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| Preface | |
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| Introductory Concepts | |
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| Basic Definitions | |
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| Polymer | |
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| Monomer | |
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| Molecular Weight and Molar Mass | |
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| End Groups | |
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| Degree of Polymerization | |
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| Copolymers | |
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| Polymerization and Functionality | |
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| Polymerization Processes | |
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| Addition or Chain Polymerization | |
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| Step Polymerization | |
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| Supramolecular Polymerization | |
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| Molecular Architecture | |
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| Classification of Polymers | |
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| Thermoplastics and Thermosets | |
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| Plastics, Fibers, and Elastomers | |
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| Polymer Nomenclature | |
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| References | |
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| Exercises | |
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| Chain Dimensions, Structures, and Transitional Phenomena | |
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| Introduction | |
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| Polymer Chains: Structures and Dimensions | |
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| Conformational Changes | |
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| Polymer Conformations in Crystals | |
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| Polymer Size in the Amorphous State | |
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| Constitutional and Configurational Isomerism | |
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| Constitutional Isomerism | |
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| Configurational Isomerism | |
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| Crystallinity in Polymers | |
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| Structure of Bulk Polymers | |
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| Thermal Transitions in Polymers | |
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| T[subscript g] and T[subscript m] | |
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| First- and Second-Order Transitions | |
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| Regions of Viscoelastic Behavior | |
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| Factors Affecting T[subscript g] | |
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| Factors Affecting T[subscript m] | |
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| Relation Between T[subscript m] and T[subscript g] | |
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| Theoretical Treatment of Glass Transition | |
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| Quantitative Effects of Factors on T[subscript g] | |
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| Chain Movements in Amorphous State | |
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| The Reptation Model | |
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| Thermodynamics of Rubber Elasticity | |
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| Stress-Strain Behavior of Crosslinked Elastomers | |
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| Nonideal Networks | |
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| References | |
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| Exercises | |
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| Polymers in Solution | |
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| Introduction | |
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| Thermodynamics of Liquid Mixtures | |
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| Low-Molecular-Weight Mixtures: van Laar Model | |
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| Polymer-Solvent Mixtures: Flory-Huggins Model | |
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| Phase Equilibria in Poor Solvents | |
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| Upper and Lower Critical Solution Temperatures | |
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| Solubility Behavior of Polymers | |
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| Swelling of Crossslinked Polymers | |
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| Determination of x from Swelling | |
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| Frictional Properties of Polymer Molecules in Dilute Solution | |
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| Viscosity of Dilute Polymer Solutions | |
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| References | |
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| Exercises | |
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| Polymer Molecular Weights | |
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| Introduction | |
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| Molecular Weight Averages | |
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| Arithmetic Mean | |
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| Number-Average Molecular Weight | |
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| Weight-Average Molecular Weight | |
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| Molecular Weights in Terms of Moments | |
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| Ratio of First and Zeroth Moments | |
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| Ratios of Higher Moments | |
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| Molecular Weight Determination | |
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| End-Group Analysis | |
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| Colligative Property Measurement | |
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| Light-Scattering Method | |
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| Dilute Solution Viscometry | |
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| Gel Permeation Chromatography | |
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| References | |
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| Exercises | |
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| Condensation (Step-Growth) Polymerization | |
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| Introduction | |
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| Rates of Polycondensation Reactions | |
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| Irreversible Polycondensation Kinetics | |
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| Reversible Polycondensation Kinetics | |
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| Number-Average Degree of Polymerization | |
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| Control of Molecular Weight | |
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| Quantitative Effect of Stoichiometric Imbalance | |
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| Molecular Weight Distribution (MWD) | |
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| Breadth of MWD | |
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| Nonlinear Step Polymerization | |
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| Branching | |
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| Crosslinking and Gelation | |
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| Recursive Approach for Average Properties | |
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| Linear Step-Growth Polymerization | |
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| Nonlinear Step-Growth Polymerization | |
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| Post-gel Properties | |
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| Polycondensation of A[subscript x]B Monomers | |
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| Dendritic and Hyperbranched Polymers | |
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| References | |
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| Exercises | |
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| Free Radical Polymerization | |
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| Introduction | |
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| Scheme of Radical Chain Polymerization | |
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| Overall Scheme | |
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| Chain Initiation | |
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| Chain Propagation | |
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| Chain Termination | |
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| Rate of Polymerization | |
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| Overall Extent of Polymerization | |
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| Experimental Determination of R[subscript p]: Dilatometry | |
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| Methods of Initiation | |
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| Thermal Decomposition of Initiators | |
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| Redox Initiation | |
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| Photochemical Initiation | |
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| Initiation by High-Energy Radiations | |
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| Thermal Initiation in Absence of Initiator | |
