000			43230cam a2200241 a 4500
999			_c12013 _d12013
001			14681151
005			20200908111254.0
008			061227s2007 flua b 001 0 eng
020			_a9781574447798 (alk. paper)
020			_a1574447793 (alk. paper)
040			_cDLC
082	0	0	_a547.7 _222 _bH6335
100	1		_aHiemenz, Paul C.,
245	1	0	_aPolymer chemistry _c/ Paul C. Hiemenz, Timothy P. Lodge.
250			_a2nd ed.
260			_aBoca Raton : _bCRC Press, _c2007
300			_axvii, 587 p. : _bill. ; _c27 cm.
650		0	_aPolymers.
650		0	_aPolymerization.
700	1		_aLodge, Timothy.
942			_cBK
505	0		_a1 Introduction to Chain Molecules .................................................................1 1.1 Introduction................................................................................................................... 1 1.2 How Big is Big? ............................................................................................................ 3 1.2.1 Molecular Weight ..............................................................................................3 1.2.2 Spatial Extent.....................................................................................................4 1.3 Linear and Branched Polymers, Homopolymers, and Copolymers ............................. 7 1.3.1 Branched Structures ...........................................................................................7 1.3.2 Copolymers ........................................................................................................9 1.4 Addition, Condensation, and Natural Polymers.......................................................... 11 1.4.1 Addition and Condensation Polymers .............................................................11 1.4.2 Natural Polymers .............................................................................................13 1.5 Polymer Nomenclature ................................................................................................ 18 1.6 Structural Isomerism.................................................................................................... 20 1.6.1 Positional Isomerization ..................................................................................20 1.6.2 Stereo Isomerization ........................................................................................21 1.6.3 Geometrical Isomerization...............................................................................22 1.7 Molecular Weights and Molecular Weight Averages................................................. 24 1.7.1 Number-, Weight-, and z-Average Molecular Weights ..................................25 1.7.2 Polydispersity Index and Standard Deviation .................................................26 1.7.3 Examples of Distributions ...............................................................................28 1.8 Measurement of Molecular Weight............................................................................. 31 1.8.1 General Considerations....................................................................................31 1.8.2 End Group Analysis.........................................................................................32 1.8.3 MALDI Mass Spectrometry ............................................................................35 1.9 Preview of Things to Come......................................................................................... 37 1.10 Chapter Summary ........................................................................................................ 38 References............................................................................................................................... 41 Further Readings...................................................................................................................... 41 2 Step-Growth Polymerization......................................................................43 2.1 Introduction................................................................................................................... 43 2.2 Condensation Polymers: One Step at a Time ............................................................... 43 2.2.1 Classes of Step-Growth Polymers .....................................................................43 Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page x 20.10.2006 1:22pm 2.2.2 First Look at the Distribution of Products ........................................................44 2.2.3 A First Look at Reactivity and Reaction Rates ................................................46 2.3 Kinetics of Step-Growth Polymerization ...................................................................... 49 2.3.1 Catalyzed Step-Growth Reactions.....................................................................50 2.3.2 How Should Experimental Data Be Compared with Theoretical Rate Laws? .....................................................................................52 2.3.3 Uncatalyzed Step-Growth Reactions.................................................................53 2.4 Distribution of Molecular Sizes .................................................................................... 56 2.4.1 Mole Fractions of Species .................................................................................56 2.4.2 Weight Fractions of Species..............................................................................58 2.5 Polyesters ....................................................................................................................... 60 2.6 Polyamides ..................................................................................................................... 64 2.7 Stoichiometric Imbalance .............................................................................................. 67 2.8 Chapter Summary .......................................................................................................... 71 Problems ................................................................................................................................. 71 References............................................................................................................................... 76 Further Reading ....................................................................................................................... 76 3 Chain-Growth Polymerization....................................................................77 3.1 Introduction .................................................................................................................... 77 3.2 Chain-Growth and Step-Growth Polymerizations: Some Comparisons....................... 77 3.3 Initiation ......................................................................................................................... 