Polymer Brushes Synthesis, Characterization and Applications

by Advincula, Rigoberto C.; Brittain, William J.; Caster, Kenneth C.; Rü; he, Jü; rgen

• ISBN13: 9783527310333
• ISBN10: 3527310339
• Edition: 1st
• Format: Hardcover
• Copyright: 2004-09-03
• Publisher: Wiley-VCH

Summary

Materials scientists, polymer chemists, surface physicists and materials engineers will find this book a complete and detailed treatise on the field of polymer brushes, their synthesis, characterization and manifold applications. In a first section, the various synthetic pathways and different surface materials are introduced and explained, followed by a second section covering important aspects of characterization and analysis in both flat surfaces and particles. These specific surface initiated polymerization (SIP) systems such as linear polymers, homopolymers, block copolymers, and hyperbranched polymers are unique compared to previously reported systems by chemisorption or physisorption. They have found their way in both large-scale and miniature applications of polymer brushes, which is covered in the last section. Such 'hairy' surfaces offer fascinating opportunities for addressing numerous problems of both academic and, in particular, industrial interest: high-quality, functional or protective coatings, composite materials, surface engineered particles, metal-organic interfaces, biological applications, micro-patterning, colloids, nanoparticles, functional devices, and many more. It is the desire of the authors that this book will be of benefit to readers who want to "brush-up on polymers".

Author Biography

Rigoberto C. Advincula is currently Associate Professor at the Department of Chemistry of the University of Houston. He obtained his bachelor's degree from the University of the Philippines in 1987 and his PhD in Chemistry at the University of Florida seven years later.<br> He was Alexander von Humboldt Research Fellow at the Max Planck Institute for Polymer Research in 1995 and the following year a Research Fellow at the Department of Chemical Engineering, Stanford University. In 2003, Dr. Advincula was one of the recipients of the Arthur K. Doolittle Award given by the Polymer Materials Science and Engineering division of the American Chemical Society. His current research interests are in the area of organic and polymer materials as applied to nanoscale building blocks and phenomena, with applications focusing on electro-optical properties, biofunctional systems, and surface modifiers.<br> <br> William J. Brittain is currently Professor at the University of Akron, Department of Polymer Science. He obtained his bachelor's degree from the University of Northern Colorado in 1977 and his PhD in Chemistry at the California Institute of Technology in 1982.<br> Following a postdoctoral fellowship at Duke University and 6 years in Central Research and Development at E. I. DuPont, he joined the Uni<br> <br> Kenneth C. Caster is currently Senior Research Scientist within the Center for Biologically Inspired Materials and Materials Systems at the Pratt School of Engineering, Duke University. He obtained his bachelor's degree from Stetson University in 1979 and his PhD in Chemistry from Duke University in 1983. He was a National Institutes of Health Postdoctoral Fellow at the University of Florida from 1983 to 1985, thereafter he spent 18 years in industrial R&D, first at Union Carbide Corporation in new product development and catalysis research, followed by 9 years at Lord Corporation, as principle investigator of new materials research in the Lord Materials Division. In 1998, Dr. Caster was joint-winner of the Lord Corporation Chemical Products Division Technical Achievement Award for innovation and development of Contact Metathesis Polymerization. He has extensive experience from basic R&D to process development, and his areas of expertise include ring-opening metathesis polymerization, organophosphorus chemistry, catalysis, ligand design and synthesis, heterocyclic chemistry, and small molecule molecular modeling.<br> <br> Jnrgen Rnhe has been Professor for Chemistry and Physics of Interfaces at the University of Freiburg since 1999 and since 2001 he is also director of the Institute for Microsystems Technology. Prior to this, he was associate professor at the Max-Planck-Institute for Polymer Research. He has been visiting scientist at the IBM Almaden Laboratories, at the RIKEN Institute in Tokyo, Japan, the Cavendish Laboratories of Physics, Stanford University and Georgia Institute for Technology. Professor Rnhe has won the prize for Chemistry awarded by the Academy of Sciences in G÷ttingen (1999) and the DECHEMA award 2001. His research interests are directed towards the development of new methods for the generation of tailor-made surfaces and the use of polymers in nanosciences and microsystems technology.

