Verfügbarkeit: The elements of polymer science and engineering

The elements of polymer science and engineering:

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Bibliographische Detailangaben
Hauptverfasser:	Rudin, Alfred (VerfasserIn), Choi, Phillip (VerfasserIn)
Format:	Buch
Sprache:	English
Veröffentlicht:	San Diego [u.a.] Elsevier/AP 2013
Ausgabe:	3. ed.
Schlagworte:	Polymers Polymerization Polymere Polymerisation Makromolekulare Chemie Lehrbuch
Online-Zugang:	Inhaltsverzeichnis
Beschreibung:	Includes bibliographical references and index
Beschreibung:	xx, 563 p. graph. Darst. 24 cm
ISBN:	9780123821782

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Datensatz im Suchindex

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adam_text	Contents Preface ..................................................................................................................X.VÜ In Memoriam ..........................................................................................................xix CHAPTER 1 Introductory Concepts and Definitions ι 1.1 Some Definitions .........................................................................1 1.1.1 Polymer .............................................................................1 1.1.2 Monomer ...........................................................................2 1.1.3 Oligomer ...........................................................................2 1.1.4 Rep e a tin g Un i t .................................................................. З 1.1.5 Representations of Polymer Structures ............................5 1.1.6 End Groups .......................................................................6 1.2 Degree of Polymenzati on ...........................................................6 1.3 Polymerization and Functionality ...............................................7 1.3.1 Polymenzati on ..................................................................7 1.3.2 Functionality .....................................................................7 1.3.3 Fatent Functionality ..........................................................9 1.4 Why Are Synthetic Polymers Useful? ......................................12 1.5 Copolymers ................................................................................16 1.5.1 Random Copolymer ........................................................16 1.5.2 Alternating Copolymer ...................................................17 1.5.3 Graft Copolymer .............................................................17 1.5.4 Block Copolymer ............................................................18 1.6 Molecular Architecture .............................................................19 1.7 Thermoplastics and Thermosets ................................................22 1.8 Elastomers, Fibers, and Plastics ................................................23 1.9 Miscellaneous Terms .................................................................26 1.10 Polymer Nomenclature .............................................................27 1.11 Constitutional Isomerism ..........................................................33 1.11.1 Positional Isomerism .....................................................33 1.11.2 Branching ......................................................................36 1.12 Configurati onal Isomerism .......................................................38 1.12.1 Geometrical Isomerism .................................................38 1.12.2 S tereoisomerism ............................................................39 1.13 Polymer Conformation ..............................................................43 VII viii Contents 1.14 Molecular Dimensions in the Amorphous State ......................47 1.14.1 Radius of Gyration and End-to-End Distance of Flexible Macromolecules .........................................47 1.14.2 Root Mean Square End-to-End Distance of Flexible Macromolecules .........................................48 References ...........................................................................................62 CHAPTER 2 Basic Principles of Polymer Molecular Weights 63 2.1 Importance of Molecular Weight Control ..................................63 2.2 Plan of This Chapter ...................................................................64 2.3 An thmetic Mean .........................................................................64 2.3.1 Number Distribution, Mn ..................................................66 2.3.2 Weight Distribution, Mw ..................................................68 2.4 Molecular Weight Averages as Ratios of Moments ...................69 2.4.1 Moments in Statistics and Mechanics ..............................69 2.4.2 Dimensions ........................................................................71 2.4.3 Arithmetic Mean as a Ratio of Moments .........................71 2.4.4 Extension to Other Molecular Weight Averages .............72 2.5 Breadth of the Distribution .........................................................74 2.6 Summarizing the Molecular Weight Distribution ......................78 2.7 Ę>MW>M„ ............................................................................79 2.8 Integral and Summative Expressions ..........................................79 2.9 Typical Molecular Weight Distributions ....................................80 Appendix 2A: Molecular Weight Averages of Blends of Broad Dì stnbution Polymers .........................................................................81 Reference .............................................................................................87 CHAPTER 3 Practical Aspects of Molecular Weight Measurements ...........................................................................89 3.1 Mn Methods ..................................................................................89 3.1.1 Ideal Solutions ..................................................................90 3.1.2 Osmotic Pressure ..............................................................92 3.1.3 Osmotic Pressure Measures, Mn ......................................94 3.1.4 Vinal Equations and Vinal Coefficients ..........................95 3.1.5 Membrane Osmometry .....................................................97 3.1.6 Vapor Phase Osmometry ................................................100 3.1.7 Ebulhometry ....................................................................103 3.1.8 Cryoscopy (Freezing Point Depression) .........................103 3.1.9 End-Group Determinations .............................................103 3.2 Light Scattering .........................................................................104 3.2.1 Terminology ....................................................................107 3.2.2 Effect of Polydispersity ..................................................108 3.2.3 Scattenng from Large Particles ......................................109 Contents ix 3.2.4 Light-Scattering Instrumentation ....................................112 3.2.5 Light Scattering from Copolymers .................................112 3.2.6 Radias of Gyration from Light-Scattering Data ............] 13 3.3 Dilute Solution Viscometry ......................................................113 3.3.1 Viscosity Average Molecular Weight Mv ......................118 3.3.2 Calibration of the Mark—Houwink-Sakurada Equation ..........................................................................120 3.3.3 Measurement of Intnnsic Viscosity ................................121 3.3.4 Single-Point Intrinsic Viscosities ...................................127 3.3.5 Solution Viscosity Terminology .....................................128 3.3.6 Solution Viscosities in Polymer Quality Control ...........128 3.3.7 Copolymers and Branched Polymers .............................129 3.4 Size Exclu sion Chiomato graphy ...............................................129 3.4.1 Experimental Arrangement .............................................129 3.4.2 Data Interpretation ..........................................................130 3.4.3 Universal Calibration for Linear Homopolymers ..........132 3.4.4 Branched Polymers ......................................................... J 38 3.4.5 Aqueous SEC ..................................................................140 3.4.6 Inhomogeneous Polymers ...............................................140 3.4.7 MALDLMS .....................................................................140 Appendix ЗА: Multigrade Motor Oils ..............................................141 References .........................................................................................147 CHAPTER 4 Mechanical Properties of Polymer Solids and Liquids ...............................................................................149 4.1 Introduction .............................................................................149 4.2 Thermal Transitions ................................................................149 4.3 Crystallization of Polymers .....................................................153 4.3.1 Degree of Cry stallini ty................................................. 155 4.3.2 Microstructure of Semicrystaľlme Polymers ................157 4.4 The Glass Transition ...............................................................165 4.4.1 Modulus—Temperature Relations .................................166 4.4.2 Effect of Polymer Structure od Tg ................................170 4.4.3 Correlations between 7m and Tg ...................................173 4.4.4 Measurement of Tg .......................................................173 4.5 Rubber Elasticity .....................................................................175 4.5.1 Qualitative Description of Elastomer Behavior ...........175 4.5.2 Rubber as an Entropy Spring .......................................177 4.6 R odlike Macromolecules .........................................................1 84 4.7 Polymer Viscoelasticity ...........................................................185 4.7.1 Phenomenologjcal Viscoelasticity ................................187 4.7.2 Linear Viscoelasticity ...................................................192 4.8 Dynamic Mechanical Behavior at Thermal Transitions ........199 Contents 4.8.1 Relaxations at Temperatures below Tg .........................201 4.9 Stress-Strain Tests .................................................................202 4.9.1 Rate and Temperature Effects ......................................205 4.10 Crazing jn Glassy Polymers ....................................................206 4.11 Fracture Mechanics .................................................................209 4.12 Toughness and Bnttleness ......................................................212 4.13 Rheology .................................................................................214 4.14 Effects of Fabrication Processes .............................................222 References .........................................................................................228 CHAPTER 5 Polymer Mixtures ....................................................................231 5.1 Compatibility ............-................................................................231 5.2 Thermodynamic Theories .........................................................232 5.2.1 Regular Solutions and Solubility Parameter ..................232 5.2.2 Flory-Huggins Theory ...................................................240 5.2.3 Modified Solubility Parameter Models ..........................247 5.3 Solvents and Plasticizers ...........................................................250 5.3.1 Solvents for Coating Resins ...........................................250 5.3.2 Plasticization »f Polymers ..............................................250 5.4 Fractionation .............