79 3.3.1 Initiation Reactions ............................................................................................80 3.3.2 Fate of Free Radicals .........................................................................................81 3.3.3 Kinetics of Initiation ..........................................................................................82 3.3.4 Photochemical Initiation ....................................................................................84 3.3.5 Temperature Dependence of Initiation Rates....................................................85 3.4 Termination.................................................................................................................... 86 3.4.1 Combination and Disproportionation ................................................................86 3.4.2 Effect of Termination on Conversion to Polymer ............................................88 3.4.3 Stationary-State Radical Concentration ............................................................89 3.5 Propagation .................................................................................................................... 90 3.5.1 Rate Laws for Propagation ................................................................................91 3.5.2 Temperature Dependence of Propagation Rates ...............................................92 3.5.3 Kinetic Chain Length.........................................................................................94 3.6 Radical Lifetime ............................................................................................................ 96 3.7 Distribution of Molecular Weights................................................................................ 99 3.7.1 Distribution of i-mers: Termination by Disproportionation .............................99 3.7.2 Distribution of i-mers: Termination by Combination.....................................102 3.8 Chain Transfer ............................................................................................................. 104 3.8.1 Chain Transfer Reactions ................................................................................105 3.8.2 Evaluation of Chain Transfer Constants .........................................................106 3.8.3 Chain Transfer to Polymer ..............................................................................108 3.8.4 Suppressing Polymerization ............................................................................109 3.9 Chapter Summary ........................................................................................................ 110 Problems ............................................................................................................................... 110 References............................................................................................................................. 114 Further Reading ..................................................................................................................... 115 Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xi 20.10.2006 1:22pm 4 Controlled Polymerization .......................................................................117 4.1 Introduction................................................................................................................ 117 4.2 Poisson Distribution for an Ideal Living Polymerization ......................................... 118 4.2.1 Kinetic Scheme..............................................................................................119 4.2.2 Breadth of the Poisson Distribution ..............................................................122 4.3 Anionic Polymerization ............................................................................................. 126 4.4 Block Copolymers, End-Functional Polymers, and Branched Polymers by Anionic Polymerization........................................................................ 129 4.4.1 Block Copolymers .........................................................................................129 4.4.2 End-Functional Polymers ..............................................................................133 4.4.3 Regular Branched Architectures....................................................................135 4.5 Cationic Polymerization ............................................................................................ 137 4.5.1 Aspects of Cationic Polymerization ..............................................................138 4.5.2 Living Cationic Polymerization ....................................................................140 4.6 Controlled Radical Polymerization ........................................................................... 142 4.6.1 General Principles of Controlled Radical Polymerization............................142 4.6.2 Particular Realizations of Controlled Radical Polymerization .....................144 4.6.2.1 Atom Transfer Radical Polymerization.........................................144 4.6.2.2 Stable Free-Radical Polymerization (SFRP).................................145 4.6.2.3 Reversible Addition-Fragmentation Transfer (RAFT) Polymerization ...............................................................................145 4.7 Polymerization Equilibrium....................................................................................... 147 4.8 Ring-Opening Polymerization ................................................................................... 150 4.8.1 General Aspects .............................................................................................150 4.8.2 Specific Examples of Living Ring-Opening Polymerizations......................152 4.8.2.1 Poly(Ethylene Oxide) ....................................................................152 4.8.2.2 Polylactide......................................................................................153 4.8.2.3 Poly(dimethyl siloxane).................................................................154 4.8.2.4 Ring-Opening Metathesis Polymerization (ROMP) .....................155 4.9 Dendrimers................................................................................................................. 156 4.10 Chapter Summary ...................................................................................................... 160 Problems ............................................................................................................................... 161 References............................................................................................................................. 163 Further Reading ..................................................................................................................... 163 5 Copolymers, Microstructure, and Stereoregularity................................165 5.1 Introduction................................................................................................................ 165 5.2 Copolymer Composition............................................................................................ 166 5.2.1 Rate Laws ......................................................................................................166 5.2.2 Composition versus Feedstock ......................................................................168 5.3 Reactivity Ratios........................................................................................................ 