyl Acrylate Copolymer Dispersion 201
Example 3-49 Radical Copolymerization of Styrene with 1,4-Divinylbenzene in Aqueous Suspension (Crosslinking Copolymerization) . . . 202
Example 3-50 Cationic Copolymerization of 1,3,5-Trioxane with 1,3-Dioxolane (Ring-Opening Copolymerization) 202
Example 3-51 Radical Copolymerization of Styrene with Maleic Anhydride (Alternating Copolymerization) 203
Example 3-52 Radical Copolymerization of Cyclohexene with Sulfur Dioxide (Alternating Copolymerization) 203
3.4.2 Block and Graft Copolymerization 204
Example 3-53 Preparation of a Block Copolymer of 4-Vinylpyridine and Styrene by Anionic Polymerization 207
Example 3-54 Preparation of a Butadiene-Styrene Block Copolymer 208
Example 3-55 Graft Copolymerization of Styrene on Polyethylene 209
3.5 References for Chapter 3 210
4 Synthesis of Macromolecular Substances by Condensation Polymerization and Stepwise Addition Polymerization 212
4.1 Condensation Polymerization (Polycondensation) 212
4.1.1 Polyesters 217
4.1.1.1 Polyesters from Hydroxycarboxylic Acids 219
4.1.1.2 Polyesters from Diols and Dicarboxylic Acids 219
Example 4-1 Preparation of a Low Molecular Weight Branched Polyester from a Diol and a Dicarboxylic Acid by Melt Condensation . . 219
Example 4-2 Preparation of a High Molecular Weight Linear Polyester from a Diol and a Dicarboxylic Acid by Condensation in Solution 221
4.1.1.3 Polyesters from Diols and Dicarboxylic Acid Derivatives 222
Example 4-3 Preparation of a Polyester from Ethylene Giycoland Dimethyl Terephthalate by Melt Condensation 223
Example 4-4 Preparation of a Polycarbonate from 4,4'-lsopropylidenediphenol (Bisphenol A) and Diphenyl Carbonate by Transesterification in the Melt 223
Example 4-5 Preparation of a Thermotropic, Main-Chain Liquid Crystalline (LC) Polymer by Interfacial Polycondensation 225
Example 4-6 Preparation of a Liquid Crystalline (LC), Aromatic Main-Chain Polyester by Polycondensation in the Melt 226
Example 4-7 Preparation and Crosslinking (Curing) of Unsaturated Polyesters 227
Example4-8 Preparation and Crosslinking (Curing) of Alkyd Resins 230
4.1.2 Polyamides 232
4.1.2.1 Polyamides from co-Aminocarboxylic Acids 234
Example 4-9 Preparation of an Aliphatic Polyamide by Polycondensation of e-Aminocaproic Acid in the Melt 234
4.1.2.2 Polyamides from Diamines and Dicarboxylic Acids 235
Example 4-10 Preparation of Nylon-6,6 from Hexamethylenediammonium Adipate (AH Salt) by Condensation in the Melt 235
4.1.2.3 Polyamides from Diamines and Dicarboxylic Acid Derivatives 236
Example 4-11 Preparation of Polyamide 6,10 from Hexamethylenediamine and Sebacoyl Dichloride in Solution and by Interfacial Polycondensation 237
Example 4-12 Microencapsulation of a Dyestuff by Interfacial Polycondensation 238
Example 4-13 Synthesis of a Lyotropic Liquid Crystalline Aromatic Polyamide from Terephthalic Acid Dichloride and Silylated 2-Chloro-1,4-phenylenediamine by Polycondensation in Solution 240
4.1.3 Phenol-Formaldehyde Resins 243
4.1.3.1 Acid-Catalyzed Phenol-Formaldehye Condensation (Novolaks) 244
Example 4-14 Acid-Catalyzed Phenol-Formaldehyde Condensation 245
4.1.3.2 Base-Catalyzed Phenol-Formaldehyde Condensation (Resols) 245
Example 4-15 Base-Catalyzed Phenol-Formaldehyde Condensation 246
4.1.4 Urea- and Melamine-Formaldehyde Condensation Products 247
4.1.4.1 Urea-Formaldehyde Resins 247
Example 4-16 Urea-Formaldehyde Condensation 248
4.1.4.2 Melamine-Formaldehyde Resins 249
Example 4-17 Melamine-Formaldehyde Condensation 250
4.1.5 Poly(alkylene Sulfide)s 251
Example 4-18 Preparation of a Poly(alkene Sulfide) from 1,2-Dichloroethane and Sodium Tetrasulfide 252
4.1.6 Polyfarylene Ether)s 253
4.1.6.1 Poly(phenylene Ether)s 254
Example 4-19 Preparation of Poly(2,6-dimethylphenylene Ether) 255
4.1.6.2 Aromatic Polysulfides [Poly(arylene Sulfide)s] 256
4.1.6.3 Poly(arylene Ether Sulfone)s 257
Example 4-20 Synthesis of Polyfarylene Ether Sulfone) from Bisphenol A and 4,4'-Dichlorodiphenyl Sulfone 258
4.1.6.4 Polyfarylene Ether Ketone)s 259
Example 4-21 Preparation of a Substituted Poly(ether Ether Ketone) from 4,4-Bis(4-hydoxyphenyl)pentanoic Acid and 4,4-Difluorobenzophenone 260
4.1.7 Polymers with Heterocyclic Rings in the Main Chain 261
