Preface |
|
xv | |
The Authors |
|
xvii | |
Chapter 1 Introduction |
|
1 | |
|
|
1 | |
|
1.2 Some Basic Definitions |
|
|
2 | |
|
1.3 Synthesis of Polymers |
|
|
4 | |
|
|
4 | |
|
1.5 Average Molar Masses and Distributions |
|
|
8 | |
|
|
10 | |
|
|
12 | |
|
1.8 The Glass Transition Temperature Tg and the Melting Temperature Tm |
|
|
14 | |
|
1.9 Elastomers, Fibers, and Plastics |
|
|
16 | |
|
1.10 Fiber-Forming Polymers |
|
|
18 | |
|
|
18 | |
|
1.12 Thermosetting Polymers |
|
|
21 | |
|
|
21 | |
|
|
25 | |
|
|
27 | |
|
|
27 | |
Chapter 2 Step-Growth Polymerization |
|
29 | |
|
|
29 | |
|
2.2 Reactivity of Functional Groups |
|
|
30 | |
|
|
31 | |
|
2.4 Control of the Molar Mass |
|
|
32 | |
|
2.5 Stoichiometric Control of Mn |
|
|
34 | |
|
|
36 | |
|
2.7 Molar Mass Distribution in Linear Systems |
|
|
38 | |
|
|
39 | |
|
2.9 Characteristics of Step-Growth Polymerization |
|
|
40 | |
|
2.10 Typical Step-Growth Reactions |
|
|
40 | |
|
|
41 | |
|
2.12 Nonlinear Step-Growth Reactions |
|
|
42 | |
|
2.13 Statistical Derivation |
|
|
43 | |
|
2.14 Comparison with Experiment |
|
|
44 | |
|
|
46 | |
|
2.16 Thermosetting Polymers |
|
|
49 | |
|
|
52 | |
|
|
56 | |
|
|
56 | |
Chapter 3 Free-Radical Addition Polymerization |
|
57 | |
|
3.1 Addition Polymerization |
|
|
57 | |
|
|
57 | |
|
3.3 Free-Radical Polymerization |
|
|
58 | |
|
|
59 | |
|
3.4.1 Initiator Efficiency |
|
|
60 | |
|
|
62 | |
|
|
62 | |
|
3.7 Steady-State Kinetics |
|
|
63 | |
|
3.8 High-Conversion Bulk Polymerizations |
|
|
65 | |
|
|
67 | |
|
3.9.1 Consequences of Chain Transfer |
|
|
70 | |
|
3.10 Inhibitors and Retarders |
|
|
70 | |
|
3.11 Activation Energies and the Effect of Temperature |
|
|
72 | |
|
3.12 Thermodynamics of Radical Polymerization |
|
|
73 | |
|
3.13 Heats of Polymerization |
|
|
76 | |
|
3.14 Polymerization Processes |
|
|
76 | |
|
3.15 Features of Free-Radical Polymerization |
|
|
79 | |
|
3.16 Controlled Radical Polymerization |
|
|
79 | |
|
3.17 Nitroxide-Mediated Polymerizations |
|
|
81 | |
|
3.18 Atom Transfer Radical Polymerization (ATRP) |
|
|
82 | |
|
|
83 | |
|
3.20 Degenerative Chain Transfer Reaction (DT) |
|
|
84 | |
|
3.21 Reversible Addition Fragmentation Chain Transfer (RAFT) |
|
|
84 | |
|
3.22 CRP of Vinyl Chloride |
|
|
87 | |
|
3.23 The Kinetics of CRP Processes |
|
|
87 | |
|
3.24 Application to Experimental Data |
|
|
90 | |
|
|
92 | |
|
|
96 | |
|
|
96 | |
Chapter 4 Ionic Polymerization |
|
99 | |
|
4.1 General Characteristics |
|
|
99 | |
|
4.2 Cationic Polymerization |
|
|
100 | |
|
4.3 Propagation by Cationic Chain Carriers |
|
|
101 | |
|
|
102 | |
|
4.5 General Kinetic Scheme |
|
|
103 | |
|
4.6 Energetics of Cationic Polymerization |
|
|
103 | |
|
4.7 Telechelic Polymers via Cationic Polymerization |
|
|
104 | |
|
4.8 Cationic Ring Opening Polymerization |
|
|
105 | |
|
|
107 | |
|
4.10 Anionic Polymerization |
|
|
108 | |
|
|
109 | |
|
4.12 Kinetics and Molar Mass Distribution in Living Anionic Systems |
|
|
110 | |
|