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| Dead-End Polymerization | |
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| Determination of Absolute Rate Constants | |
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| Nonsteady-State Kinetics | |
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| Chain Length and Degree of Polymerization | |
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| Kinetic Chain Length | |
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| Mode of Chain Termination | |
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| Average Lifetime of Kinetic Chains | |
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| Chain Transfer | |
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| Degree of Polymerization | |
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| Chain Transfer to Polymer | |
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| Allylic Transfer | |
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| Deviations from Ideal Kinetics | |
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| Primary Radical Termination | |
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| Initiator-Monomer Complex Formation | |
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| Degradative Initiator Transfer | |
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| Autoacceleration | |
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| Inhibition/Retardation of Polymerization | |
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| Inhibition/Retardation Kinetics | |
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| Effects of Temperature | |
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| Rate of Polymerization | |
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| Degree of Polymerization | |
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| Polymerization-Depolymerization Equilibrium | |
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| Molecular Weight Distribution | |
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| Low-Conversion Polymerization | |
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| High-Conversion Polymerization | |
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| Polymerization Processes | |
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| Emulsion Polymerization | |
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| Photoemulsion Polymerization | |
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| "Grafting-from" Polymerization | |
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| Living Radical Polymerization | |
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| Reversible Termination by Coupling | |
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| Atom Transfer Radical Polymerization | |
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| Degenerative Chain Transfer | |
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| Reversible Addition-Fragmentation Chain Transfer | |
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| References | |
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| Exercises | |
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| Chain Copolymerization | |
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| Introduction | |
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| Binary Copolymer Composition - Terminal Model | |
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| Significance of Monomer Reactivity Ratios | |
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| Types of Copolymerization | |
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| Instantaneous Copolymer Composition | |
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| Integrated Binary Copolymer Equation | |
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| Evaluation of Monomer Reactivity Ratios | |
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| The Q-e Scheme | |
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| Sequence Length Distribution | |
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| Rate of Binary Free-Radical Copolymerization | |
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| Multicomponent Copolymerization: Terpolymerization | |
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| Deviations from Terminal Model | |
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| Penultimate Model | |
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| Complex-Participation Model | |
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| Copolymerization and Crosslinking | |
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| Vinyl and Divinyl Monomers of Equal Reactivity | |
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| Vinyl and Divinyl Monomers of Different Reactivities | |
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| One Group of Divinyl Monomer Having Lower Reactivity | |
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| Block and Graft Copolymerization | |
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| Block Copolymerization | |
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| Graft Copolymerization | |
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| References | |
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| Exercises | |
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| Ionic Chain Polymerization | |
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| Introduction | |
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| Ionic Polymerizability of Monomers | |
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| Anionic Polymerization | |
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| Anionic Initiation | |
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| Termination Reactions | |
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| Polymerization with Complete Dissociation of Initiator | |
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| Polymerization with Incomplete Dissociation of Initiator | |
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| Polymerization with Simultaneous Propagation and Termination | |
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| Anionic Copolymerization | |
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| Reactivity Groups | |
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| Block Copolymers | |
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| Cationic Polymerization | |
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| Cationic Initiation | |
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| Propagation of Cationic Chain | |
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| Chain Transfer and Termination | |
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| Kinetics | |
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| Molecular Weight Distribution | |
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| Cationic Copolymerization | |
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| References | |
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| Exercises | |
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| Coordination Addition Polymerization | |
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| Introduction | |
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| Ziegler-Natta Catalysts | |
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| Catalyst Composition | |
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| Nature of the Catalyst | |
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| Evolution of the Titanium-Aluminum System | |
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| Mechanism of Ziegler-Natta Polymerization | |
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| Mechanism of Stereospecific Placement | |
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| Bimetallic and Monometallic Mechanisms | |
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| Kinetics of Ziegler-Natta Polymerization | |
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| Typical Shapes of Kinetic Curves | |
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| Effect of Catalyst Particle Size | |
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| Chain Termination | |
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| Kinetic Models | |
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| Supported Metal Oxide Catalysts | |
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| Polymerization Mechanism | |
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| Ziegler-Natta Copolymerization | |
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| Metallocene-Based Ziegler-Natta Catalysts | |
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| Catalyst Composition | |
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| The Active Center | |
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| Polymerization Mechanism | |
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| Kinetic Models | |
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| Immobilized Metallocene Catalysts | |
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| Oscillating Metallocene Catalysts | |
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| References | |
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| Exercises | |
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| Ring-Opening Polymerization | |
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| Introduction | |
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| Polymerization Mechanism and Kinetics | |
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| Cyclic Ethers/Epoxides | |
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| Lactams | |
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| Lactones | |
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| References | |
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| Exercises | |
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| Conversion of Units | |
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| Fundamental Constants | |