Synthesis and Applications of Copolymers

Understanding the reactivity of monomers is crucial in creating copolymers and determining the outcome of copolymerization. Covering the fundamental aspects of polymerization, Synthesis and Applications of Copolymers explores the reactivity of monomers and reaction conditions that ensure that the newly formed polymeric materials exhibit desired properties. Referencing a wide-range of disciplines, the book provides researchers, students, and scientists with the preparation of a diverse variety of copolymers and their recent developments, with a particular focus on copolymerization, crystallization, and techniques like nanoimprinting and micropatterning.

Table of Contents:
Preface xii Contributors xv SECTION I SYNTHESIS OF COPOLYMERS 1 1 Trends in Synthetic Strategies for Making (CO)Polymers 3 Anbanandam Parthiban 1.1 Background and Introduction, 3 1.2 Significance of Control Over Arrangement of Monomers in Copolymers, 5 1.3 Chain-Growth Condensation Polymerization, 5 1.3.1 Sequential Self-Repetitive Reaction (SSRR), 6 1.3.2 Poly(phenylene Oxide)s by Chain-Growth Condensation Polymerization, 8 1.3.3 Hydroxybenzoic Acids as AA′ Type Monomer in Nucleophilic Aliphatic Substitution Polymerization, 8 1.4 Sequence-Controlled Polymerization, 9 1.4.1 Sequence-Controlled Copolymers of N-Substituted Maleimides, 10 1.4.2 Alternating Copolymers by Ring-Opening Polymerization, 10 1.4.3 Selective Radical Addition Assisted by a Template, 11 1.4.4 Alternating AB-Type Sequence-Controlled Polymers, 11 1.4.5 Metal-Templated ABA Sequence Polymerization, 11 1.4.6 Sequence-Controlled Vinyl Copolymers, 12 1.4.7 Sequence-Regulated Polymerization Induced by Dual-Functional Template, 13 1.5 Processing of Thermoset Polymers: Dynamic Bond Forming Processes and Self-Healing Materials, 13 1.5.1 Plasticity of Networked Polymers Induced by Light, 14 1.5.2 Radically Exchangeable Covalent Bonds, 14 1.5.3 Self-Repairing Polyurethane Networks, 15 1.5.4 Temperature-Induced Self-Healing in Polymers, 15 1.5.5 Diels–Alder Chemistry at Room Temperature, 15 1.5.6 Trithiocarbonate-Centered Responsive Gels, 16 1.5.7 Shuffling of Trithiocarbonate Units Induced by Light, 16 1.5.8 Processable Organic Networks, 17 1.6 Miscellaneous Developments, 17 1.6.1 Atom Transfer Radical Polymerization (ATRP) Promoted by Unimolecular Ligand-Initiator Dual-Functional Systems (ULIS), 17 1.6.2 Unsymmetrical Ion-Pair Comonomers and Polymers, 20 1.6.3 Imidazole-Derived Zwitterionic Polymers, 21 1.6.4 Post-Modification of Polymers Bearing Reactive Pendant Groups, 22 1.7 Conclusion, 23 References, 24 2 Functional Polyolefins from the Coordination Copolymerization of Vinyl Monomers 29 Fabio Di Lena and Jõao A. S. Bomfim 2.1 Molecular Aspects of Olefin Coordination to Metals, 29 2.2 Fundamentals of Homopolymerization of Alkenes, 30 2.3 Copolymerization of Ethene and other Alkenes, 34 2.4 Copolymerization of Alkenes and Carbon Monoxide, 35 2.5 Copolymerization of Alkenes and Polar Vinyl Monomers, 37 2.5.1 Migratory Insertion Polymerization, 37 2.5.2 Polymerization via a Dual Radical/Migratory Insertion Pathway, 40 2.5.3 Coordinative Group Transfer Polymerization, 41 2.6 Copolymerization of Polar Vinyl Monomers and Carbon Monoxide, 41 2.7 Why are Phosphine–Sulfonate Ligands so Special? 