4.1.7.1 Polyimides 262
Example 4-22 Preparation of a Polyimide from Pyromellitic Dianhydride and 4,4'-Oxydianiline by Polycydocondensation 263
4.1.7.2 Poly(benzimidazole)s 263
4.1.8 Polysiloxanes 264
Example 4-23 Ring-Opening Polymerization of a Cyclic Oligosiloxane to a Linear, High Molecular Weight Polysiloxane with Hydroxy End Groups; Curing of the Polymer 266
Example 4-24 Equilibration of a Silicone Elastomer to a Silicone Oil with Trimethylsilyl End Groups 267
4.2 Stepwise Addition Polymerizations 268
4.2.1 Polyurethanes 268
4.2.1.1 Linear Polyurethanes 269
Example 4-25 Preparation of a Linear Polyurethane from 1,4-Butanediol and Hexamethylene Diisocyanate in the Melt 270
Example 4-26 Preparation of a Linear Polyurethane from 1,4-Butanediol and Hexamethylene Diisocyanate in Solution 271
4.2.1.2 Branched and Crosslinked Polyurethanes 271
4.2.2 Epoxy Resins 273
Example 4-27 Preparation of Epoxy Resins from Bisphenol A and Epichlorohydrin 275
4.3 References for Chapter 4 277
5 Modification of Macromolecular Substances 279
5.1 Chemical Conversion of Macromolecular Substances 279
Example 5-1 Polyvinyl Alcohol) byTransesterification of Polyvinyl acetate); Reacetylation of Polyvinyl Alcohol) 287
Example 5-2 Preparation of Poly(vinylbutyral) 288
Example 5-3 Saponification of a Copolymer of Styrene and Maleic Anhydride 289
Example 5-4 Preparation of Linear Poly(ethylenimine) by Saponification of Polyoxazoline 289
Example 5-5 Acetylation of Cellulose 290
Example 5-6 Preparation of Trimethylcellulose 291
Example 5-7 Preparation of Sodium Carboxymethylcellulose 292
Example5-8 Esterification of Cellulose with p-Toluenesulfonyl Chloride . . 292
Example 5-9 Acetylation of the Semi-Acetal End Groups of Poly(oxymethylene) with Acetic Anhydride 293
5.2 Crosslinking of Macromolecular Substances 294
Example 5-10 Crosslinking of Chlorinated Nylon-6,6 by Irradiation 295
Example 5-11 Vulcanization of a Butadiene-Styrene Copolymer (SBR). . . . 297
Example 5-12 Preparation of a Cation Exchanger by Sulfonation of Crosslinked Polystyrene 300
Example 5-13 Preparation of a Cation Exchanger by Sulfonation of a Phenol-Formaldehyde Condensation Polymer 301
Example 5-14 Preparation of an Anion Exchanger from Crosslinked Polystyrene by Chloromethylation and Amination 301
5.3 Degradation of Macromolecular Substances 302
Example 5-15 Thermal Depolymerization of Poly(oc-methylstyrene) and of Polyimethyl Methacrylate) 305
Example 5-16 Thermal Depolymerization of Poly(oxymethylene) 305
Example 5-17 Oxidative Degradation of Polyvinyl Alcohol) with Periodic Acid 306
Example 5-18 Hydrolytic Degradation of an Aliphatic Polyester 307
Example 5-19 Hydrolytic Degradation of Cellulose and Separation of the Hydrolysis Products by Chromatography 308
5.4 Modification of Polymers by Additives 308
5.4.1 Addition of Stabilizers 309
Example 5-20 Suppression of the Thermo-Oxidative Crosslinking of Polyisoprene by Addition of an Antioxidant 310
Example 5-21 Suppression of theThermal Dehydrochlorination of Polyvinyl Chloride) by Addition of Stabilizers 311
5.4.2 Addition of Plasticizers 312
Example 5-22 Polymerization of Styrene in Presence of Paraffin Oil (External Plasticization) 313
5.4.3 Addition of Fillers and Reinforcing Materials 313
Example 5-23 Preparation of a Composite Material from an Unsaturated Polyester Resin and Glass Fibers 314
5.5 Mixtures of Polymers (Polymer Blends) 314
5.5.1 Properties of Polymer Blends 316
5.5.2 Preparation of Polymer Blends 317
5.5.2.1 Concerted Precipitation from Solution 317
Example 5-24 Preparation of Polymer Blends from Solution 318
5.5.2.2 Coprecipitation of Polymer Latices 320
5.5.2.3 Mixing of Polymer Melts 320
Example 5-25 Preparation of Polymer Blends from the Melt 320
5.5.2.4 Polymerization of Monomers Containing Other Dissolved Polymers ... 321
5.6 Stretching and Foaming of Polymers 322
Example 5-26 Preparation of Foamable Polystyrene and of Polystyrene Foam 323
Example5-27 Preparation of a Urea/Formaldehyde Foam 325
5.6.1 Preparation of Polyurethane Foams 326
Example 5-28 Preparation of a Flexible Polyurethane Foam 327
Example 5-29 Preparation of a Rigid Polyurethane Foam 327
5.7 References for Chapter 5 327
Subject Index