4.13 Metal Alkyl Initiators |
|
|
114 | |
|
4.14 Solvent and Gegen Ion Effects |
|
|
114 | |
|
4.15 Anionic Ring-Opening Polymerization |
|
|
114 | |
|
|
116 | |
|
|
118 | |
|
|
119 | |
Chapter 5 Linear Copolymers and Other Architectures |
|
121 | |
|
5.1 General Characteristics |
|
|
121 | |
|
|
122 | |
|
5.3 The Copolymer Equation |
|
|
122 | |
|
5.4 Monomer Reactivity Ratios |
|
|
123 | |
|
5.5 Reactivity Ratios and Copolymer Structure |
|
|
124 | |
|
5.6 Monomer Reactivities and Chain Initiation |
|
|
127 | |
|
5.7 Influence of Structural Effects on Monomer Reactivity Ratios |
|
|
127 | |
|
|
127 | |
|
|
129 | |
|
|
129 | |
|
5.9 Alternating Copolymers |
|
|
131 | |
|
5.10 Block Copolymer Synthesis |
|
|
133 | |
|
5.10.1 Transformation Reactions |
|
|
135 | |
|
|
137 | |
|
|
138 | |
|
|
139 | |
|
5.10.1.4 Step-Growth ATRP |
|
|
139 | |
|
5.10.2 Coupling Reactions |
|
|
140 | |
|
5.10.3 Use of CRP Methods |
|
|
142 | |
|
5.11 Graft Copolymer Synthesis |
|
|
145 | |
|
5.12 Statistical and Gradient Copolymers |
|
|
147 | |
|
5.13 Complex Molecular Architectures |
|
|
148 | |
|
|
149 | |
|
|
150 | |
|
|
151 | |
|
5.14.3 Dendrimer Molecular Weight |
|
|
152 | |
|
5.14.4 Properties of Dendrimers |
|
|
153 | |
|
5.14.5 Applications of Dendrimers |
|
|
154 | |
|
|
155 | |
|
|
156 | |
|
|
156 | |
Chapter 6 Polymer Stereochemistry |
|
157 | |
|
|
157 | |
|
|
157 | |
|
|
158 | |
|
6.3.1 Monotactic Polymers |
|
|
159 | |
|
|
160 | |
|
|
160 | |
|
|
162 | |
|
6.5 Conformation of Stereoregular Polymers |
|
|
163 | |
|
6.6 Factors Influencing Stereoregulation |
|
|
165 | |
|
6.7 Homogeneous Stereospecific Cationic Polymerizations |
|
|
167 | |
|
6.8 Homogeneous Stereoselective Anionic Polymerizations |
|
|
168 | |
|
6.9 Homogeneous Diene Polymerization |
|
|
170 | |
|
|
172 | |
|
|
172 | |
|
|
173 | |
|
|
173 | |
Chapter 7 Polymerization Reactions Initiated by Metal Catalysts and Transfer Reactions |
|
175 | |
|
7.1 Polymerization Using Ziegler–Natta Catalysts |
|
|
175 | |
|
7.2 Nature of the Catalyst |
|
|
176 | |
|
7.3 Nature of Active Centers |
|
|
177 | |
|
|
177 | |
|
7.5 Monometallic Mechanism |
|
|
178 | |
|
|
180 | |
|
7.7 Ring-Opening Metathesis Polymerization (ROMP) |
|
|
181 | |
|
|
182 | |
|
7.9 Bicyclo- and Tricyclomonomers |
|
|
183 | |
|
|
184 | |
|
|
184 | |
|
7.12 Group Transfer Polymerization (GTP) |
|
|
186 | |
|
7.13 Aldol Group Transfer Polymerization |
|
|
187 | |
|
7.14 Metallocene Catalysts |
|
|
188 | |
|
7.14.1 Metallocene/Aluminoxane Catalysts |
|
|
189 | |
|
|
189 | |
|
7.14.3 Cationic Metallocenes |
|
|
192 | |
|
7.14.4 Mechanism of Stereoregulation |
|
|
192 | |
|
|
193 | |
|
|
194 | |
|
|
194 | |
|
|
194 | |
Chapter 8 Polymers in Solution |
|
197 | |
|
8.1 Thermodynamics of Polymer Solutions |
|
|
197 | |
|
8.2 Ideal Mixtures of Small Molecules |
|
|
197 | |
|
|
199 | |
|
8.4 Flory–Huggins Theory: Entropy of Mixing |
|
|
199 | |
|
8.5 Enthalpy Change on Mixing |
|
|
203 | |
|
8.6 Free Energy of Mixing |
|
|
204 | |
|