43 2.8 Telechelic and End-Capped Macromolecules, 44 2.9 On the Use of Chemoinformatics for a More Rapid Development of the Field, 44 2.10 Conclusion and Outlook, 45 References, 46 3 General Aspects of Copolymerization 54 Alex Van Herk 3.1 Copolymerization in Chain Reactions, 54 3.1.1 Derivation of the Copolymerization Equation, 55 3.1.2 Types of Copolymers, 57 3.1.3 Polymerization Rates in Copolymerizations, 59 3.2 Measuring Copolymerization Parameters, 60 3.3 Influence of Reaction Conditions, 63 3.4 Short-Chain Effects in Copolymerization, 63 3.5 Synthesis of Block Copolymers With Controlled Chain Architecture, 64 References, 66 4 Polymers Bearing Reactive, Pendant Cyclic Carbonate (CC) Group: Syntheses, Post-Polymerization Modifications, and Applications 67 Satyasankar Jana 4.1 Introduction, 67 4.2 Cyclic Carbonate (CC) Monomers and Polymers, 68 4.2.1 Cyclic Carbonate (CC) Monomers and Their Synthesis, 68 4.2.2 Polymerization of Cyclic Carbonate (CC) Monomers, 75 4.2.3 Alternative Route to Synthesize Pendant CC (Co)polymers by CO2 Addition/Fixation Reaction, 83 4.3 Chemical Modification of Pendant CC Polymers, 85 4.4 Applications of Pendant CC Polymers, 88 4.4.1 Fixing CO2 into Polymer, 88 4.4.2 Surface Coating, 90 4.4.3 Solid or Gel Polymer Electrolyte for Lithium-Ion Batteries, 90 4.4.4 Enzyme Immobilization, 91 4.4.5 Photopolymerization, 91 4.4.6 Polymer Blends, 92 4.5 Conclusion, 92 References, 93 5 Monomers and Polymers Derived from Renewable or Partially Renewable Resources 101 Anbanandam Parthiban 5.1 Building Blocks from Renewable Resources, 101 5.2 Polyesters Incorporated with Isosorbide, 105 5.2.1 Poly(hydroxy ester)s Derived from Macrolides, 106 5.2.2 Semicrystalline Polymers from Fatty Acids, 107 5.2.3 Cyclic Ester Derived from a Natural Precursor, 107 5.2.4 Polymerization of Dilactone Derived from 12-Hydroxy Stearic Acid, 107 5.2.5 Thermoplastic Elastomers Derived from Polylactide and Polymenthide, 108 5.3 Rosin and Developments Associated with Rosin, 110 5.3.1 Polyamides and Polyesters Derived from Modified Levopimeric Acid, 110 5.3.2 Radical Polymerization of Modified Dehydroabietic Acid, 112 5.3.3 ATRP of Vinyl Monomers Derived from Dehydroabietic Acid, 112 5.3.4 Block Copolymers Derived from Dehydroabietic Acid Derivative, 112 5.4 Polyurethanes from Vegetable Oils, 113 5.4.1 Polyurethanes Derived from Plant Oil Triglycerides, 114 5.4.2 Long-Chain Unsaturated Diisocyanates Derived from Fatty Acids of Vegetable Origin, 114 5.5 CO2 as Renewable Resource Comonomer, 115 5.6 Renewable Triblock Copolymer-Based Pressure-Sensitive Adhesives (PSA), 115 5.7 Photocurable Renewable Resource Polyester, 116 5.8 Renewable Resource-Derived Waterborne Polyesters, 116 5.8.1 Polyesters Made Up of Isosorbide and Succinic Acid, 117 5.8.2 Polyesters Modified with Citric Acid, 117 5.9 Polymers Formed by Combining Renewable Resource Monomers with that Derived from Petroleum Feedstock, 117 5.10 Conclusion and Outlook, 120 References, 121 6 Microporous Organic Polymers: Synthesis, Types, and Applications 125 Shujun Xu and Bien Tan 6.1 Introduction, 125 6.2 Preparations of MOPS, 126 6.2.1 Polymers of Intrinsic Microporosity, 126 6.2.2 Hypercrosslinked Polymer, 132 6.2.3 Covalent Organic Frameworks, 134 6.2.4 Conjugated Microporous Polymers, 138 6.3 Hydrogen Adsorption, 141 6.3.1 HCPs for Hydrogen Adsorption, 142 6.3.2 PIMs for Hydrogen Adsorption, 144 6.3.3 COFs for Hydrogen Adsorption, 145 6.3.4 CMPs for Hydrogen Adsorption, 145 6.4 Carbon Dioxide Capture, 145 6.5 Separations, 149 6.5.1 HCPs for Separations, 150 6.5.2 PIMs for Separations, 153 6.5.3 CMPs for Separations, 153 6.6 Catalysis, 153 6.7 Prospect, 155 References, 156 7 Dendritic Copolymers 165 Srinivasa Rao Vinukonda 7.1 Introduction, 165 7.2 Synthesis Approaches or Strategies, 166 7.2.1 AB2 + A2 Approach, 166 7.2.2 AB2 + AB Approach, 167 7.2.3 B3 + A2 + B2 Approach (Biocatalyst), 167 7.2.4 Macromonomers Approach, 167 7.2.5 Dendrigraft Approach, 171 7.2.6 Linear–Dendritic Copolymers, 173 7.2.7 Living Anionic Polymerization, 178 7.2.8 Controlled Living Radical Polymerization, 185 7.2.9 Click Chemistry, 194 7.3 Properties of Dendritic Copolymers, 198 7.3.1 Molecular Weight and Molecular Weight Distribution, 198 7.3.2 Degree of Branching (DB), 200 7.3.3 