170 5.3.1 Effects of r Values.........................................................................................171 5.3.2 Relation of Reactivity Ratios to Chemical Structure....................................173 5.4 Resonance and Reactivity.......................................................................................... 175 5.5 A Closer Look at Microstructure .............................................................................. 179 5.5.1 Sequence Distributions ..................................................................................180 5.5.2 Terminal and Penultimate Models ................................................................183 5.6 Copolymer Composition and Microstructure: Experimental Aspects ...................... 185 5.6.1 Evaluating Reactivity Ratios from Composition Data .................................186 Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xii 20.10.2006 1:22pm 5.6.2 Spectroscopic Techniques..............................................................................188 5.6.3 Sequence Distribution: Experimental Determination ...................................190 5.7 Characterizing Stereoregularity ................................................................................. 193 5.8 A Statistical Description of Stereoregularity ............................................................ 196 5.9 Assessing Stereoregularity by Nuclear Magnetic Resonance................................... 200 5.10 Ziegler¿Natta Catalysts ............................................................................................. 205 5.11 Single-Site Catalysts .................................................................................................. 208 5.12 Chapter Summary ...................................................................................................... 211 Problems ............................................................................................................................... 212 References............................................................................................................................. 216 Bibliography .......................................................................................................................... 216 6 Polymer Conformations ...........................................................................217 6.1 Conformations, Bond Rotation, and Polymer Size..................................................... 217 6.2 Average End-to-End Distance for Model Chains ....................................................... 219 Case 6.2.1 The Freely Jointed Chain .......................................................................220 Case 6.2.2 The Freely Rotating Chain .....................................................................221 Case 6.2.3 Hindered Rotation Chain ........................................................................222 6.3 Characteristic Ratio and Statistical Segment Length.................................................. 223 6.4 Semiflexible Chains and the Persistence Length........................................................ 225 6.4.1 Persistence Length of Flexible Chains............................................................227 6.4.2 Worm-Like Chains ..........................................................................................228 6.5 Radius of Gyration....................................................................................................... 229 6.6 Spheres, Rods, and Coils ............................................................................................. 234 6.7 Distributions for End-to-End Distance and Segment Density .................................... 235 6.7.1 Distribution of the End-to-End Vector............................................................236 6.7.2 Distribution of the End-to-End Distance.........................................................239 6.7.3 Distribution about the Center of Mass ............................................................240 6.8 Self-Avoiding Chains: A First Look ........................................................................... 241 6.9 Chapter Summary ........................................................................................................ 242 Problems ............................................................................................................................... 242 References............................................................................................................................. 244 Further Reading ..................................................................................................................... 245 7 Thermodynamics of Polymer Solutions .................................................247 7.1 Review of Thermodynamic and Statistical Thermodynamic Concepts ..................... 247 7.2 Regular Solution Theory ............................................................................................. 249 7.2.1 Regular Solution Theory: Entropy of Mixing.................................................249 7.2.2 Regular Solution Theory: Enthalpy of Mixing ...............................................251 7.3 Flory¿Huggins Theory................................................................................................. 254 7.3.1 Flory¿Huggins Theory: Entropy of Mixing by a Quick Route ......................255 7.3.2 Flory¿Huggins Theory: Entropy of Mixing by a Longer Route ....................255 7.3.3 Flory¿Huggins Theory: Enthalpy of Mixing ..................................................257 7.3.4 Flory¿Huggins Theory: Summary of Assumptions ........................................258 7.4 Osmotic Pressure ......................................................................................................... 258 7.4.1 Osmotic Pressure: General Case .....................................................................259 7.4.1.1 Number-Average Molecular Weight ...............................................261 7.4.2 Osmotic Pressure: Flory¿Huggins Theory ......................................................263 Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xiii 20.10.2006 1:22pm 7.5 Phase Behavior of Polymer Solutions......................................................................... 