Caneba Free-Radical Retrograde-Precipitation Polymerization (FRRPP)

Novel Concept, Processes, Materials, and Energy Aspects
1. Auflage 2010
ISBN: 978-3-642-03025-3
Verlag: Springer
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 310 Seiten

Providing insight on the free-radical retrograde-precipitation polymerization process, this volume examines the phenomenological aspects in comparison to other materials, such as nanoscale confinement behavior and nucleated hot spots.

Autoren/Hrsg.

Caneba, Gerard

Inhaltsverzeichnis

1;Preface;6
2;Contents;9
3;1 Background;13
3.1;1.1 Phase Separation Thermodynamics;16
3.1.1;1.1.1 Thermodynamics of Polymer Solutions;16
3.1.1.1;1.1.1.1 Flory--Huggins Theory;16
3.1.1.2;1.1.1.2 Flory--Prigogine--Patterson Equation-of-State Theory;18
3.1.2;1.1.2 Liquid--Liquid Phase Equilibria of Polymer Solutions;19
3.1.2.1;1.1.2.1 Binodal Equations;19
3.1.2.2;1.1.2.2 Spinodal Equations;20
3.1.2.3;1.1.2.3 Measurement of Binodal and Spinodal Curves;21
3.1.3;1.1.3 The LCST Phenomenon in Experimental Polymer/Small-Molecule Systems;24
3.1.3.1;1.1.3.1 LCST and the FRRPP Process;25
3.1.3.2;1.1.3.2 Measurement of LCST-Based Ternary Phase Diagrams Using Cloudpoint Experimentation;27
3.1.4;1.1.4 Nomenclature;34
3.1.4.1;1.1.4.1 Alphabet Symbols;34
3.1.4.2;1.1.4.2 Subscripts;35
3.1.4.3;1.1.4.3 Superscripts;35
3.1.4.4;1.1.4.4 Greek Symbols;35
3.2;1.2 Polymer Transport Processes;36
3.2.1;1.2.1 Fluid Flow;36
3.2.2;1.2.2 Heat Transfer;38
3.2.3;1.2.3 Diffusional Mass Transfer;40
3.2.4;1.2.4 Nomenclature;47
3.2.4.1;1.2.4.1 Alphabets;47
3.2.4.2;1.2.4.2 Subscripts;48
3.2.4.3;1.2.4.3 Superscripts;48
3.2.4.4;1.2.4.4 Greek Symbols;48
3.2.4.5;1.2.4.5 Other Symbols;48
3.3;1.3 Conventional Polymerization Kinetics and Processes;49
3.3.1;1.3.1 Free-Radical Kinetics;50
3.3.2;1.3.2 Polymerization Processes;56
3.3.3;1.3.3 Copolymerization Kinetics;58
3.3.4;1.3.4 Nomenclature;59
3.3.4.1;1.3.4.1 Alphabets;59
3.3.4.2;1.3.4.2 Subscripts;59
3.3.4.3;1.3.4.3 Superscripts;59
3.3.4.4;1.3.4.4 Greek Symbols;60
3.3.4.5;1.3.4.5 Other Symbols;60
3.4;1.4 Phase Separation Kinetics in Nonreactive Polymer Systems;60
3.4.1;1.4.1 Phase Separation Mechanisms;60
3.4.1.1;1.4.1.1 Nucleation and Growth;62
3.4.1.2;1.4.1.2 Spinodal Decomposition;62
3.4.1.3;1.4.1.3 Coarsening;63
3.4.2;1.4.2 Mathematical Modeling of Structure Evolution in Phase Separating Polymer Systems;63
3.4.2.1;1.4.2.1 Binary Polymer/Solvent Systems;64
3.4.2.2;1.4.2.2 Ternary System;73
3.4.3;1.4.3 Experimental Efforts;76
3.4.3.1;1.4.3.1 Light Scattering Studies;77
3.4.3.2;1.4.3.2 Morphological Studies;83
3.4.4;1.4.4 Determination of Phenomenological Diffusivities from Numerical and Experimental Data;98
3.4.5;1.4.5 Nomenclature;100
3.4.5.1;1.4.5.1 Alphabets;100
3.4.5.2;1.4.5.2 Subscripts;101
3.4.5.3;1.4.5.3 Superscripts;101
3.4.5.4;1.4.5.4 Greek Symbols;101
3.4.5.5;1.4.5.5 Other Symbols;101
3.5;1.5 Phase Separation Kinetics in Reactive Polymer Systems;101
3.5.1;1.5.1 Derivation of the Spinodal Decomposition Equation with the Reaction Term;102
3.5.2;1.5.2 Numerical Simulation for Reactive Polymer Phase Separation Systems;104
3.5.2.1;1.5.2.1 Microscopic Calculation;106
