Chemistry and physics of macromolecules : final report of the Sonderforschungsbereich "Chemie und Physik der Makromolek¨ule" 1969-1987

목차 (Table of Contents)

• CONTENTS
• 1. General Introduction = 1
• 1.1. Polymer Science in the Federal Republic of Germany = 1
• 1.2. Objectives and Developments of the Sonderforschungsbereich 41 = 2
• 1.3. Topics and Results = 4
• 1.3.1. Pathways to New Polymers = 4
• 1.3.2. Kinetics, Mechanisms, and Polymer Characterization = 7
• 1.3.3. New Methods in Polymer Physics = 8
• 1.3.4. Conformation and Interaction of Macromolecules in Polymer Systems = 8
• 1.3.5. Macropolecules in Motion = 9
• 1.3.6. Cooperative Phenomena in Polymers = 10
• 1.4. References = 11
• 2. From Oligonuclear Phenolic Compounds to Calixarenes / Volker B$$\ddot{o}$$hmer ; Hermann K$$\ddot{a}$$mmerer = 13
• 2.1. Introduction = 13
• 2.2. Synthesis of Structurally Uniform Oligomers = 14
• 2.2.1. General Principles, Protective Groups = 14
• 2.2.2. Linear Oligomers = 15
• 2.2.3. Cyclic Oligomers, Calixarenes = 16
• 2.2.4. Chemical Modifications = 19
• 2.2.5. Synthetic Matrix Reactions = 21
• 2.3. Phenolic Oligomers in the Solid State = 23
• 2.3.1. Cyclic Oligomers = 23
• 2.3.2. Linear Compounds = 25
• 2.4. Reactions and Properties in Solution = 26
• 2.4.1. Spectroscopic Studies = 26
• 2.4.2. Acidity, pK-Values = 27
• 2.4.3. Kinetic Studies = 29
• 2.4.4. Complexation of Cations, Host-Guest Interactions = 30
• 2.5. Concluding Remarks = 32
• 2.6. References = 32
• 3. Synthesis of Monodisperse Oligomers / Manfred Rothe = 39
• 3.1. Introduction : Importance of Oligomers = 39
• 3.2. Synthesis of Monodisperse Oligomers = 41
• 3.2.1. Oligomer Formation = 41
• 3.2.2. Principles of Oligomer Synthesis = 42
• 3.2.3. Synthesis of Monodisperse Oligoamides, Homo-Oligopeptides, and Sequential Oligopeptides = 44
• 3.2.3.1. Linear Oligoamides of the Nylon Type and Collagen Models = 44
• 3.2.3.2. Cyclic Oligoamides of the Nylon Type = 50
• 3.3. Physical Properties of Synthesized Monodisperse Oligoamides and Oligopeptides = 53
• 3.3.1. Chain-Length Dependence of the Conformation of Linear Oligo-L-Prolines = 53
• 3.3.2. Ring-Size Dependence of Physical Properties = 56
• 3.4. Outlook = 58
• 3.5. References = 58
• 4. Telechelic Oligomers / Walter Heitz = 61
• 4.1. Introduction = 61
• 4.2. Telechelics by Cationic Polymerization = 63
• 4.3. Telechelics by Anionic Polymerization = 70
• 4.4. Telechelics by Radical Polymerization = 71
• 4.4.1. Mechanistic Aspects = 72
• 4.4.1.1. Elementary Steps = 72
• 4.4.1.2. Dead End Polymerization = 74
• 4.4.1.3. The Initiator = 78
• 4.4.1.4. Monomers = 81
• 4.5. Telechelics by Metal Catalyzed Reactions = 90
• 4.6. Telechelic Hard Segments = 91
• 4.7. References = 93
• 5. Cyclic and Macrocyclic Compounds / Hartwig H$$\ddot{o}$$cker ; Rolf C. Schulz = 97
• 5.1. Introduction = 97
• 5.2. Ring-Chain Equilibria = 98
• 5.3. Cycloolefins and Cycloparaffins Obtained by Metathesis Polymerization of Cyclomonoolefins = 98
• 5.4. Properties of Cycloolefins and Cycloparaffins = 102
• 5.5. Cyclic Oligomers of Cycloacetals = 104