264 7.5.1 Overview of the Phase Diagram......................................................................265 7.5.2 Finding the Binodal .........................................................................................268 7.5.3 Finding the Spinodal........................................................................................269 7.5.4 Finding the Critical Point ................................................................................270 7.5.5 Phase Diagram from Flory¿Huggins Theory ..................................................271 7.6 What is in x?................................................................................................................ 275 7.6.1 x from Regular Solution Theory .....................................................................275 7.6.2 x from Experiment...........................................................................................276 7.6.3 Further Approaches to x..................................................................................278 7.7 Excluded Volume and Chains in a Good Solvent ...................................................... 280 7.8 Chapter Summary ........................................................................................................ 283 Problems ............................................................................................................................... 284 References............................................................................................................................. 287 Bibliography .......................................................................................................................... 288 8 Light Scattering by Polymer Solutions...................................................289 8.1 Introduction: Light Waves........................................................................................... 289 8.2 Basic Concepts of Scattering....................................................................................... 291 8.2.1 Scattering from Randomly Placed Objects .....................................................292 8.2.2 Scattering from a Perfect Crystal ....................................................................292 8.2.3 Origins of Incoherent and Coherent Scattering ..............................................293 8.2.4 Bragg¿s Law and the Scattering Vector ..........................................................294 8.3 Scattering by an Isolated Small Molecule .................................................................. 296 8.4 Scattering from a Dilute Polymer Solution................................................................. 298 8.5 The Form Factor and the Zimm Equation .................................................................. 304 8.5.1 Mathematical Expression for the Form Factor ...............................................305 8.5.2 Form Factor for Isotropic Solutions ................................................................306 8.5.3 Form Factor as qRg P 1 ..................................................................................307 8.5.4 Zimm Equation ................................................................................................307 8.5.5 Zimm Plot ........................................................................................................308 8.6 Scattering Regimes and Particular Form Factors........................................................ 312 8.7 Experimental Aspects of Light Scattering .................................................................. 314 8.7.1 Instrumentation ................................................................................................316 8.7.2 Calibration........................................................................................................317 8.7.3 Samples and Solutions.....................................................................................319 8.7.4 Refractive Index Increment .............................................................................319 8.8 Chapter Summary ........................................................................................................ 320 Problems ............................................................................................................................... 321 Bibliography .......................................................................................................................... 325 Further Reading ..................................................................................................................... 325 9 Dynamics of Dilute Polymer Solutions ...................................................327 9.1 Introduction: Friction and Viscosity............................................................................ 327 9.2 Stokes¿ Law and Einstein¿s Law................................................................................. 330 9.2.1 Viscous Forces on Rigid Spheres....................................................................331 9.2.2 Suspension of Spheres .....................................................................................332 9.3 Intrinsic Viscosity ........................................................................................................ 334 9.3.1 General Considerations....................................................................................334 9.3.2 Mark¿Houwink Equation ................................................................................336 Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xiv 20.10.2006 1:22pm 9.4 Measurement of Viscosity ........................................................................................ 341 9.4.1 Poiseuille Equation and Capillary Viscometers ...........................................341 9.4.2 Concentric Cylinder Viscometers .................................................................345 9.5 Diffusion Coefficient and Friction Factor ................................................................ 346 9.5.1 Tracer Diffusion and Hydrodynamic Radius................................................347 9.5.2 Mutual Diffusion and Fick¿s Laws...............................................................348 9.6 Dynamic Light Scattering ......................................................................................... 354 9.7 Hydrodynamic Interactions and Draining ................................................................ 357 9.8 Size Exclusion Chromatography............................................................................... 360 9.8.1 Basic Separation Process ..............................................................................361 9.8.2 Separation Mechanism ..................................................................................365 9.8.3 Two Calibration Strategies ...........................................................................367 9.8.3.1 Limitations of Calibration by Standards.......................................367 9.8.3.2 Universal Calibration ....................................................................368 9.8.4 Size Exclusion Chromatography Detectors ..................................................369 9.8.4.1 RI Detector ....................................................................................369 9.8.4.2 uv¿vis Detector .............................................................................370 9.8.4.3 Light Scattering Detector..............................................................371 9.8.4.4 Viscometer.....................................................................................372 9.9 Chapter Summary...................................................................................................... 