3.5.2.2;1.5.2.2 Macroscopic Calculation;106
3.5.3;1.5.3 Results and Discussion;107
3.5.4;1.5.4 Nomenclature;108
3.5.4.1;1.5.4.1 Alphabets;108
3.5.4.2;1.5.4.2 Subscripts;109
3.5.4.3;1.5.4.3 Superscripts;109
3.5.4.4;1.5.4.4 Greek Symbols;110
3.5.4.5;1.5.4.5 Other Symbols;110
3.6;References;110
4;2 The FRRPP Concept;114
4.1;2.1 Connection to Nanotechnology;114
4.1.1;2.1.1 Formation of Reactive Polymer Nanoparticles;115
4.1.2;2.1.2 Agglomeration of Nanoparticles in a Stirred Vessel;118
4.1.3;2.1.3 Light Scattering;120
4.1.4;2.1.4 Proton and 13 C-NMR Studies;121
4.1.5;2.1.5 IR Imaging Study;123
4.1.6;2.1.6 Coil-to-Globule Transition;127
4.2;2.2 Local Heating and Energy Analysis of the FRRPP Process;128
4.2.1;2.2.1 Notional Concept;128
4.2.2;2.2.2 Case Studies;129
4.2.2.1;2.2.2.1 Case 1 -- Pressure Control Stirred-Tank Batch Reactor;129
4.2.2.2;2.2.2.2 Case 2 -- Mathematical Modeling of Hot Spots in Precipitation Polymerization Systems;132
4.2.3;2.2.3 Energy Analysis of Cases 1--2;135
4.2.3.1;2.2.3.1 Adiabatic Temperature Rise;135
4.2.3.2;2.2.3.2 Actual Overall Reactive Particle Temperature;136
4.2.3.3;2.2.3.3 Carbonization Temperatures;136
4.2.3.4;2.2.3.4 Data Interpretation;136
4.2.4;2.2.4 Glass Tube Reactor Experiment with Release of Reaction Fluid;137
4.2.4.1;2.2.4.1 Experimental Setup;137
4.2.4.2;2.2.4.2 Procedure;137
4.2.4.3;2.2.4.3 Results and Discussion;138
4.2.5;2.2.5 Nomenclature;141
4.2.5.1;2.2.5.1 Alphabets;141
4.2.5.2;2.2.5.2 Subscripts;141
4.2.5.3;2.2.5.3 Superscripts;141
4.2.5.4;2.2.5.4 Greek Symbols;142
4.2.5.5;2.2.5.5 Other Symbols;142
4.3;2.3 FRRPP Polymerization Kinetics;142
4.3.1;2.3.1 Polystyrene/Styrene-Based FRRPP Systems;142
4.3.1.1;2.3.1.1 Phase Diagram Results;142
4.3.1.2;2.3.1.2 Conversion and Molecular Weight Distributions;143
4.3.1.3;2.3.1.3 Studies of Radical Populations;152
4.3.2;2.3.2 Poly(Methacrylic Acid)/Methacrylic Acid/Water System;155
4.3.2.1;2.3.2.1 Results;155
4.3.2.2;2.3.2.2 Discussion of Results;158
4.4;2.4 Predictions of FRRPP Behavior Through the CoilGlobule Transition;159
4.4.1;2.4.1 Thermodynamics of Ternary Polystyrene/Styrene/Ether System;161
4.4.2;2.4.2 Mass Transport Phenomena;162
4.4.3;2.4.3 Calculation of Kinetic Parameters and Polymer Formation Behavior;166
4.4.4;2.4.4 Thermal Analysis;169
4.4.5;2.4.5 Nomenclature;173
4.4.5.1;2.4.5.1 Alphabets;173
4.4.5.2;2.4.5.2 Subscripts;174
4.4.5.3;2.4.5.3 Superscripts;174
4.4.5.4;2.4.5.4 Greek Symbols;174
4.4.5.5;2.4.5.5 Other Symbols;174
4.5;2.5 Physicochemical Quantitative Description of FRRPP;175
4.5.1;2.5.1 Nomenclature;181
4.5.1.1;2.5.1.1 Alphabets;181
4.5.1.2;2.5.1.2 Subscripts;181
4.5.1.3;2.5.1.3 Superscripts;181
4.5.1.4;2.5.1.4 Greek Symbols;181
4.5.1.5;2.5.1.5 Other Symbols;181
4.6;References;182
5;3 Polymerization Processes;184
5.1;3.1 Statistical Polymerizations (Homopolymerizations and Multipolymerizations);184
5.1.1;3.1.1 Introduction;184
5.1.2;3.1.2 Theory;185
5.1.2.1;3.1.2.1 Statistical Effects of Reactivity Ratios;185
5.1.2.2;3.1.2.2 Effects of Phase Behavior;186
5.1.3;3.1.3 Experimental;187
5.1.3.1;3.1.3.1 S/AA System;187
5.1.3.2;3.1.3.2 VA/AA System;188
5.1.4;3.1.4 Results and Discussion;190
5.1.4.1;3.1.4.1 S/AA System;190
