Polymer Science, Engineering, and Sustainability, 2 Volume Set

Chapter 1: Introduction to Polymers and Polymer Types

• • 1.1 Introduction to Polymers
• • 1.1.1 Basic Concepts
• • 1.1.2 History
• • 1.1.3 Mechanical and Rheological Properties
• • 1.1.3.1 Mechanical Properties
• • 1.1.3.2 Rheological Properties
• • 1.1.4 Polymer States
• • 1.1.5 Molecular Weight
• • 1.1.5.1 Moments of the Molar Mass Distribution
• • 1.1.6 Main Types and Uses
• • 1.2 Classification of Polymers
• • 1.2.1 Classification Based on Structure
• • 1.2.2 Classification Based on Mechanism
• • 1.2.2.1 Step-Growth Polymerization (SGP)
• • 1.2.2.2 Chain or Chain-growth Polymerization (CP)
• • 1.2.3 Classification by Chain Topology
• • 1.2.4 Other Classification Criteria
• • 1.2.4.1 Homo and Copolymers
• • 1.2.4.2 Origin
• • 1.2.4.3 Biodegradability and Sustainability
• • 1.2.4.4 Production Volume
• • 1.3 Nomenclature
• • 1.3.1 Conventional Nomenclature
• • 1.3.2 IUPAC Structure-based Nomenclature
• • 1.3.3 Trade, Common Names, and Abbreviations
• • 1.4 Further Reading

Chapter 2: Polycondensation

• • 2.1 Introduction
• • 2.1.1 General Principles
• • 2.1.2 Number-Average Degree of Polymerization
• • 2.1.3 Molecular Weight Distribution
• • 2.1.4 Polymers Obtained by Polycondensation Polymerization
• • 2.2 Polycondensation Kinetics
• • 2.3 Polyamides
• • 2.3.1 Polyamidation
• • 2.3.2 Aromatic Polyamides
• • 2.4 Polyimides
• • 2.5 Polyesters
• • 2.5.1 Polyesters from Diols
• • 2.5.2 Polyethers
• • 2.5.3 Polyurethanes
• • 2.5.4 Polyureas
• • 2.5.5 Polycarbonates
• • 2.5.6 Polysulfones
• • 2.5.7 Polybenzimidazole
• • 2.5.8 Depolymerization and Recycling
• • 2.6 Inorganic Condensation Polymers
• • 2.6.1 Polysiloxanes
• • 2.6.2 Polysilanes
• • 2.6.3 Polyphosphazenes
• • 2.7 Dendrimers
• • 2.8 Thermoset Polycondensation Polymers
• • 2.8.1 Polyester Resins
• • 2.8.2 Epoxy Resins
• • 2.8.3 Alkyd Resins
• • 2.8.4 Phenolic Resins
• • 2.8.5 Urea-Formaldehyde Resins
• • 2.9 Bio-based Step-Growth Polymers
• • 2.10 Bio-based Polycondensation Polymers
• • 2.10.1 Dicarboxylic Acids and Diols
• • 2.10.2 Hydroxy Acids and Hydroxyl Esters
• • 2.10.3 Amino Acids and Lactams
• • 2.10.4 Diamines
• • 2.11 Controlled Molecular Weight Condensation Polymers
• • 2.11.1 Solid Phase Synthesis
• • 2.11.2 Use of Macromonomers in Condensation Reactions

Chapter 3: Free-Radical Polymerization

• • 3.1 Introduction
• • 3.2 Basic Mechanism
• • 3.2.1 Chemical Initiation
• • 3.2.2 Propagation
• • 3.2.3 Termination
• • 3.3 Other Free Radical Reactions
• • 3.3.1 Chain Transfer to Small Species
• • 3.3.2 Chain Transfer to Monomer
• • 3.3.3 Chain Transfer to Initiator
• • 3.3.4 Chain Transfer to Solvent and Chain Transfer Agents
• • 3.3.5 Chain Transfer to Impurities
• • 3.3.6 Chain Transfer to Polymer
• • 3.3.7 Backbiting
• • 3.3.8 Reactions to Internal and Terminal Double Bonds and Crosslinking
• • 3.3.9 Inhibition
• • 3.4 Kinetics and Polymerization Rate
• • 3.4.1 Diffusion-Controlled (DC) Effects
• • 3.5 Molecular Weight and Molecular Weight Distribution
• • 3.5.1 Full Molecular Weight Distribution
• • 3.6 Experimental Determination of Rate Constants
• • 3.7 Thermodynamics of Polymerization