-................................................................251 5.5 Practical Aspects of Polymer Blending ....................................254 5.5.1 Objectives in Making Blends .........................................254 5.5.2 Blending Operations .......................................................254 5.5.3 Procedures to Retard or Eliminate Demixing of Polymer Mixtures .......................................................257 5.6 Reinforced Elastomers ..............................................................266 5.7 Reinforced Plastics ....................................................................266 References .........................................................................................273 CHAPTER 6 Diffusion in Polymers ............................................................275 6.1 Introduction ...............................................................................275 6.2 Fick sLaws ...............................................................................276 6.3 Diffusion Coefficients ...............................................................278 6.4 Mutual Diffusion .......................................................................279 6.5 Self-Diffusion of Polymer Chains in Dilute Polymer Solutions...- .................................................................281 6.5.1 Brownian Motion ............................................................282 6.5.2 Langevin Dynamics ........................................................286 6.5.3 Rouse Model.. .................................................................291 6.5.4 Zimm Model ...................................................................293 6.6 Self-Diffusion of Solvent in Polymers .....................................294 Contents xi 6.6.1 Transition State Theory — Diffusion in Simple Liquids .............................................................................294 6.6.2 Free Volume Theory .......................................................298 References .........................................................................................304 CHAPTER 7 Step-Growth Polymerizations 305 7.1 Condensation and Addition Polymers ......................................305 7.2 Step-Growth and Cham-Growth Polymerizations ....................308 7.3 Requirements for Step-Growth Polymerization .......................311 7.3.1 Speed of Step-Growth Polymerizations .........................313 7.3.2 Side Reactions in Step-Growth Polymerization .............313 7.4 Polymer Size and Extent of Conversion of Functional Groups in Equilibrium Step-Growth Polymerizations .........315 7.4.1 Basic Assumptions ..........................................................315 7.4.2 Number Average Degree of Polymerization in Step-Growth Reactions ...............................................317 7.4.3 Molecular Weight Distribution in Equilibrium S tep- Growth Polymerizations .........................................324 7.5 Interfacial and Solution Polymerizations of Acid Chlorides and Other Reactive Monomers .................................331 7.6 Step-Growth Copolymenzations ...............................................333 References .........................................................................................339 CHAPTER 8 Free-Radical Polymerization 341 8.1 Scope .......................................................................................341 8.2 PolymerizabiJity of Monomers ...............................................341 8.3 Overall Kinetics of Radical Polymerization ...........................343 8.3.1 Initiation ........................................................................344 8.3.2 Propagation ...................................................................345 8.3.3 Termination ...................................................................346 8.3.4 Rate of Polymerization .................................................347 8.3.5 Integrated Rate of Polymerization Expression .............349 8.4 A Note on Termination Rate Constants ..................................350 8.5 Methods of Producing Radical s ..............................................351 8.5.1 Thermal Decomposition of Initiators ...........................351 8.5.2 Redox Sources ..............................................................352 8.5.3 Photochemical Initiation ...............................................354 8.5.4 Other Initiation Methods ..............................................355 8.5.5 Initiator Efficiency ........................................................355 8.5.6 Measurement of kđ ........................................................357 8.6 Length of the Kinetic Chain and Number Average Degree of Polymerization of the Polymer ..........................357 xii Contents 8.7 Modes of Termination .............................................................359 8.8 Cham Transfer .........................................................................359 8.8.1 Transfer to Initiator ......................................................362 8.8.2 Transfer to Monomer ...................................................362 8.8.3 Transfer to Solvent and Cham Transfer Agents ..........364 8.8.4 Cham Transfer to Polymer ...........................................366 8.8.5 All y lie Transfer ............................................................368 8.9 Inhibition and Retardation ......................................................369 8.10 Readily Observable Features of Free-Radical Polymerizations ...................................................................371 8.11 Radical Lifetimes and Concentrations ....................................372 8.12 Determination of fep and kt ......................................................374 8.13 Deviations from Ideal Kinetics ...............................................374 8.13.1 Diffusion Control of Termination ..............................375 8.13.2 Autoacceleration .........................................................375 8.14 Molecular Weight Distribution ...............................................377 8.14.1 Low-Conversion Polymerization ...............................377 8.14.2 High-Conversion Polymerization ...............................379 8.15 Free-Radical Techniques for Polymers with Narrower Molecu] ar Weight Di stnbu ti ons............................. 380 8.16 Effects of Temperature ...........................................................381 8.16.1 Rate and Degree of Polymerization ...........................381 8.16.2 Polymerization—Depolymerization Equilibrium ........383 8.17 Free-Radical Polymerization Processes ..................................386 References .........................................................................................388 CHAPTER 9 Copolymerization ....................................................................391 9.1 Chain-Growth Copolymerization ............................................391 9.2 Simple Copolymer Equation ...................................................392 9.3 Copolymer Structure Inferences from Reactivity Ratios .......395 9.3.1 Random Copolymers ....................................................395 9.3.2 Alternating Copolymers ...............................................397 9.3.3 Long Sequences of One Monomer ..............................398 9.3.4 Block Copolymers ........................................................398 9.4 Azeotropic Compositions ........................................................398 9.5 Integrated Binary Copolymer Equation ..................................400 9.6 Determination of Reactivity Ratios ........................................402 9.7 Multicomponent Copolymerizations .......................................406 9.8 Sequence Distribution in Copolymers ....................................407 9.9 Gel Formation During Copolymerization and Cross-Linking ...............................................................410 Contents xiii 9.10 Reactivities of Radicais and Monomers .................................412 9.10.1 Resonance Effects ......................................................412 9.10.2 Polar Effects ...............................................................413 9.10.3 Stenc Effects ..............................................................415 9.11 Analysis of Reactivity Data ....................................................415 9.12 Effect of Reaction Conditions ................................................417 9.12.1 Temperature ................................................................417 9.12.2 Pressure .......................................................................418 9.12.3 Medium ........................................................................418 9.12.4 Effects of Complex Formation ..................................419 9.13 Rates of Free-Radical Copolymerizations ..............................420 9.14 Alternative Copolymenzation Models ....................................420 References .........................................................................................424 CHAPTER 10 Dispersion and Emulsion Polymerizations 427 10.1 Dispersion Polymerization ......................................................427 10.2 Emulsion Polymerization ........................................................430 10.2.1 Harkins—Smith—Ewart Mechanism ..........................434 10.2.2 Role of Surfactants .....................................................437 10.2.3 Surfactant-Free Emulsion Polymerizations ................438 10.2.4 Mechanism of Emulsion Polymerization ...................439 10.2.5 Heterogeneous Polymer Particles ...............................441 10.3 Other Ingredients in Emulsion Recipes ..................................445 10.4 Emulsion Polymerization Processes .......................................446 References .........................................................................................447 CHAPTER 11 Ionic and Coordinated Polymerizations 449 11.1 Comparison of Ionic and Free-Radical Polymerizations .......449 11.2 Anionie Polymenzation ..........................................................450 11.2.1 Overview .....................................................................450 11.2.2 Amomc Initiation .......................................................452 11.2.3 Anionie Propagation ...................................................457 11.2.4 Termination Reactions ...............................................460 11.2.5 Temperature Effects ...................................................461 11.2.6 Anionie Copolymenzation Reactions ........................461 11.2.7 Stereochemistry of Amomc Diene Polymerization ...464 11.3 Group Transfer Polymerization ..............................................465 11.4 Catiomc Polymerization ..........................................................467 11.4.1 Overview .....................................................................467 11.4.2 Initiation of Polymerization of Vinyl Monomers ......469 11.4.3 Propagation Reactions ................................................472 xiv Contents 11.4.4 Tennination and Transfer Processes ..........................473 11.4.5 Kinetics of Cationic Polymerization of Olefins .........475 11.4.6 Temperature Effects ....................................................477 11.4.7 Polymerization of Vinyl and Cyclic Ethers ...............478 11.4.8 Living Cationic Polymerizations ................................479 11.5 Coordination Polymerization ..................................................479 11.5.1 Ziegler-Natta Catalysts .............................................480 11.5.2 Kinetics of Ziegler— Natta Polymerizations ...............482 11.5.3 Practical Features of Ziegler— Natta Polymerizations ...........................................................483 11.5.4 Comparisons of cis-l^-Polydienes ............................485 11.5.5 Metallocene Catalysts .................................................487 11.6 Olefin Metathesis Catalysts ....................................................490 References .........................................................................................493 