372 Problems............................................................................................................................. 373 References ........................................................................................................................... 378 Further Reading................................................................................................................... 379 10 Networks, Gels, and Rubber Elasticity .................................................381 10.1 Formation of Networks by Random Cross-Linking............................................... 381 10.1.1 Definitions .................................................................................................381 10.1.2 Gel Point....................................................................................................383 10.2 Polymerization with Multifunctional Monomers ................................................... 386 10.2.1 Calculation of the Branching Coefficient.................................................387 10.2.2 Gel Point....................................................................................................388 10.2.3 Molecular-Weight Averages .....................................................................389 10.3 Elastic Deformation ................................................................................................ 392 10.4 Thermodynamics of Elasticity ................................................................................ 394 10.4.1 Equation of State.......................................................................................394 10.4.2 Ideal Elastomers ........................................................................................396 10.4.3 Some Experiments on Real Rubbers ........................................................397 10.5 Statistical Mechanical Theory of Rubber Elasticity: Ideal Case ........................... 398 10.5.1 Force to Extend a Gaussian Chain ...........................................................400 10.5.2 Network of Gaussian Strands....................................................................402 10.5.3 Modulus of the Gaussian Network ...........................................................403 10.6 Further Developments in Rubber Elasticity ........................................................... 406 10.6.1 Non-Gaussian Force Law..........................................................................406 10.6.2 Front Factor ...............................................................................................407 10.6.3 Network Defects........................................................................................408 10.6.4 Mooney¿Rivlin Equation ..........................................................................409 10.7 Swelling of Gels...................................................................................................... 410 10.7.1 Modulus of a Swollen Rubber ..................................................................411 10.7.2 Swelling Equilibrium ................................................................................412 Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xv 20.10.2006 1:22pm 10.8 Chapter Summary.................................................................................................... 414 Problems............................................................................................................................. 416 References ........................................................................................................................... 418 Further Reading................................................................................................................... 418 11 Linear Viscoelasticity .............................................................................419 11.1 Basic Concepts ........................................................................................................ 419 11.1.1 Stress and Strain........................................................................................421 11.1.2 Viscosity, Modulus, and Compliance .......................................................421 11.1.3 Viscous and Elastic Responses .................................................................422 11.2 Response of the Maxwell and Voigt Elements ...................................................... 423 11.2.1 Transient Response: Stress Relaxation .....................................................423 11.2.2 Transient Response: Creep........................................................................426 11.2.3 Dynamic Response: Loss and Storage Moduli.........................................427 11.2.4 Dynamic Response: Complex Modulus and Complex Viscosity ............430 11.3 Boltzmann Superposition Principle ........................................................................ 431 11.4 Bead¿Spring Model................................................................................................. 433 11.4.1 Ingredients of the Bead¿Spring Model.....................................................433 11.4.2 Predictions of the Bead¿Spring Model.....................................................434 11.5 Zimm Model for Dilute Solutions, Rouse Model for Unentangled Melts .................................................................................................. 440 11.6 Phenomenology of Entanglement ........................................................................... 445 11.6.1 Rubbery Plateau ........................................................................................445 11.6.2 Dependence of Me on Molecular Structure ..............................................448 11.7 Reptation Model...................................................................................................... 451 11.7.1 Reptation Model: Longest Relaxation Time and Diffusivity...................452 11.7.2 Reptation Model: Viscoelastic Properties ................................................455 11.7.3 Reptation Model: Additional Relaxation Processes .................................457 11.8 Aspects of Experimental Rheometry ...................................................................... 459 11.8.1 Shear Sandwich and Cone and Plate Rheometers....................................459 11.8.2 Further Comments about Rheometry........................................................461 11.9 Chapter Summary .................................................................................................... 462 Problems............................................................................................................................. 462 References ........................................................................................................................... 465 Further Reading................................................................................................................... 