Chapter 4: Reversible-Deactivation Radical Polymerization (RDRP)

• • 4.1 Introduction to RDRP
• • 4.1.1 Terminology for RDRP
• • 4.1.1.1 RDRP with Unimolecular Activation – Stable radical-mediated Polymerization
• • 4.1.1.2 RDRP with Bimolecular Activation – Atom-Transfer Radical Polymerization
• • 4.1.1.3 RDRP with Activation by Degenerative Chain Transfer – Degenerative Chain-Transfer Radical Polymerization
• • 4.1.1.4 Multiple Mechanism RDRP
• • 4.2 Nitroxide-Mediated Polymerization (NMP)
• • 4.2.1 Historical Background
• • 4.2.2 Polymer Chemistry of NMP
• • 4.2.2.1 Mechanistic Aspects and Chemical Routes
• • 4.2.2.2 Nitroxides Most Commonly Used
• • 4.2.2.3 Structure Control and Macromolecular Architectures
• • 4.2.3 A Polymer Reaction Engineering (PRE) View of NMP
• • 4.2.3.1 Kinetics and Mathematical Modeling
• • 4.2.3.2 Dispersed-Phase Polymerizations
• • 4.2.3.3 NMP in scCO2
• • 4.2.3.4 Continuous NMP
• • 4.2.4 Applications and Perspectives
• • 4.2.5 Closing Remarks
• • 4.3 Atom-Transfer Radical Polymerization (ATRP)
• • 4.3.1 Normal ATRP
• • 4.3.2 ATRP Variants
• • 4.3.3 Future Outlook
• • 4.4 Reversible-Addition-Fragmentation Chain-Transfer Polymerization (RAFT)
• • 4.4.1 RAFT Mechanism
• • 4.4.2 Monomers in RAFT Polymerization
• • 4.4.3 Initiation and Termination in RAFT Polymerization
• • 4.4.4 RAFT Agents
• • 4.4.4.1 Z Group Selection
• • 4.4.4.2 R Group Selection
• • 4.4.4.3 Other Considerations in RAFT Agent Selection
• • 4.4.5 Sequence-defined Oligomers
• • 4.4.6 (Multi)Block Copolymer Synthesis
• • 4.4.7 Star Synthesis
• • 4.5 Other RDRP Systems
• • 4.5.1 Degenerative Transfer Controlled Radical Polymerization Mediated by Organotellurium (TERP)
• • 4.5.2 Degenerative Transfer RDRP Mediated by Organostibine (SBRP) and Organobismuthine (BIRP)
• • 4.5.3 Iodine Transfer Polymerization (ITP) and Variants
• • 4.5.4 Reversible Chain-Transfer Catalyzed Polymerization (RTCP)
• • 4.5.5 Organometallic Mediated Radical Polymerization
• • 4.6 RDRP in Aqueous Dispersions
• • 4.6.1 Introduction
• • 4.6.2 Nitroxide-mediated Polymerization (NMP)
• • 4.6.2.1 Emulsion Polymerization
• • 4.6.2.2 Miniemulsion Polymerization
• • 4.6.2.3 Microemulsion Polymerization
• • 4.6.3 Atom-Transfer Radical Polymerization (ATRP)
• • 4.6.3.1 Emulsion Polymerization
• • 4.6.3.2 Miniemulsion Polymerization
• • 4.6.3.3 Microemulsion Polymerization
• • 4.6.4 Reversible-Addition-Fragmentation Chain-Transfer (RAFT) Polymerization
• • 4.6.4.1 Emulsion Polymerization
• • 4.6.4.2 Miniemulsion Polymerization
• • 4.6.4.3 Microemulsion Polymerization
• • 4.6.5 Tellurium-Mediated Radical Polymerization (TERP)
• • 4.6.6 Iodine Transfer Polymerization
• • 4.6.7 Concluding Remarks

