Block Copolymers: Synthetic Strategies, Physical Properties, and Applications

435 Pages·2002·5.392 MB·English

by  Nikos Hadjichristidis, Stergios Pispas, George Floudas

BlockCopolymers:SyntheticStrategies,PhysicalProperties,andApplications.
NikosHadjichristidis,StergiosPispasandGeorgeFloudas
Copyright2003JohnWiley&Sons,Inc.
ISBN:0-471-39436-X
BLOCK COPOLYMERS
BLOCK COPOLYMERS
Synthetic Strategies, Physical
Properties, and Applications
NIKOS HADJICHRISTIDIS
STERGIOS PISPAS
GEORGE FLOUDAS
A John Wiley & Sons, Inc., Publication
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LibraryofCongressCataloging-in-PublicationData:
Hadjichristidis,Nikos,1943-
Blockcopolymers:syntheticstrategies,physicalproperties,and
applications/NikosHadjichristidis,StergiosPispas,GeorgeFloudas.
p. cm.
Includesindex.
ISBN0-471-39436-X(cloth:acid-freepaper)
1.Blockcopolymers. I.Pispas,Stergios,1967- II.Floudas,George,
1961- III.Title.
QD382.B5H332003
5470.84–dc21 2002014989
PrintedintheUnitedStatesofAmerica.
10 9 8 7 6 5 4 3 2 1
To Our Wives
Dina, Hara, and Maria
CONTENTS
Preface xiii
Abbreviations and Symbols xvii
III BLOCK COPOLYMER SYNTHESIS 1
1 BLOCK COPOLYMERS BY ANIONIC POLYMERIZATION 3
1. Synthesis of AB Diblock Copolymers / 4
2. Synthesis of Triblock Copolymers / 11
3. Linear Block Copolymers With More Than Three Blocks / 23
2 BLOCK COPOLYMERS BY CATIONIC POLYMERIZATION 28
1. Synthesis of AB Diblock Copolymers / 29
2. Synthesis of Triblock Copolymers / 40
3 BLOCK COPOLYMERS BY LIVING FREE
RADICAL POLYMERIZATION 47
1. Synthesis of AB Diblock Copolymers / 48
2. Synthesis of ABATriblock Copolymers / 58
vii
viii
CONTENTS
3. Synthesis of ABC Triblock Terpolymers and
ABCD Tetrablock Quarterpolymers / 61
4 BLOCK COPOLYMERS BY GROUP TRANSFER
POLYMERIZATION 65
1. Synthesis of AB Diblock Copolymers / 66
2. Synthesis of ABATriblock Copolymers / 72
3. Synthesis of ABC Triblock Terpolymers / 75
5 BLOCK COPOLYMERS BY RING OPENING
METATHESIS POLYMERIZATION 80
1. Synthesis of AB Diblock Copolymers / 82
2. Synthesis of ABATriblock Copolymers / 88
6 SYNTHESIS OF BLOCK COPOLYMERS BY A
COMBINATION OF DIFFERENT POLYMERIZATION
METHODS 91
1. Synthesis of Block Copolymers by Anionic to
Cationic Mechanism Transformation / 92
2. Synthesis of Block Copolymers by Anionic to
Living Free Radical Mechanism Transformation / 94
3. Synthesis of Block Copolymers by Cationic to
Anionic Mechanism Transformation / 97
4. Synthesis of Block Copolymers by Cationic to
Onium Mechanism Transformation / 98
5. Synthesis of Block Copolymers by Cationic to
Living Free Radical Mechanism Transformation / 100
6. Synthesis of Block Copolymers by Living Free
Radical to Cationic Mechanism Transformation / 102
7. Synthesis of Block Copolymers by Ring Opening Metathesis
to Living Free Radical Mechanism Transformation / 103
8. Synthesis of Block Copolymers by Ring Opening
Metathesis to Group Transfer Mechanism Transformation / 104
9. Other Combinations / 105
10. Bifunctional (DUAL) Initiators / 107
11. Synthesis of Block Copolymers by Direct Coupling
of Preformed Living Blocks / 107
12. Synthesis of Block Copolymers by Coupling of
End-functionalized Prepolymers / 110
ix
CONTENTS
7 SYNTHESIS OF BLOCK COPOLYMERS BY
CHEMICAL MODIFICATION 114
1. Hydrogenation / 115
2. Hydrolysis / 116
3. Quaternization / 117
4. Sulfonation / 118
5. Hydroboration/Oxidation / 119
6. Epoxidation / 121
7. Chloro/BromoMethylation / 121
8. Hydrosilylation / 123
8 NONLINEAR BLOCK COPOLYMERS 126
1. Star Block Copolymers / 126
2. Graft Copolymers / 134
3. Miktoarm Star Copolymers / 142
4. Other Complex Architectures / 156