CHAPTER 12 Polymer Reaction Engineering 495 12.1 Scope .......................................................................................495 12.2 Step-Growth Polymerizations .................................................495 12.3 Chain-Growth Polymerizations ...............................................498 12.4 Homogeneous and Heterogeneous Polymerization Processes .................................................................................499 12.4.1 Homogeneous Systems ...............................................499 12.4.2 Heterogeneous Systems ..............................................501 12.5 Batch, Semibatch, and Continuous Processes ........................510 12.6 Polymerization Reactors .........................................................510 12.6.1 Batch Reactors ............................................................511 12.6.2 Tubular Reactors .........................................................512 12.6.3 Continuous Stirred Tank Reactors ..............................513 References .........................................................................................520 CHAPTER 13 Biopolymers...........................................................................521 13.1 Introduction .............................................................................521 13.2 Natural Polymers ................................................................. !...522 13.2.1 Natural Rubbers ..........................................................522 13.2.2 Polysacchandes ...........................................................523 13.3 Bio-Based Polymers (Bioplastics) ..........................................527 13.3.1 Extraction and Modification of Natural Polymers in Plants ......................................................527 13.3.2 Polymerization of Bio-monomers ..............................529 13.3.3 Production of Polymers by Microorganisms ..............530 13.4 Biopolymer Blends and Biocomposites .................................531 Contents xv 13.4.1 Biopolymer Blends..................................................... 531 13.4.2 Biocomposites.............................................................532 13.5 Future of Bioplastic Products .................................................532 References......................................................................................... 534 Appendix A ............................................................................................................537 Appendix В ............................................................................................................539 Index ......................................................................................................................549
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author	Rudin, Alfred Choi, Phillip
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dewey-hundreds	500 - Natural sciences and mathematics
dewey-ones	547 - Organic chemistry
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dewey-search	547.7
dewey-sort	3547.7
dewey-tens	540 - Chemistry and allied sciences
discipline	Chemie / Pharmazie Werkstoffwissenschaften Chemie Chemie-Ingenieurwesen
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genre_facet	Lehrbuch
id	DE-604.BV040798405
illustrated	Illustrated
indexdate	2024-07-10T00:34:06Z
institution	BVB
isbn	9780123821782
language	English
oai_aleph_id	oai:aleph.bib-bvb.de:BVB01-025778553
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physical	xx, 563 p. graph. Darst. 24 cm
publishDate	2013
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publisher	Elsevier/AP
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spelling	Rudin, Alfred Verfasser aut The elements of polymer science and engineering Alfred Rudin, Phillip Choi 3. ed. San Diego [u.a.] Elsevier/AP 2013 xx, 563 p. graph. Darst. 24 cm txt rdacontent n rdamedia nc rdacarrier Includes bibliographical references and index Polymers Polymerization Polymere (DE-588)4046699-1 gnd rswk-swf Polymerisation (DE-588)4046704-1 gnd rswk-swf Makromolekulare Chemie (DE-588)4168684-6 gnd rswk-swf (DE-588)4123623-3 Lehrbuch gnd-content Makromolekulare Chemie (DE-588)4168684-6 s DE-604 Polymere (DE-588)4046699-1 s 1\p DE-604 Polymerisation (DE-588)4046704-1 s 2\p DE-604 Choi, Phillip Verfasser aut Digitalisierung UB Regensburg application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=025778553&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis 1\p cgwrk 20201028 DE-101 https://d-nb.info/provenance/plan#cgwrk 2\p cgwrk 20201028 DE-101 https://d-nb.info/provenance/plan#cgwrk
spellingShingle	Rudin, Alfred Choi, Phillip The elements of polymer science and engineering Polymers Polymerization Polymere (DE-588)4046699-1 gnd Polymerisation (DE-588)4046704-1 gnd Makromolekulare Chemie (DE-588)4168684-6 gnd
subject_GND	(DE-588)4046699-1 (DE-588)4046704-1 (DE-588)4168684-6 (DE-588)4123623-3
title	The elements of polymer science and engineering
title_auth	The elements of polymer science and engineering
title_exact_search	The elements of polymer science and engineering
title_full	The elements of polymer science and engineering Alfred Rudin, Phillip Choi
title_fullStr	The elements of polymer science and engineering Alfred Rudin, Phillip Choi
title_full_unstemmed	The elements of polymer science and engineering Alfred Rudin, Phillip Choi
title_short	The elements of polymer science and engineering
title_sort	the elements of polymer science and engineering
topic	Polymers Polymerization Polymere (DE-588)4046699-1 gnd Polymerisation (DE-588)4046704-1 gnd Makromolekulare Chemie (DE-588)4168684-6 gnd
topic_facet	Polymers Polymerization Polymere Polymerisation Makromolekulare Chemie Lehrbuch
url	http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=025778553&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA
work_keys_str_mv	AT rudinalfred theelementsofpolymerscienceandengineering AT choiphillip theelementsofpolymerscienceandengineering

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