Chapter 5: Coordination Polymerization

• • 5.1 Introduction
• • 5.2 Polyolefin Types
• • 5.3 Catalysts Types
• • 5.3.1 Phillips Catalyst
• • 5.3.2 Classical Ziegler–Natta Catalysts
• • 5.3.2.1 Conjugated and Nonconjugated Dienes Polymerizations
• • 5.3.3 Single-Site Catalysts
• • 5.3.3.1 Metallocenes and Constrained Geometry Catalysts
• • 5.3.3.2 Nonmetallocene Early Transition Metal-Based SSCs
• • 5.3.3.3 Late Transition Metal Catalysts
• • 5.3.3.4 Supported Single-Site Catalysts
• • 5.4 Coordination Polymerization Mechanism
• • 5.5 Polymerization Kinetics and Mathematical Modeling
• • 5.5.1 Polymer Microstructural Models
• • 5.6 Modeling Particle-Scale Phenomena
• • 5.7 Polymerization Reactor Models

Chapter 6: Copolymerization

• • 6.1 Introduction
• • 6.1.1 What Are Copolymers?
• • 6.1.2 Commercial Copolymer Examples
• • 6.1.2.1 Step-Growth Copolymerization
• • 6.2 Types of Copolymers
• • 6.2.1 Statistical Copolymers
• • 6.2.2 Alternating Copolymers
• • 6.2.3 Block Copolymers
• • 6.2.4 Gradient Copolymers
• • 6.2.5 Graft Copolymers
• • 6.2.6 Notes on Nomenclature
• • 6.3 Copolymer Composition and Microstructure
• • 6.3.1 Terminal Model Kinetics
• • 6.3.1.1 Copolymer Composition Behavior
• • 6.3.2 Other Copolymerization Models
• • 6.3.2.1 Penultimate Model
• • 6.3.2.2 Depropagation Models
• • 6.3.2.3 Models Involving the Participation of Complexes
• • 6.3.2.4 Model Discrimination
• • 6.3.3 Reactivity Ratio Estimation
• • 6.3.4 Sequence Length Distribution
• • 6.3.5 Composition Measurement Methods
• • 6.3.6 Extensions to Multicomponent Copolymerization
• • 6.4 Reaction Condition Considerations
• • 6.4.1 Copolymerization Rate
• • 6.4.2 Effect of Temperature
• • 6.4.3 Reaction Medium
• • 6.4.4 Monomer Concentration Effects
• • 6.4.5 Effect of Pressure
• • 6.4.6 Achieving Uniform Copolymer Composition
• • 6.4.6.1 Policy I
• • 6.4.6.2 Policy II
• • 6.5 Reversible-Deactivation Radical Copolymerization (RDRcoP)
• • 6.5.1 Reactivity Ratios for Linear Structures
• • 6.5.2 Conventional Copolymerizations and RDRcoP Leading to Nonlinear Structures (Effect of Branching and Cross linking)
• • 6.6 Copolymerization Systems Including Bio-Based Monomers

Chapter 7: Anionic Polymerization

• • 7.1 Introduction
• • 7.2 Living Anionic Polymerization
• • 7.2.1 Molecular Weight Control
• • 7.2.2 Molecular Weight Distribution
• • 7.3 General Considerations
• • 7.3.1 Monomers
• • 7.3.2 Solvents
• • 7.3.3 Initiators
• • 7.3.4 Initiation by Electron Transfer Alkali Metals
• • 7.3.4.1 Radical Anions
• • 7.3.5 Initiation by Nucleophilic Addition
• • 7.3.5.1 Alkyllithium Compounds
• • 7.3.5.2 Organoalkali Initiators
• • 7.3.5.3 Organoalkaline Earth Initiators
• • 7.3.5.4 Ate Complexes
• • 7.3.5.5 Difunctional Initiators
• • 7.3.5.6 Functionalized Initiators
• • 7.3.5.7 1,1-Diphenylmethyl Carbanions
• • 7.4 Kinetics and Mechanism of Polymerization