ISBN: 3-540-64378-8
TITLE: Macromolecular Science and Engineering
AUTHOR: Tanabe, Yoshikazu (Ed.)
TOC:

Preface V 
Contents VII 
List of Contributors XV 
1 Introduction 1 
Part I. Chemical Reactions 
2 Metallocene Catalyzed Polymerization of Methylmethacrylate 7 
Akira Miyazawa 
2.1 Introduction 7 
2.2 Polymerization of Methacrylates 7 
2.2.1 Syndiospecific Polymerization of MMA 8 
2.3 Polymerization Mechanism of Syndiotactic PMMA 10 
2.3.1 Polymerization Mechanism Initiated by Lanthanocene 
Complexes 10 
2.3.2 Polymerization Mechanism Initiated by Cationic
Zirconocene Catalyst 10 
2.4 Isospecific Polymerization of MMA 12 
2.5 Conclusion 13 
3 Radical Isomerization Polymerization 17 
Jun-ichi Sugiyama 
3.1 Introduction 17 
3.2 Vinylcyclopropanes 17 
3.3 Cyclic Vinyl Ethers 21 
3.4 Cyclic Ketene Acetals 22 
3.5 Miscellaneous 28 
3.5.1 Allyl Isomerization 28 
3.5.2 Aromatization 29 
3.5.3 Polyenes 29 
3.5.4 Future of Radical Isomerization. Polymerization 29 
4 High Pressure Solid State Polymerization 33 
Hiroshi Yamawaki, Katsutoshi Aoki 
4.1 Introduction 33 
4.2 Experimental Technique for High-Pressure Research 33 
4.2.1 High-Pressure Cell 33 
4.2.2 Determination of Pressure 34 
4.2.3 Microscope Observation 34 
4.3 Spectrometry under High Pressure 35 
4.3.1 Raman Measurement 35 
4.3.2 Infrared Measurement 35 
4.4 Phase Transition and Polymerization 37 
4.4.1 Hydrogen Cyanide 37 
4.4.2 Acetylene 38 
5 Biodegradable Polymers 41 
Masao Kunioka 
5.1 Introduction 41 
5.2 Microbial Polyesters 42 
5.3 Microbial Poly(Amino Acid)s 43 
5.4 Microbial Polysaccharides 47 
5.5 Chemically Synthesized Biodegradable Polymer 47 
Part II. Specialty Polymers 
6 Polymer Objects: Towards New Polymer Architectures 53 
Toshimi Shimizu 
6.1 Introduction 53 
6.2 New Polymer Architectures 53 
6.3 Interlocked Polymers 54 
6.3.1 Polycatenane 54 
6.3.2 Polyrotaxane 56 
6.3.3 Conjugated Poly-Catenated Rotaxane 57 
6.4 Dendrimer 58 
6.5 Supramolecular Self-Assembly 63 
6.6 Concluding Remarks 67 
7 Thermo-Responsive Polymer Gels 71 
Hisao Ichijo, Ryoichi Kishi 
7.1 Introduction 71 
7.2 Preparation and Swelling Properties of Poly(Vinyl Methyl Ether) 
Hydrogel 72 
7.3 Fast Responsive PVME Hydrogels Having Microporous
Structure 74 
7.4 Fast Responsive PNIPAAm Hydrogels Having Microporous 
Structure 75 
7.5 Thermo-Reversible Adsorption of Nonionic Surfactants on PVME 
Gel 76 
7.6 Swelling of PVME Gel in Ionic Surfactant Solutions 78 
7.7 Control of Enzyme Activity 80 
7.8 Application for Thermo-Responsive Devices 81 
7.9 Conclusion 82 
8 Biomimetic Membranes 85 
Norihiko Minoura 
8.1 Introduction 85 
8.2 Mimics of the Taste Cell 85 
8.3 Mimics of the Retina 89 
8.4 Selective Transport of Molecules 91 
9 Polymeric Membranes for Separation 95 
Kenji Haraya, Shuguang Li, Kensaku Mizoguchi 
9.1 Introduction 95 
9.2 Structure and Various Kinds of Separation Membranes 96 
9.2.1 Microfiltration (MF) 98 
9.2.2 Ultra-Filtration (UF) 98 
9.2.3 Reverse Osmosis (RO) and Nanofiltration (NF) 99 
9.2.4 Pervaporation (PV) 101 
9.3 Gas Separation Membranes 103 
9.3.1 Transport Mechanism 103 
9.3.2 Membrane Structures 105 
9.3.3 Membrane Materials 106 
9.3.3.1 Glassy Polymers 107 
9.3.3.2 Rubbery Polymers 117 
9.3.4 Permeability Prediction 121 
10 Metal Clusters Dispersed in Organic Materials 125 
Yukimichi Nakao 
10.1 Introduction 125 
10.2 Metal Organosols 125 
10.2.1 Reduction in the Solution 125 
10.2.2 Interphase Migration 127 
10.2.3 Metal-Dissolving Organic Solvents 130 
10.2.4 Methods from Bulk Metals 130 
10.3 Metal Cluster-Containing Solid Sols 131 
10.3.1 Solidification of Organosols 131 
10.3.2 Thermal Decomposition in Solid Solution 132 
10.3.3 Microphase Separation 132 
10.3.4 Migration of Clusters 133 
11 Organic Magnetic Materials 137 
Kazuhisa Murata 
11.1 Introduction 137 