• 5.6. Synthesis of Cyclophanes via Polycombination Reaction Induced by Electron Transfer to Divinylidene Compounds = 107
• 5.7. Macrocyclic Polystyrene = 109
• 5.8. Concluding Remarks = 113
• 5.9. References = 113
• 6. Kinetics of Copolymerization / Dietrich Braun ; Wojeiech K. Czerwinski = 115
• 6.1. Introduction = 115
• 6.2. Experimental Methods = 116
• 6.3. Binary Copolymerization = 117
• 6.3.1. Classical Rate Model = 117
• 6.3.2. Model of Diffusion Controlled Termination = 118
• 6.3.3. Penultimate Model = 119
• 6.3.4. Supplementary Concepts = 120
• 6.3.5. Experimental Results = 121
• 6.4. Ternary Copolymerization = 127
• 6.4.1. Classical Rate Model for Three Homopolymerizable Memomers = 128
• 6.4.2. Model of Diffusion Controlled Termination = 131
• 6.4.3. Experimental Results = 133
• 6.5. Conclusions = 135
• 6.6. References = 137
• 7. Free Radical Polymerization : From Spontaneous Initiation up to the Glass Transition State / G$$\ddot{u}$$nther Meyerhoff ; G$$\ddot{u}$$nter V. Schulz ; J$$\ddot{u}$$rgen Lingnau = 141
• 7.1. Introduction = 141
• 7.2. Experimental Approach = 142
• 7.2.1. Kinetic Experiments = 142
• 7.2.2. Identification and Kinetics of Formation of Side Products = 143
• 7.2.3. Determination of Molecular Weight Distributions = 143
• 7.3. Spontaneous Polymerization = 148
• 7.3.1. The Spontaneous Polymerization on Styrene = 149
• 7.3.2. The Spontaneous Polymerization on Methacrylates = 150
• 7.3.2.1. General Aspects = 150
• 7.3.2.2. The Oligomers = 151
• 7.3.2.3. Solvent Effects = 153
• 7.3.2.4. Other Acrvlates = 155
• 7.3.2.5. "Chemical Simulation" = 155
• 7.3.2.6. The Mechanism and its Formal Description = 157
• 7.4. Kinetics for Medium and High Conversions = 159
• 7.4.1. Kinetics of the Initiated Polymerization below the Onset of the Gel Effect = 159
• 7.4.2. Kinetics of the Initiated Polymerization beyond the Onset of the Gel Effect up to the Glass Transition Point = 160
• 7.4.3. Results of the Polymerization Experiments = 161
• 7.4.4. Rate Constants and Diffusion Mechanisms = 164
• 7.4.5. Chain Length and Conversion = 165
• 7.5. Conclusion = 166
• 7.6. References = 166
• 8. Kinetics and Mechanisms of Anionic and Group Transfer Polymerization / Axel H. E. M$$\ddot{u}$$ller ; Hartwig H$$\ddot{o}$$cker ; G$$\ddot{u}$$nter V. Schulz = 171
• 8.1. Introduction = 171
• 8.2. Polymerization of Styrene = 173
• 8.2.1. Ions and Ion Pairs = 173
• 8.2.2. Contact and Solvent-Separated Ion Pairs = 176
• 8.3. Polymerization of Acrylic Monomers = 179
• 8.3.1. Potential Problems = 179
• 8.3.2. Methyl Methacrylate = 181
• 8.3.3. Other Methacrylates = 191
• 8.3.3.1. Homopolymerization = 191
• 8.3.3.2. Copolymerization = 192
• 8.3.4. Polymerization in Non-Polar Solvents = 194
• 8.4. Group Transfer Polymerization of Methacrylates = 196
• 8.4.1. Introduction = 196
• 8.4.2. General Considerations = 197
• 8.4.3. Kinetic Investigations = 199
• 8.4.4. Control of Molecular Weight Distribution = 202
• 8.5. References = 204
• 9. Molecular Engineering of Liquid Crystalline Polymers / Helmut Ringsdorf ; Ingrid Voigi-Martin ; Joachim Wendorff ; Renate W$$\ddot{u}$$stefeld ; Rudolf Zentel = 211
• 9.1. Introduction : Self Organizaing Systems = 211