8.7 Limitations of the Flory–Huggins Theory |
|
|
205 | |
|
|
206 | |
|
8.9 Flory–Krigbaum Theory |
|
|
208 | |
|
8.10 Location of the Theta Temperature |
|
|
210 | |
|
8.11 Lower Critical Solution Temperatures |
|
|
213 | |
|
8.12 Solubility and the Cohesive Energy Density |
|
|
216 | |
|
8.13 Polymer–Polymer Mixtures |
|
|
219 | |
|
8.14 Kinetics of Phase Separation |
|
|
223 | |
|
|
224 | |
|
|
227 | |
|
|
227 | |
Chapter 9 Polymer Characterization — Molar Masses |
|
229 | |
|
|
229 | |
|
9.2 Molar Masses, Molecular Weights, and SI Units |
|
|
229 | |
|
9.3 Number-Average Molar Mass Mn |
|
|
229 | |
|
|
230 | |
|
9.5 Colligative Properties of Solutions |
|
|
230 | |
|
|
231 | |
|
|
234 | |
|
9.7.1 Scattering from Large Particles |
|
|
236 | |
|
9.8 Dynamic Light Scattering |
|
|
239 | |
|
|
240 | |
|
9.9.1 Viscosity-Average Molecular Weight |
|
|
242 | |
|
9.10 Gel Permeation Chromatography |
|
|
243 | |
|
|
247 | |
|
|
248 | |
|
|
251 | |
|
|
252 | |
Chapter 10 Polymer Characterization — Chain Dimensions, Structures, and Morphology |
|
253 | |
|
10.1 Average Chain Dimensions |
|
|
253 | |
|
10.2 Freely Jointed Chain Model |
|
|
254 | |
|
|
255 | |
|
|
255 | |
|
10.5 Treatment of Dilute Solution Data |
|
|
256 | |
|
10.5.1 The Second Virial Coefficient |
|
|
256 | |
|
10.5.2 Expansion Factor α |
|
|
257 | |
|
|
258 | |
|
10.5.4 Indirect Estimates of Unperturbed Chain Dimensions |
|
|
259 | |
|
10.5.5 Influence of Tacticity on Chain Dimensions |
|
|
259 | |
|
10.6 Nuclear Magnetic Resonance (NMR) |
|
|
260 | |
|
10.7 Infrared Spectroscopy |
|
|
262 | |
|
|
264 | |
|
10.9 Wide-Angle and Small-Angle Scattering |
|
|
265 | |
|
10.9.1 Wide-Angle X-Ray Scattering |
|
|
266 | |
|
10.9.2 Small-Angle X-Ray Scattering (SAXS) |
|
|
267 | |
|
10.9.3 Small-Angle Neutron Scattering (SANS) |
|
|
268 | |
|
|
271 | |
|
10.10.1 Optical Microscopy |
|
|
272 | |
|
10.10.2 Scanning Electron Microscopy |
|
|
273 | |
|
10.10.3 Transmission Electron Microscopy |
|
|
274 | |
|
10.10.4 Atomic Force Microscopy and Scanning Tunneling Microscopy |
|
|
274 | |
|
|
276 | |
|
|
277 | |
|
|
277 | |
Chapter 11 The Crystalline State and Partially Ordered Structures |
|
279 | |
|
|
279 | |
|
11.2 Mechanism of Crystallization |
|
|
279 | |
|
11.3 Temperature and Growth Rate |
|
|
281 | |
|
|
282 | |
|
11.4.1 Effect of Crystallite Size on Melting |
|
|
282 | |
|
11.5 Thermodynamic Parameters |
|
|
282 | |
|
11.6 Crystalline Arrangement of Polymers |
|
|
285 | |
|
11.6.1 Factors Affecting Crystallinity and Tm |
|
|
285 | |
|
|
285 | |
|
11.6.1.2 Intermolecular Bonding |
|
|
286 | |
|
|
287 | |
|
11.6.1.4 Branching and Molar Mass |
|
|
287 | |
|
11.7 Morphology and Kinetics |
|
|
287 | |
|
|
287 | |
|
|
288 | |
|
|
288 | |
|
|
289 | |
|
11.8.4 Crystallization from the Melt |
|
|
289 | |
|
|
291 | |
|
11.9 Kinetics of Crystallization |
|
|
292 | |
|
11.9.1 Isothermal Crystallization |
|
|
293 | |
|
11.9.2 The Avrami Equation |
|
|
293 | |
|
11.9.3 Deviations from Avrami Equation |