11.2 Magnetic Properties 137 
11.3 Organic Magnetic Materials 139 
11.3.1 Molecular Magnets 139 
11.3.2 Polymeric Magnets 143 
11.3.3 Carbon Magnets 143 
12 Nonlinear Optical Materials 151 
Hiro Matsuda, Yoshikazu Tanabe 
12.1 Introduction 151 
12.1.1 Nonlinear Optical Effect 151 
12.1.2 Measurement of Hyperpolarizability and Nonlinear
Optical Susceptibilities 154 
12.1.3 Poling 155 
12.2 Second-Order Nonlinear Optical Materials 156 
12.2.1 Trade-off Relation between Second-Order Optical
Nonlinearities and Transparency 156 
12.2.2 Second-Order Nonlinear Optical Crystals 156 
12.3 Electro-optic Effect 158 
12.3.1 Guest-Host Systems 158 
12.3.2 Side-Chain Polymers 158 
12.3.3 Main-Chain Polymers 159 
12.3.4 Crosslinked Systems 160 
12.3.5 Sol-Gel Glasses 161 
12.3.6 Electro-optic Devices 161 
12.4 Photorefractive Effect 162 
12.5 Third-Order Nonlinear Optical Materials 163 
12.5.1 Switching Devices 163 
12.5.2 Polydiacetylene 164 
12.5.3 Other Polymers and Molecules 166 
Part III. Polymer Processing 
13 Laser Processing of Polymers 171 
Akira Yabe 
13.1 Introduction 171 
13.2 Polymer Processing by Laser Ablation 172 
13.2.1 Laser Ablation of Polymer 172 
13.3 Etching: Micromachining 175 
13.3.1 Surface Modification 177 
13.3.2 Deposition: Thin Film Preparation 182 
13.4 Polymer Processing by Laser-Induced Chemical Reaction 184 
13.4.1 Laser-Induced Chemical Reactions 184 
13.4.2 Surface Modification 185 
13.5 Summary 187 
14 Solid-Phase Forming and Mechanical Properties of Polymers 191 
Kazuo Nakayama, Akira Kaito 
14.1 Introduction 191 
14.2 Hot Drawing of Ultrahigh Molecular Weight Polyethylene 192 
14.2.1 Characteristics of Ultrahigh Molecular Weight
Polyethylene 192 
14.2.2 Drawing of Ultrahigh Molecular Weight Polyethylene 192 
14.2.3 Mechanical Properties of Drawn UHMW-PE Sheets 193 
14.2.4 Structure of Drawn UHMW-PE 194 
14.3 Hydrostatic Extrusion 195 
14.3.1 Hydrostatic Extrusion Method 195 
14.3.2 Tube Extrusion of High Density PE 196 
14.3.3 Extrusion of Heat-Treated UHMW-PE 197 
14.4 Rolling of Films 200 
14.4.1 Application of Various Rolling Methods 200 
14.4.2 Rolling of Polypropylene Sheets 201 
14.4.3 Rolling of Multilayer Polymer Sheets 202 
14.5 Roller-Drawing of Polymers 203 
14.5.1 Roller-Drawing Method 203 
14.5.2 Mechanical Properties of Roller-Drawn Sheet 205 
14.5.3 Higher-Order Structure of Roller-Drawn Polymer Sheet 206 
14.6 Preparation of Ultra-Thin Polymer Films by Mechanical
Deposition 207 
14.6.1 Mechanical Deposition Method 207 
14.6.2 Highly Oriented Films of Poly(dimethylsilane)
by Mechanical Deposition 208 
14.6.3 Oriented Films of Poly(p-phenylene) by Mechanical
Deposition 210 
Part IV. New Measurements 
15 Precise Measurement of Molecular Weight 217 
Shinichi Kinugasa 
15.1 Introduction 217 
15.2 Accuracy and Precision 218 
15.3 Size Exclusion Chromatography 218 
15.4 Size Exclusion Chromatography with Multiple Detection 221 
15.5 Light Scattering 223 
15.6 Nuclear Magnetic Resonance (NMR) 224 
15.7 Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass 
Spectrometry (MALDI-TOFMS) 225 
15.8 Uniform Oligomers 227 
16 Surface Forces in Polymeric Systems 231 
Masakatsu Hato, Satomi Ohnishi, Masami Murata 
16.1 Introduction 231 
16.2 Methods 231 
16.2.1 Surface Force Apparatus (SFA) 231 
16.2.2 The Colloid Probe Technique 233 
16.3 Interactions between Polymer Layers in Liquids 234 
16.3.1 Interactions between Neutral Polymers 234 
16.4 Attractive Forces Between "Hydrophobic" Surfaces Across Water 242 
16.5 Concluding Remarks 246 
Part V. Structure and Properties 
17 Structure of Organic Thin Films 253 
Kiyoshi Yase 
17.1 Introduction 253 
17.2 Problems and their Solutions in TEM Observation of Organic 
and Polymer Materials 254 
17.3 High Resolution Observation of Organic and Polymer Thin Films 254 
17.3.1 Phthalocyanine Thin Films 254 