• 9.2. Molecular Architecture of Liquid Crystalline Polymers = 212
• 9.2.1. Liquid Crystalline Polymers with Rod-like Mesogens = 218
• 9.2.1.1. Synthesis and Structure-Property Relations of LC Side Group Polymers = 218
• 9.2.1.2. Synthesis and Structure-Property Relationships of Main Chain Polymers = 224
• 9.2.1.3. Molecular Engineering of LC-Polymers : Side Group and Main Chain LC Systems = 224
• 9.2.2. Liquid Crystalline Polymers with Disc-like Mesogents = 228
• 9.2.2.1. Polymers with Discotic Phases = 231
• 9.2.2.2. Polymers with Sanidic Phases = 233
• 9.2.3. Functionalized Liquid Crystalline Polymers = 237
• 9.2.3.1. Dye Containing Polymers = 237
• 9.2.3.2. Photosensitive Liquid Crystalline Polymers = 238
• 9.2.3.3. Liquid Crystalline Elastomers = 242
• 9.3. Molecular Architecture and Physical Properties = 247
• 9.3.1. The Amorphous, Crystalline and Liquid Crystalline State of Matter = 247
• 9.3.2. Fluctuations in Liquid Crystalline Polymers = 248
• 9.3.2.1. Defining Fluctuations = 248
• 9.3.2.2. Kerr Relaxation Studies on Orientational Fluctuations = 249
• 9.3.2.3. Small Angle X-Ray Scattering Studies on Orientational Correlations in Side Group Polymers = 252
• 9.3.3. High Resolution Electronmicroscopy as a Tool for visualizing Smectic Structures = 253
• 9.3.3.1 Introduction = 253
• 9.3.3.2. Sample Preparation = 254
• 9.3.3.3. Structural Information Obtained by Electron Microscopy = 254
• 9.3.3.4. Image Analysis and Processing = 260
• 9.3.3.5. Conclusion = 262
• 9.4. References = 262
• 10. Thermodynamics and Rheology of Polymer Solutions / Bernhard A. Wolf = 273
• 10.1. Pressure, the Neglected Variable = 274
• 10.1.1. Thermodynamics = 274
• 10.1.1.1. Pressure Dependence of Polymer Solubility = 274
• 10.1.1.2. Pressure Dependence of Interaction Parameters = 276
• 10.1.2. Viscometry = 277
• 10.1.2.1. Intrinsic Viscosities = 277
• 10.1.2.2. Activation Volumes = 278
• 10.2. On the Role of Chain Length = 279
• 10.2.1. Development of Incompatibility = 280
• 10.2.1.1. Experiments with Oligomers = 280
• 10.2.1.2. Solubility Parameter Theory = 280
• 10.2.2. Molecular Weight Dependence of Pair Interactions = 282
• 10.2.2.1. Theoretical Concept = 282
• 10.2.2.2. Experimental Results and Discussion = 283
• 10.3. Interrelation of Thermodynamic and Rheological Properties = 286
• 10.3.1. Flow under Different Thermodynamic Conditions = 286
• 10.3.1.1. The Pull-along Effect = 286
• 10.3.1.2. Thermoreversible Gelation = 287
• 10.3.2. Phase Separation of Flowing Polymer Solutions = 289
• 10.3.2.1. Experimental Results = 289
• 10.3.2.2. Theory and Discussion = 289
• 10.4. Outlook = 292
• 10.5. References = 293
• 11. Polymer Diffusion as Studied by Holographic Grating Techniques / Hans Sillescu = 295
• 11.1. Introduction = 295
• 11.2. Physical Principles and Experimental Aspects = 296
• 11.2.1. Hologram Formation = 296
• 11.2.2. Hologram Reading by Forced Rayleigh Scattering = 297
• 11.2.3. Analysis of Diffusion Experiments = 299
• 11.2.4. Photo-Labeling and Sample Preparation = 300
• 11.3. Applications = 302
• 11.3.1. Diffusion of Polymer Chains by Reptation and other Transport Mechanisms = 302
