Physical Aspects of Polymer Self-Assembly

P. R. Sundararajan, PhD, DSc, is a Professor in the Department of Chemistry at Carleton University in Ontario, Canada and has over 40 years of academic and industry experience in polymer chemistry. He has held positions as the NSERC-Xerox Industrial Research Chair Professor, Director of the Ottawa Carleton Chemistry Institute, Associate Chair of Graduate Affairs at the university, and Principal Scientist, Manager, and Project Leader at the Xerox Research Center of Canada. His current research focuses on the morphology of self-assembly systems, macromolecular nanotechnology, organo- and polymer gels and the morphology of polymer composites in confined systems. He is a winner of the Macromolecular Science and Engineering Award of the Chemical Institute of Canada, Materials Chemistry Award of the Canadian Materials Society and is a Fellow of the Chemical Institute of Canada. He was the President of the Canadian Society for Chemistry and the Chair of the Chemical Institute of Canada.

• Preface xi1 Introduction 11.1 Polymer Tacticity 11.2 Big versus Small 51.3 Entanglement 51.4 Excluded Volume 81.5 Free Volume 101.6 Self‐Assembly 101.7 Polymer Self‐Assembly 12References 132 Molecular Forces 172.1 Van der Waals Interaction 172.2 Hydrogen Bond 212.3 C─H…π Interaction 272.4 Halogen Bond 292.5 Other Hydrogen Bonds 302.6 Coulombic Interaction 31References 333 Features of Self‐Assembly 373.1 Self‐Sorting—Small Molecules 373.2 Polymer Self‐Sorting 433.3 Concentration‐Dependent Association 483.4 Polymer–Guest Molecule Recognition 493.5 Sergeant–Soldier Phenomenon 553.6 Majority Rules 613.7 Chain Folding 653.8 Foldamers 793.9 Single Chain Polymer Crystals and Nanoparticles 91References 99Further Reading 1044 Supramolecular Macromolecules and Polymers 1054.1 Supramolecular Macromolecules 1054.2 Supramolecular Polymers 1104.3 Modular Supramolecules 1234.4 Solvent Influence 1274.5 Comb Polymers 140References 149Further Reading 1525 Block Copolymers 1535.1 Theoretical Aspects 1535.2 Diblock Copolymers 1585.3 Organic/Inorganic Diblocks 1655.4 Blends of Diblock Copolymers 1705.5 Diblock/Homopolymer Blends 1725.6 BCP/Small‐Molecular Supramolecular Association 1755.7 Triblock Copolymers 1775.8 Some Applications of Gyroid Morphology 1905.9 Graphoepitaxy 2015.10 Porous Structures 2115.11 Crystalline Block Copolymers 2235.12 Nanotechnology 223References 225Further Reading 2306 Rotaxanes and Polyrotaxanes 2316.1 Definitions and Early Work 2316.2 Cyclodextrins for Inclusion 2376.3 Selective Threading 2446.4 Micelles of Double‐Hydrophilic Block Copolymers via Rotaxane Formation 2496.5 Homopolymer Micelles 2526.6 Linear and Cyclic PDMS 2536.7 Abrasion Resistance 2546.8 Beyond Linear Polymers and α‐, β‐, and γ‐CDs 2566.9 Insulated Molecular Wires 2586.10 Molecular Switches and Machines 2606.11 Supramolecular Oligomeric and Polymeric Rotaxanes 2686.12 Rotaxane and Polyrotaxane‐Based Muscles 270References 277Further Reading 2807 Polymer Gels 2817.1 One‐Dimensional Growth 2817.2 Definitions and Classifications 2837.3 Gels with Noncrystallizable Polymers 2857.4 Gels with Crystallizable Polymers 2957.5 Add a Sergeant to the Soldiers to Cause Gelation 3007.6 π‐Interaction‐Mediated Gelation 3087.7 Polymer Compatibilized Small Molecule/Polymer Gels 3167.8 Monomer Self‐Assembly and Polymer Gels 3187.9 Poor Man’s Rheology 321References 3248 Small‐Molecule Self‐Assembly in Polymer Matrices 3298.1 Phase Separation in Charge Transport Polymer Layers 3298.2 Glass Transition and Diffusion of Small Molecules 3318.3 Subsurface Self‐Assembly of Small Molecules in Polymer Matrices 3338.4 Solvent Effect on Self‐Assembly of Small Molecules in Polymer Matrices 3388.5 Polymer‐Compatibilized Small‐Molecule Assembly in Polymer Matrices 3438.6 Polymerization‐Induced Phase Separation and Reaction‐Induced Phase Separation 3448.7 PIPS for LC Displays 3458.8 PIPS with Supramolecular Assembly 3478.9 PIPS for Porous Structures 3478.10 Surfactant/Polymer Assembly 350References 356Index 359