465 12 Glass Transition......................................................................................467 12.1 Introduction ............................................................................................................. 467 12.1.1 Definition of a Glass .................................................................................467 12.1.2 Glass and Melting Transitions ..................................................................468 12.2 Thermodynamic Aspects of the Glass Transition .................................................. 470 12.2.1 First-Order and Second-Order Phase Transitions.....................................471 12.2.2 Kauzmann Temperature ............................................................................473 12.2.3 Theory of Gibbs and DiMarzio ................................................................474 12.3 Locating the Glass Transition Temperature ........................................................... 476 12.3.1 Dilatometry................................................................................................476 12.3.2 Calorimetry................................................................................................478 12.3.3 Dynamic Mechanical Analysis .................................................................480 Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xvi 20.10.2006 1:22pm 12.4 Free Volume Description of the Glass Transition.................................................. 481 12.4.1 Temperature Dependence of the Free Volume ........................................482 12.4.2 Free Volume Changes Inferred from the Viscosity .................................483 12.4.3 Williams¿Landel¿Ferry Equation.............................................................485 12.5 Time¿Temperature Superposition........................................................................... 488 12.6 Factors That Affect the Glass Transition Temperature.......................................... 493 12.6.1 Dependence on Chemical Structure..........................................................493 12.6.2 Dependence on Molecular Weight ...........................................................494 12.6.3 Dependence on Composition ....................................................................494 12.7 Mechanical Properties of Glassy Polymers ............................................................ 498 12.7.1 Basic Concepts ..........................................................................................498 12.7.2 Crazing, Yielding, and the Brittle-to-Ductile Transition .........................500 12.7.3 Role of Chain Stiffness and Entanglements .............................................503 12.8 Chapter Summary.................................................................................................... 506 Problems............................................................................................................................. 507 Bibliography....................................................................................................................... 510 Further Reading................................................................................................................... 510 13 Crystalline Polymers...............................................................................513 13.1 Introduction and Overview ..................................................................................... 513 13.2 Structure and Characterization of Unit Cells ......................................................... 515 13.2.1 Classes of Crystals ....................................................................................515 13.2.2 X-Ray Diffraction .....................................................................................517 13.2.3 Examples of Unit Cells .............................................................................520 13.3 Thermodynamics of Crystallization: Relation of Melting Temperature to Molecular Structure ............................................................................................ 523 13.4 Structure and Melting of Lamellae......................................................................... 528 13.4.1 Surface Contributions to Phase Transitions..............................................528 13.4.2 Dependence of Tm on Lamellar Thickness...............................................529 13.4.3 Dependence of Tm on Molecular Weight .................................................532 13.4.4 Experimental Characterization of Lamellar Structure .............................534 13.5 Kinetics of Nucleation and Growth ........................................................................ 538 13.5.1 Primary Nucleation ...................................................................................539 13.5.2 Crystal Growth ..........................................................................................541 13.6 Morphology of Semicrystalline Polymers .............................................................. 547 13.6.1 Spherulites .................................................................................................547 13.6.2 Nonspherulitic Morphologies....................................................................550 13.7 Kinetics of Bulk Crystallization ............................................................................. 554 13.7.1 Avrami Equation .......................................................................................554 13.7.2 Kinetics of Crystallization: Experimental Aspects ..................................559 13.8 Chapter Summary.................................................................................................... 564 Problems............................................................................................................................. 565 References ........................................................................................................................... 568 Further Reading................................................................................................................... 568 Appendix .........................................................................................................569 A.1 Series Expansions ...............................................................................................................569 A.2 Summation Formulae..........................................................................................................570 Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Page Proof page xvii 20.10.2006 1:22pm A.3 Transformation to Spherical Coordinates...........................................................................571 A.4 Some Integrals of Gaussian Functions ...............................................................................572 A.5 Complex Numbers ..............................................................................................................574