|
|
294 | |
|
|
294 | |
|
11.11 Historical Development of Polymer Liquid Crystals |
|
|
296 | |
|
11.12 Liquid Crystalline Phases |
|
|
297 | |
|
11.13 Identification of the Mesophases |
|
|
300 | |
|
11.14 Lyotropic Main-Chain Liquid Crystal Polymers |
|
|
302 | |
|
11.15 Thermotropic Main-Chain Liquid Crystal Polymers |
|
|
304 | |
|
11.16 Side-Chain Liquid Crystal Polymers |
|
|
309 | |
|
11.17 Chiral Nematic Liquid Crystal Polymers |
|
|
311 | |
|
|
314 | |
|
|
318 | |
|
|
318 | |
Chapter 12 The Glassy State and Glass Transition |
|
321 | |
|
|
321 | |
|
|
321 | |
|
12.3 Relaxation Processes in the Glassy State |
|
|
321 | |
|
12.4 Glass Transition Region |
|
|
323 | |
|
12.4.1 The Glass Transition Temperature, Tg |
|
|
323 | |
|
12.4.2 Experimental Demonstration of Tg |
|
|
324 | |
|
12.4.2.1 Measurement of Tg from V–T Curves |
|
|
325 | |
|
|
326 | |
|
12.4.3 Factors Affecting Tg |
|
|
327 | |
|
12.4.3.1 Chain Flexibility |
|
|
328 | |
|
|
328 | |
|
12.4.3.3 Configurational Effects |
|
|
330 | |
|
12.4.3.4 Effect of Cross-Links on Tg |
|
|
330 | |
|
12.5 Theoretical Treatments |
|
|
330 | |
|
12.5.1 The Free-Volume Theory |
|
|
331 | |
|
12.5.2 Gibbs–Di Marzio Thermodynamic Theory |
|
|
335 | |
|
|
336 | |
|
12.6 Dependence of Tg on Molar Mass |
|
|
337 | |
|
12.7 Structural Relaxation and Physical Aging |
|
|
338 | |
|
|
339 | |
|
|
342 | |
|
|
343 | |
Chapter 13 Rheology and Mechanical Properties |
|
345 | |
|
13.1 Introduction to Rheology |
|
|
345 | |
|
13.2 The Five Regions of Viscoelastic Behavior |
|
|
346 | |
|
|
347 | |
|
13.3.1 Shear Dependence of Viscosity |
|
|
349 | |
|
13.3.2 Kinetic Units in Polymer Chains |
|
|
351 | |
|
13.3.3 Effect of Chain Length |
|
|
352 | |
|
13.3.4 Temperature Dependence of η |
|
|
353 | |
|
13.3.5 Concentration Dependence of Viscosity |
|
|
353 | |
|
13.3.6 Time-Dependent Behavior |
|
|
354 | |
|
13.4 Mechanical Properties |
|
|
355 | |
|
13.4.1 Interrelation of Moduli |
|
|
357 | |
|
13.5 Mechanical Models Describing Viscoelasticity |
|
|
357 | |
|
13.6 Linear Viscoelastic Behavior of Amorphous Polymers |
|
|
360 | |
|
|
360 | |
|
13.6.2 Stress—Strain Measurements |
|
|
363 | |
|
13.6.3 Effect of Temperature on Stress—Strain Response |
|
|
363 | |
|
13.6.4 Boltzmann Superposition Principle |
|
|
364 | |
|
|
365 | |
|
13.7 Dynamic Mechanical and Dielectric Thermal Analysis |
|
|
366 | |
|
13.7.1 Dynamic Mechanical Thermal Analysis (DMTA) |
|
|
366 | |
|
13.7.2 Dielectric Thermal Analysis (DETA) |
|
|
369 | |
|
13.7.3 Comparison Between DMTA and DETA |
|
|
371 | |
|
13.8 Time—Temperature Superposition Principle |
|
|
373 | |
|
|
377 | |
|
13.10 A Molecular Theory for Viscoelasticity |
|
|
378 | |
|
13.11 The Reptation Model |
|
|
380 | |
|
|
382 | |
|
|
387 | |
|
|
388 | |
Chapter 14 The Elastomeric State |
|
389 | |
|
14.1 General Introduction |
|
|
389 | |
|
|
390 | |
|
14.2 Experimental Vulcanization |
|
|
391 | |
|
14.3 Properties of Elastomers |
|
|
391 | |
|