Intrinsic Viscosity, 202 7.4 Applications of Dendritic Copolymers, 203 References, 204 SECTION II APPLICATIONS OF COPOLYMERS 215 8 A New Class of Ion-Conductive Polymer Electrolytes: CO2/Epoxide Alternating Copolymers With Lithium Salts 217 Yoichi Tominaga 8.1 Introduction, 217 8.2 Experimental, 220 8.2.1 Preparation of Monomers and Catalyst, 220 8.2.2 Copolymerization of Epoxides with CO2, 220 8.2.3 Preparation of Electrolyte Membranes, 222 8.2.4 Measurements, 222 8.3 Results and Discussion, 222 8.3.1 NMR Characterization, 222 8.3.2 Characteristics of Polycarbonates, 224 8.3.3 Thermal Analysis of Polycarbonates, 225 8.3.4 Impedance Measurement of Copolymers, 228 8.3.5 FT-IR Measurement, 231 8.3.6 PEC System: Effect of Salt Concentration, 232 8.4 Conclusion, 235 References, 236 9 Block Copolymer Nanopatterns as Enabling Platforms for Device Applications—Status, Issues, and Challenges 239 Sivashankar Krishnamoorthy 9.1 Introduction, 239 9.2 Block Copolymer Templates for Pattern Transfer Applications, 240 9.2.1 Dimensional Scalability and Fine-Tunability Down to Sub-10 nm Length Scales, 240 9.2.2 Directing Self-Assembly of Block Copolymers, 241 9.2.3 Block Copolymers for Directed Nanoscale Synthesis and Self-Assembly, 244 9.2.4 High Resolution Nanolithography, 244 9.2.5 Nanomanufacturing Material Patterns for Applications, 245 9.2.6 Top-Down Patterning of Block Copolymer Nanostructures, 249 9.3 Specific Instances in Exploitation of Block Copolymers in Device Applications, 251 9.3.1 Memory Devices, 251 9.3.2 Integrated Circuit Elements, 254 9.3.3 Photovoltaic and Optoelectronics Applications, 255 9.3.4 Sensors, 256 9.3.5 Nanoporous Membranes for Size-Exclusive Filtration or Sensing, 261 9.4 Conclusions, 263 References, 263 10 Stimuli-Responsive Copolymers and Their Applications 274 He Tao 10.1 Introduction, 274 10.2 Temperature-Responsive Copolymers and Applications, 275 10.2.1 Temperature-Responsive Copolymers Based on LCST, 276 10.3 pH-Responsive Copolymers and Applications, 284 10.3.1 pH-Responsive Segments, 285 10.3.2 Polymer Nanoparticles/Micelles Prepared from pH-Responsive Copolymers, 287 10.3.3 pH-Responsive Surfaces and Hydrogels, 287 10.3.4 Typical Applications of pH-Responsive Copolymers, 289 10.4 Biologically Responsive Copolymers and Applications, 290 10.4.1 Glucose-Responsive Copolymers and Applications, 290 10.5 Field-Responsive Copolymers and Applications, 293 10.5.1 Electric-Responsive Copolymers, 294 10.5.2 Magneto-Responsive Copolymers, 294 10.5.3 Light-Responsive Copolymers, 295 10.6 Conclusion, 297 References, 297 11 Pharmaceutical Polymers 307 Natarajan Venkatesan and Hideki Ichikawa 11.1 Introduction to Pharmaceutical Polymers, 307 11.2 Applications of Pharmaceutical Polymers, 308 11.2.1 Polymers as Excipients, 308 11.2.2 Functional Excipients, 317 11.2.3 Drug Delivery Agents, 320 11.2.4 Solubility and Bioavailability Enhancement, 322 11.2.5 Transdermal Drug Delivery, 324 11.2.6 Novel Polymeric Hydrogels for Drug Delivery Applications, 324 11.3 Summary, 329 References, 329 12 Polymer Conjugates of Proteins and Drugs to Improve Therapeutics 334 Parijat Kanaujia and Ajazuddin 12.1 Introduction, 334 12.2 Polymers for Therapeutic Conjugation, 335 12.2.1 Poly(ethylene Glycol) Protein Conjugate, 336 12.2.2 Significance of PEG, 337 12.2.3 Chemistry of Protein–PEG Conjugation, 338 12.2.4 Biofate of PEGylated Proteins, 348 12.3 PEGylated Proteins in Clinical Practice, 351 12.3.1 PEG Conjugate with Low Molecular Weight Drugs, 351 12.3.2 PEG Structures for Small-Molecule PEGylation, 351 12.3.3 Advantages of PEGylated Drugs, 355 12.4 N-(2-Hydroxypropyl) Methacrylamide (HPMA) Copolymer Conjugate, 358 12.5 Poly(l-Glutamic Acid) Conjugates, 362 12.6 Polysialic Acid (PSA) Conjugates, 363 12.7 Conclusion, 364 References, 365 Index 373