17.3.2 Polymer Thin Films 257 
17.3.3 Fatty Acids 260 
17.4 Electron Spectroscopic Imaging of Plasma-Polymerized Films 261 
17.5 Summary 265 
18 Molecular Motions in Bulk Polymers 267 
Yoshikazu Tanabe 
18.1 Chain Dynamics 267 
18.1.1 Experimental Observations 267 
18.1.2 Computer Simulation of Polymer Chain Motions in the 
Bulk State 269 
18.1.3 Effects of Torsional Librations 274 
18.2 Glass Transition 275 
18.2.1 Experimental Features of the Glass Transition 275 
18.2.2 Trapping Diffusion Model of the Glass Transition 278 
18.3 Cis-Trans Thermal Isomerization of Polyacetylene 280 
19 Computer Simulation of Polymers 287 
Masao Doi 
19.1 Introduction 287 
19.2 Mean Field Monte Carlo Method 287 
19.2.1 The Principle 287 
19.2.2 Application to Rigid Zig-Zag Molecules 289 
19.3 Mean Field Calculation for Polymers 290 
19.3.1 General Formulation 290 
19.3.2 Application to Polymers Grafted on Solid Surfaces 292 
19.4 Dynamical Mean Field Calculation 293 
19.4.1 Principle of Calculation 293 
19.4.2 Phase Separation 295 
19.4.3 Ordering of Block Copolymers 295 
19.4.4 Dynamics of Polymer Adsorption 296 
19.5 Summary and Future Challenges 298 
20 Morphology Development during Melt Processing of
Immiscible Polymer Blends 301 
Shin Horiuchi, Kazuo Nakayama 
20.1 Introduction 301 
20.2 Drop Breakup and Coalescence in Polymer Blends 302 
20.2.1 Morphology Development during the Initial Stages of 
Blending 302 
20.2.2 Breakup/Coalescence Equilibrium 303 
20.2.3 Compatibilization-Suppression of Coalescence 305 
20.3 Effect of Shear Flow on the Phase Behavior 308 
20.4 Ternary Blends-Manipulation of Phase Formation 310 
20.4.1 Prediction of Phase Formation in Non-Reactive Ternary 
Blends 310 
20.4.2 Conversion of Phase Formation by Addition of a
Diblock Copolymer 312 
20.4.3 Manipulation of the Phase Formation by Interfacial 
Chemical Reaction 313 
20.5 Summary 317 
21 Electronic Structure of Conductive and Conjugated
Polymers 319 
Yoshikazu Tanabe 
21.1 Intramolecular Electronic State 319 
21.1.1 pi-Conjugated Polymers 319 
21.1.2 sigma-Conjugated Polymers 333 
21.2 Intermolecular Charge Transport 335 
21.3 Metallic Conduction 341 
22 Organic Electroluminescent Devices 345 
Noriyuki Takada, Shogo Saito 
22.1 Introduction 345 
22.2 Principle and Structures of Electroluminescent Devices 345 
22.3 Materials for EL Devices 346 
22.4 Rational Selection of Organic Materials for Multilayer
EL Devices 347 
22.5 Effects of Dopant Molecules on EL Characteristics 349 
22.6 Confinement of Excitons within the EML-a Device
of Molecular Size 351 
22.7 Size Effects in Organic EL Devices 353 
22.8 Strongly Directed Emission from Controlled-Spontaneous-Emission 
EL Devices 355 
22.9 Laser Action from Organic Thin Films 360 
22.10 Conclusions 361 
23 Optical and Electrical Properties of C_60, C_70, Nanotubes and 
Endohedral Fullerenes 363 
Said Kazaoui, Nobutsugu Minami 
23.1 Introduction 363 
23.2 C60 and C70 Fullerenes 364 
23.2.1 Molecular Geometry and Electronic Structure of C_60 364 
23.2.2 Properties of C_60 Solids 366 
23.3 Intermolecular Chaxge-Transfer States in C_60 and C_70 Solids 368 
23.3.1 Evidence for Intermolecular Charge-Tansfer States 368 
23.3.2 Dynamic Behavior of Excited States in Solid Fullerenes 371 
23.3.3 Photocarrier Generation Dynamics in Solid Fullerenes 373 
23.4 Applications 373 
23.4.1 Xerographic Photoreceptors 373 
23.4.2 Photovoltaic Devices 376 
23.5 Endohedral Fullerenes 379 
23.5.1 Definition 379 
23.5.2 Electronic Structure and Properties 379 
23.6 Electrical and Optical Properties of Carbon Nanotubes 381 
23.6.1 Definition and Electronic Structure of Nanotubes 382 
23.6.2 Production, Purification and Elaboration Methods 384 
23.6.3 Experimental Characterization of NT 384 
23.7 Conclusions and Perspectives 387 
Subject Index 393 
END