III MOLECULAR CHARACTERIZATION OF
BLOCK COPOLYMERS 173
9 MOLECULAR CHARACTERIZATION OF
BLOCK COPOLYMERS 175
1. Purification of Block Copolymers by Fractionation / 175
2. Molecular Characterization / 177
III SOLUTION PROPERTIES OF
BLOCK COPOLYMERS 195
10 DILUTE SOLUTIONS OF BLOCK COPOLYMERS IN
NONSELECTIVE SOLVENTS 197
11 DILUTE SOLUTIONS OF BLOCK COPOLYMERS IN
SELECTIVE SOLVENTS 203
1. Thermodynamics of Micellization / 203
2. Phenomenology of Block Copolymer Micellar Structure / 206
3. Experimental Techniques for Studying Micelle Formation / 207
4. Equilibrium Structure of Block Copolymer Micelles / 215
x
CONTENTS
5. Effect of Architecture / 219
6. Kinetics of Micellization / 222
7. Solubilization of Low Molecular Weight Substances in
Block Copolymer Micelles / 224
8. Ionic Block Copolymer Micelles / 225
12 ADSORPTION OF BLOCK COPOLYMERS AT
SOLID-LIQUID INTERFACES 232
1. Phenomenology of Block Copolymer Adsorption / 232
2. Experimental Techniques for Studying Block
Copolymer Adsorption / 235
3. Theories of Block Copolymer Adsorption / 242
4. Experiments on Block Copolymer Adsorption / 246
IV PHYSICAL PROPERTIES OF
BLOCK COPOLYMERS 255
13 THEORY 257
1. Strong Segregation Limit (SSL) / 257
2. Weak Segregation Limit (WSL) / 259
3. Structure Factor / 261
4. Intermediate Segregation Limit (ISL) and
Self-consistent Field Theory (SCFT) / 263
14 STRUCTURE FACTOR AND CHAIN ARCHITECTURE 268
1. Graft Copolymers / 269
2. A B Star Block Copolymers / 274
n n
3. (AB) STAR COPOLYMERS / 277
n
4. ABATriblock Copolymers / 280
5. Tapered Block Copolymers / 281
6. Multiblock Copolymers / 282
15 BLOCK COPOLYMER PHASE STATE 286
1. Fluctuation Effects / 287
2. Conformational Asymmetry / 290
3. The Known Phase Diagrams / 292
4. The PEO-PI Phase Diagram / 294
5. The PS-PI-PEO Phase Diagram / 295
xi
CONTENTS
16 VISCOELASTIC PROPERTIES OF
BLOCK COPOLYMERS 298
1. Localization of the (Apparent) Order-to-Disorder Transition / 300
2. Viscoelastic Spectrum of Block Copolymers / 301
3. Viscoelastic Response of Ordered Phases / 303
4. Flow-induced Alignment of Block Copolymer Melts / 305
17 PHASE TRANSFORMATION KINETICS 313
1. Detection and Analysis of the Ordering Kinetics / 314
2. The Equilibrium Order-to-disorder Transition Temperature / 318
3. Effect of Fluctuations / 320
4. Grain Growth / 322
5. Effect of Block Copolymer Architecture / 325
6. Transitions Between Different Ordered States / 327
18 BLOCK COPOLYMERS WITH STRONGLY
INTERACTING GROUPS 335
1. Cylinder-forming Functionalized SI Diblock Copolymers / 337
2. Lamellar-forming Functionalized Diblock and
Triblock Copolymers / 340
3. ABC Block Copolymers With a Short but Strongly
Interacting Middle Block / 342
4. Effect of Salt on the Lamellar Spacing and
Microdomain Morphology / 344
19 BLOCK COPOLYMER MORPHOLOGY 346
1. Rod-Coil Copolymers / 346
2. ABC Triblock Terpolymers / 352
3. More Complexity With ABCs / 353
4. ABC Miktoarm Star Terpolymers With Amorphous Blocks / 355
5. ABC Star Terpolymers With Crystallizable Blocks / 357
6. Architecture-induced Phase Transformations / 358
20 BLOCK COPOLYMER DYNAMICS 362
1. DynamicStructureFactorofDisorderedDiblockCopolymers / 362
2. Dynamic Structure Factor of Ordered Diblock Copolymers / 366
3. Dielectric Relaxation in Diblock Copolymers in
the Disordered and Ordered Phases / 370
xii
CONTENTS
4. Dynamic Interfacial Width in Block Copolymers / 373
5. Dielectric Relaxation in Block Copolymer/
Homopolymer Blends / 376
V APPLICATIONS 383
21 BLOCK COPOLYMER APPLICATIONS 385
1. Commercialized Applications / 386
2. Potential Applications / 397
Index 409