• 11.3.2. Diffusion of Polymer Rings, Microgels, and Stars = 305
• 11.3.3. Diffusion of Monomer Dyes at the Glass Transition of Amorphous Polymers = 307
• 11.4. References = 310
• 12. Deuteron NMR. A New Tool for Investigation Order and Dynamics in Polymers / Hans wolfgang Spiess ; Hans Sillescu = 313
• 12.1. Introduction = 313
• 12.2. Techniques = 314
• 12.2.1. Dynamics = 314
• 12.2.1.1. Slow Motion and Solid Echo Spectra = 314
• 12.2.1.2. Spin-Alignment = 319
• 12.2.1.3. Spin Lattice Relaxation = 320
• 12.2.1.4. Distribution of Correlation Times = 321
• 12.2.2. Order = 322
• 12.2.2.1. Orientational Distribution = 322
• 12.2.2.2. Expansion in Terms of Spherical Functions = 324
• 12.2.2.3. $$^{13}$$C-MAS-NMR = 326
• 12.3. Experimental Examples = 329
• 12.3.1. Dynamics = 329
• 12.3.1.1. Chain Motion in Linear Polyethylene = 329
• 12.3.1.2. Molecular Motion and Mechanical Properties of Polycarbonate = 330
• 12.3.1.3. Molecular Motion in Interfacial Regions of Segmented Polyurethanes = 332
• 12.3.1.4. Motion of Mesogens in Liquid Crystalline Polymers = 333
• 12.3.1.5. Mobility of Lipid Chains in Polymer Model Membranes = 335
• 12.3.2. Order = 337
• 12.3.2.1. Molecular Order in Liquid Christalline Polymers = 337
• 12.3.2.2. Drawn Fibres of Poly(ethyleneterephthalate)(PET) = 339
• 12.3.3. Overview of the $$^{2}$$H-NMR in Polymers = 341
• 12.4. New Developments : Two-dimensional $$^{2}$$H-NMR = 341
• 12.5. References = 344
• 13. The Kerr Effect as Applied to the Investigation of Polymers / Bernd-J. Jungnickel ; Joachim H. Wendorff = 349
• 13.1. Introduction = 340
• 13.2. Fundamentals = 350
• 13.2.1. Experimental Setup and Procedure = 350
• 13.2.2. Basic Theoretical Relations = 352
• 13.2.3. Information Content of the Effect = 356
• 13.3. Glassy-Amorphous Polymers = 357
• 13.3.1. Theoretical Considerations = 358
• 13.3.2. Experimental Investigations and Results = 361
• 13.3.3. Discussion = 364
• 13.4. Liquid Crystalline Polymers = 365
• 13.4.1. Introduction : Pretransitional Effects = 365
• 13.4.2. Kerr Effect and Order Parameter Fluctuations = 366
• 13.4.2.1. Static Properties = 366
• 13.4.2.2. Dynamical Properties = 367
• 13.4.3. Kerr Effect Studies on Liquid Crystalline Side Chain Polymers = 368
• 13.5. References = 374
• 14. Concentration Fluctuations and Kinetics of Phase Separation in Polymer Blends / Gert Strobl = 377
• 14.1. Introduction = 377
• 14.2. Theory = 378
• 14.2.1. Phase Behaviour of Polymer Blends = 378
• 14.2.2. Concentration Fluctuations in Thermal Equilibrium = 381
• 14.2.3. Kinetics of Unmixing = 382
• 14.3. Small Angle X-Ray Scattering Studies = 385
• 14.3.1. Polystyrene／Poly(styrene-co-bromostyrene) Blends = 385
• 14.3.2. Static Structure Factors = 386
• 14.3.3. Relaxation after T-Jumps within the One-Phase Region = 389
• 14.3.4. Kinetics of Spinodal Decomposition = 393
• 14.4. References = 395
• 15. Collective Dynamics in Polymeric Liquids as Measured by Quasi-elastic Light- and Neutron Scattering / Erhard W. Fischer ; Bernd Ewen ; Gerhard Meier = 397
• 15.1. The Dynamics of Density Fluctuations as Measured by Quasi-elastic Light Scattering = 397