5.1.4.2;3.1.4.2 VA/AA System;192
5.1.5;3.1.5 Nomenclature;197
5.1.5.1;3.1.5.1 Alphabets;197
5.1.5.2;3.1.5.2 Subscripts;197
5.1.5.3;3.1.5.3 Superscripts;199
5.1.5.4;3.1.5.4 Greek Symbols;199
5.1.5.5;3.1.5.5 Other Symbols;199
5.2;3.2 Staged Multipolymerizations;199
5.2.1;3.2.1 Straightforward Addition of Another Monomer(s);200
5.2.2;3.2.2 Interstage Rapid Cooling Method;201
5.2.3;3.2.3 Emulsion FRRPP;203
5.2.4;3.2.4 Emulsification of First-Stage Radicals;203
5.2.5;3.2.5 Radicalized Polymer Particulates;206
5.3;References;209
6;4 Product Materials;210
6.1;4.1 Homopolymers and Statistical Multipolymers;210
6.1.1;4.1.1 Homopolymers;210
6.1.1.1;4.1.1.1 Polystyrene (PS);210
6.1.1.2;4.1.1.2 Poly(methacrylic acid) (PMAA);213
6.1.1.3;4.1.1.3 Poly(vinylidene chloride) (PVDC);213
6.1.2;4.1.2 Statistical Multipolymers;214
6.1.2.1;4.1.2.1 PS-Based Statistical Multipolymers;214
6.1.2.2;4.1.2.2 VDC-Based Statistical Multipolymers;217
6.1.2.3;4.1.2.3 Poly(vinyl acetate)-Based Statistical Multipolymers;218
6.2;4.2 Block Multipolymers;220
6.3;4.3 Reactive Polymer Intermediates;224
6.3.1;4.3.1 PS-Based Intermediates;224
6.3.2;4.3.2 VDC Copolymer-Based Intermediates;225
6.3.3;4.3.3 VA/AA-Based Intermediates;233
6.4;4.4 Polymer Surfactants;234
6.5;4.5 Polymer Foams from the FRRPP Process;239
6.5.1;4.5.1 Vinyl Acetate-Acrylic Acid Copolymer Foams;239
6.5.2;4.5.2 Vinylidene Chloride Copolymer-Based Foams;239
6.5.3;4.5.3 VDC Multipolymer Nanocomposites in Polyurethane Foams;245
6.6;4.6 Coatings;249
6.6.1;4.6.1 Polystyrene-Poly(Dimethyl Siloxane) (PS--PDMS) Coatings;249
6.6.2;4.6.2 VA/AA with SWCNTs;255
6.7;4.7 Bottom-Up Micropatterning of Polymers;258
6.8;References;261
7;5 Related Energy Application of FRRPP Products;263
7.1;5.1 Surfactant-Based Waterflooding for Subterranean Oil Recovery;263
7.1.1;5.1.1 Introduction;263
7.1.2;5.1.2 Theory;271
7.1.3;5.1.3 Experimental;271
7.1.3.1;5.1.3.1 Sandpack Oil Recovery Studies;271
7.1.3.2;5.1.3.2 Core Rock Study;273
7.1.4;5.1.4 Results and Discussion;273
7.2;5.2 Foamflooding Subterranean Enhanced Oil Recovery;275
7.2.1;5.2.1 Introduction;275
7.2.2;5.2.2 Experimental;277
7.2.3;5.2.3 Results and Discussion;277
7.3;5.3 Bitumen Recovery from Surface Sources;282
7.3.1;5.3.1 Introduction;282
7.3.2;5.3.2 Experimental;283
7.3.2.1;5.3.2.1 Extraction of Heavy Crude Oil from Standard Sand;283
7.3.2.2;5.3.2.2 Tar Sands Studies;284
7.3.3;5.3.3 Results and Discussion;284
7.4;References;289
8;6 Outlook;291
8.1;6.1 Polymers for Defense and Homeland Security;291
8.1.1;6.1.1 Labeled Surfactants;291
8.1.2;6.1.2 Specialty Surfaces;294
8.1.3;6.1.3 Other Applications;296
8.2;6.2 Conceptual Connections to Nuclear Material Systems;297
8.2.1;6.2.1 Energy-Producing Isotopes;297
8.2.2;6.2.2 Nuclear Waste Materials;300
8.3;6.3 Fuel Cell Membranes;303
8.3.1;6.3.1 Proton Exchange Membrane (PEM) Fuel Cells;303
8.3.2;6.3.2 Hydroxide Exchange Membrane Alkali Fuel Cells (HEMFCs);304
8.4;6.4 Medical Applications;305
8.4.1;6.4.1 Nanoparticle Polymers;305
8.4.1.1;6.4.1.1 Homogeneous Polymer Nanoparticles;305
8.4.1.2;6.4.1.2 Heterogeneous Nanoparticles;305
8.4.2;6.4.2 Patterned Polymers;306
8.5;References;306
9;Appendix;308
10;Index;315