14.4 Thermodynamic Aspects of Rubberlike Elasticity |
|
|
392 | |
|
|
394 | |
|
14.6 Distribution Function for Polymer Conformation |
|
|
395 | |
|
14.7 Statistical Approach |
|
|
398 | |
|
14.7.1 Experimental Stress—Strain Results |
|
|
398 | |
|
14.7.1.1 Simple Extension |
|
|
398 | |
|
14.7.1.2 Simple Compression |
|
|
400 | |
|
|
400 | |
|
14.7.1.4 Large Elastic Deformation |
|
|
400 | |
|
14.8 Swelling of Elastomeric Networks |
|
|
400 | |
|
|
401 | |
|
14.10 Resilience of Elastomers |
|
|
403 | |
|
|
405 | |
|
|
408 | |
|
|
408 | |
Chapter 15 Structure—Property Relations |
|
409 | |
|
15.1 General Considerations |
|
|
409 | |
|
15.2 Control of Tm and Tg |
|
|
409 | |
|
|
410 | |
|
15.2.2 Intermolecular Bonding |
|
|
411 | |
|
15.3 Relation Between Tm and Tg |
|
|
413 | |
|
|
413 | |
|
15.5 Dependence of Tm and Tg on Copolymer Composition |
|
|
414 | |
|
|
417 | |
|
|
419 | |
|
15.8 Crystallinity and Mechanical Response |
|
|
420 | |
|
15.9 Application to Fibers, Elastomers, and Plastics |
|
|
422 | |
|
|
422 | |
|
15.10.1 Chemical Requirements |
|
|
423 | |
|
15.10.1.1 Linear Polyesters |
|
|
425 | |
|
15.10.2 Mechanical Requirements for Fibers |
|
|
426 | |
|
15.10.2.1 Spinning Techniques |
|
|
426 | |
|
15.10.2.1.1 Melt Spinning |
|
|
426 | |
|
15.10.2.1.2 Wet and Dry Spinning |
|
|
426 | |
|
15.10.2.2 Drawing, Orientation, and Crystallinity |
|
|
427 | |
|
15.10.2.3 Modulus and Chain Stiffness |
|
|
428 | |
|
|
428 | |
|
15.11 Aromatic Polyamides |
|
|
429 | |
|
|
431 | |
|
15.13 Elastomers and Cross-Linked Networks |
|
|
434 | |
|
|
435 | |
|
15.13.2 Creep in Cross-Linked Polymers |
|
|
435 | |
|
|
435 | |
|
|
435 | |
|
15.14.1 Plastic Selection for Bottle Crate Manufacture |
|
|
437 | |
|
15.14.2 Medical Applications |
|
|
438 | |
|
15.15 High-Temperature Speciality Polymers |
|
|
439 | |
|
|
446 | |
|
|
446 | |
|
|
448 | |
|
|
453 | |
|
|
454 | |
Chapter 16 Polymers for the Electronics Industry |
|
455 | |
|
|
455 | |
|
16.2 Polymer Resists for IC Fabrication |
|
|
455 | |
|
16.3 The Lithographic Process |
|
|
456 | |
|
|
457 | |
|
|
458 | |
|
|
459 | |
|
|
459 | |
|
16.5.1 Positive Photoresists |
|
|
459 | |
|
16.5.2 Negative Photoresists |
|
|
460 | |
|
16.6 Electron Beam Sensitive Resists |
|
|
463 | |
|
|
463 | |
|
|
464 | |
|
16.7 X-ray and Ion Sensitive Resists |
|
|
464 | |
|
16.8 Electroactive Polymers |
|
|
465 | |
|
16.9 Conduction Mechanisms |
|
|
466 | |
|
16.10 Preparation of Conductive Polymers |
|
|
467 | |
|
|
469 | |
|
|
472 | |
|
16.13 Polyheterocyclic Systems |
|
|
474 | |
|
|
475 | |
|
|
475 | |
|
|
476 | |
|
16.15 Poly(Phenylene Sulfide) |
|
|
476 | |
|
16.16 Poly(1,6-heptadiyne) |
|
|
476 | |
|
|
476 | |
|
16.18 Photonic Applications |
|
|
477 | |
|
16.19 Light-Emitting Polymers |
|
|
477 | |
|
|
478 | |
|
|
478 | |
|
16.21 Langmuir—Blodgett Films |
|
|
481 | |
|
16.22 Optical Information Storage |
|
|
483 | |
|
16.23 Thermorecording on Liquid Crystalline Polymers |
|
|
486 | |
|
|
487 | |
|
|
487 | |
Index |
|
489 | |