• 15.1.1. The Theory of Light Scattering from an Isotropic Viscoelastic Medium = 397
• 15.1.2. The Comparison between theory and Experiment = 403
• 15.1.3. Data Evaluation of PCS Results = 404
• 15.1.4. Connection between Molecular and Collective Dynamics = 406
• 15.1.5. Separation of Primary and Secondary Relaxation Processes in Polymethacrylates = 411
• 15.2. The Dynamics of Concentration Fluctuations in a Compatible Binary Polymer Blend = 414
• 15.3. Rayleigh-Brillouim Spectroscopy of Structurally Relaxing Liquids = 420
• 15.3.1. Inelastic Scattering from a Liquid Consisting of Linear Chain Molecules = 420
• 15.3.2. Hypersonic Relaxation in a Viscoelastic Non-polymeric Liquid = 422
• 15.4. Collective Fluctuations of Chain Segments in Dense Liquid Polymer Systems as Studied by Neutron Spin Echo Spectroscopy = 424
• 15.4.1. Neutron Spin Echo = 424
• 15.4.2. Segmental Diffusion in Polymer Melts and Concentrated Solutions = 426
• 15.4.3. Unattached Polymer Chains in Permanent Networks = 434
• 15.4.4. Diffusive Motion of Cross-links = 435
• 15.5. Conclusions = 439
• 15.6. References = 441
• 16. Structure and Properties of Semicrystalline Polymers / Erhard W. Fischer ; Manfred Stamm ; Ingrid G. Voigi-Martin = 445
• 16.1. Introduction = 445
• 16.2. Morphology of Semicrystalline Polymers = 446
• 16.2.1. Comparison of Different Techniques = 446
• 16.2.2. Small Angle X-Ray Scattering(SAXS) = 446
• 16.2.3. Electron Microscopy(EM) = 448
• 16.3. Chain Conformation in the Crystalline State = 455
• 16.3.1. General Considerations = 455
• 16.3.2. Experimental Techniques = 458
• 16.3.3. Small Angle Neutron Scattering(SANS) = 460
• 16.4. Crystallization and Melting = 466
• 16.4.1. Investigation of the Crystallization and Melting Process = 466
• 16.4.2. Stress Induced Crystallization = 468
• 16.5. Blockcopolymers with Crystalline Blocks = 471
• 16.5.1. Morphology and Models = 471
• 16.5.2. SAXS and SANS Investigations = 472
• 16.6. Conclusions = 473
• 16.7. References = 474
• 17. Chain Conformation and Local Order in Amorphous Polymers / Erhard W. Fischer ; Ingrid G. Voigi-Martin = 477
• 17.1. Introduction = 477
• 17.2. Chain Conformation = 479
• 17.3. Short-range Positional Order = 484
• 17.4. Direct Structural Observation = 488
• 17.5. Orientational Order = 490
• 17.6. Density Fluctuations = 494
• 17.7. References = 496
• 18. Theory of Dense Polymer Systems / Kurt Binder ; Kurt Kremer ; Ingeborg Carmesin ; Alla Sariban = 499
• 18.1. Introduction = 500
• 18.2. Mean Field Theories of Polymer Mixtures = 501
• 18.2.1. Spinodal Decomposition of Polymer Alloys = 502
• 18.2.2. Effects of Polydispersity and Shear = 505
• 18.2.3. Wetting of Polymer Mixtures = 508
• 18.3. Scaling and Computer Simulation Investigations = 511
• 18.3.1. Phase Separation of A-chain - B-chain - Solvent Systems = 512
• 18.3.2. Dynamics of a polymer in a Tube : Test of the Reptation Concept = 519
• 18.3.3. Molecular Dynamics Simulation of a Polymer Melt = 523
• 18.4. Conclusions = 526
• 18.5. References = 528
• Appendix : Documentation of the Sonderforschungsbereich 41 = 533