Table of Contents

Preface	xv
List of Contributors	xvii
Polymer Brushes: On the Way to Tailor-Made Surfaces	1	(32)
Jurgen Ruhe
Growth of Polymer Molecules at Surfaces: Introductory Remarks	1	(2)
Coatings: From First Principles to High-Tech Applications	3	(3)
Surface-Coating Techniques	6	(4)
Surface-Attached Polymers	10	(3)
Polymer Brushes: General Features	13	(2)
Theory of Polymer Brushes	15	(3)
Synthesis of Polymer Brushes	18	(4)
Polymer Brushes as Functional Materials	22	(2)
Microstructured Polymer Brushes	24	(4)
Surface-Initiated Polymerization: The Overall Picture	28	(5)
Part I Synthesis	33	(154)
Recent Advances in Polymer Brush Synthesis	35	(16)
Anthony M. Cranville
William J. Brittain
Introduction	35	(2)
``Grafting To'' Synthesis Technique	37	(4)
``Grafting From'' Synthesis Technique	41	(10)
Polymer Brushes by Atom Transfer Radical Polymerization	51	(18)
Jeffrey Pyun
Tomasz Kowalewski
Krzysztof Matyjaszewski
Introduction	51	(1)
Polymer Brushes on Flat Surfaces	52	(5)
Controlled ATRP from Flat Surfaces	53	(1)
Block Copolymer Brushes on Flat Surfaces	54	(1)
Stimuli-Responsive Ultrathin Films from ``Grafting To'' Approach	55	(2)
Polymer Brushes from Particles	57	(6)
Spherical Brushes from Inorganic Colloids	58	(1)
Multilayered Core-Shell Colloids	58	(3)
Imaging of Individual Spherical Brushes	61	(2)
Modification of Carbon Black Fillers	63	(1)
Molecular Brushes	63	(6)
Synthesis of Molecular Brushes from Linear Polymeric Macroinitiators	64	(1)
Molecular Brushes from Dendritic Macroinitiators	65	(4)
Polymer Brushes by Atom Transfer Radical Polymerization Initiated from Macroinitiator Synthesized on the Surface	69	(18)
Viktor Klep
Bogdan Zdyrko
Yong Liu
Igor Luzinov
Introduction	69	(3)
Experimental	72	(1)
Results and Discussion	73	(14)
Synthesis of Macroinitiator for ATRP	73	(4)
ATRP from Macroinitiator	77	(10)
Synthesis of Polypeptide Brushes	87	(18)
Henning Menzel
Peter Witte
Introduction	87	(1)
Preparation of Peptide Brushes by ``Grafting To''	88	(2)
Preparation of Peptide Brushes by Grafting From Polymerization	90	(5)
Mechanisms of NCA Polymerization	90	(3)
Amine-Initiated Grafting From Polymerizations in Solution	93	(1)
Other Techniques for Amine-Initiated Grafting From Polymerizations	94	(1)
Preparation of Peptide Brushes by Living Grafting From Polymerization	95	(10)
Copolymerization Approach	95	(4)
Alloc-Amide Approach	99	(6)
Bottle Brush Brushes: Ring-Opening Polymerization of Lactide from Poly(hydroxyethyl methacrylate) Surfaces	105	(14)
Jong-Bum Kim
Wenxi Huang
Chun Wang
Merlin Bruening
Gregory L. Baker
Introduction	105	(4)
Synthesis of PHEMA-g-PLA	109	(5)
Conclusions and Implications for Future Studies	114	(1)
Experimental Section	115	(4)
Materials	115	(1)
Preparation of Monomer Solution and Substrates	115	(1)
Ring-Opening Polymerization from PHEMA Surface	115	(1)
Analytical Methods	115	(4)
Preparation of Well-Defined Organic-Inorganic Hybrid Nanostructures using Living Cationic Surface-Initiated Polymerization from Silica Nanoparticles	119	(10)
Il-Jin Kim
Su Chen
Rudolf Faust
Introduction	119	(1)
Experimental Section	120	(2)
Materials	120	(1)
Characterization	120	(1)
Synthesis of Immobilized Macroinitiators	121	(1)
Results and Discussion	122	(7)
Living Cationic Surface-Initiated Polymerization of IB from Silica Nanoparticles in the Presence of Sacrificial Free Initiator	122	(3)
Living Cationic Surface-Initiated Polymerization of IB from Silica Macroinitiators	125	(4)
Photoinitiated Polymerization from Self-Assembled Monolayers	129	(22)
Daniel J. Dyer
Jianxin Feng
Charles Fivelson
Rituparna Paul
Rolf Schmidt
Tongfeng Zhao
Introduction	129	(2)
Substrates	131	(2)
Silicon, Silica and Glass	131	(1)
Planar Gold	131	(2)
Nanoparticles	133	(1)
Photoinitiated Radical Polymerization Mechanisms	133	(2)
Free Radicals	133	(1)
Photosensitizers	134	(1)
Photo-Iniferters	135	(1)
Polymerization from AIBN-type SAMs	135	(8)
Design and Synthesis	135	(2)
Monolayer Characterization	137	(1)
Polymerization of Styrene	138	(5)
Conclusions and Future Studies	143	(1)
Experimental	144	(7)
Initiator Synthesis	144	(1)
Polymerizations	145	(1)
Reflection Absorption Infrared Spectroscopy (FT-RAIRS) Measurements	146	(1)
Ellipsometry	146	(1)
X-Ray Photoelectron Spectroscopy (XPS)	146	(1)
Molecular Weight Measurements	147	(1)
Molecular Modeling	147	(4)
Recent Advances in the Synthesis and Rearrangement of Block Copolymer Brushes	151	(16)
Stephen G. Boyes
Anthony M. Granville
Marina Baum
Bulent Akgun
Brian K. Mirous
William J. Brittain
Introduction and Background	151	(2)
Controlled/``Living'' Free Radical Polymerization	153	(1)
Atom Transfer Radical Polymerization (ATRP)	153	(1)
Synthesis of Block Copolymer Brushes	154	(6)
Diblock Copolymer Brushes	154	(4)
Triblock Copolymer Brushes	158	(2)
Rearrangement of Block Copolymer Brushes	160	(7)
Rearrangement of Diblock Copolymer Brushes	160	(7)
Surface-Grafted Hyperbranched Polymers	167	(20)
Hideharu Mori
Axel H. E. Muller
Introduction	167	(3)
``Grafting To'' Approach	170	(2)
Synthesis of 2D Hybrids by ``Grafting To''	170	(1)
Synthesis of 3D Hybrids by ``Grafting To''	171	(1)
Multi-Step Grafting Approach	172	(1)
``Grafting To-Grafts''	172	(1)
``Grafting From-Grafts''	173	(1)
``Grafting From'' Approach	173	(14)
Synthesis of 2D Hybrids by Surface-Initiated, Self-Condensing Vinyl (Co)polymerization	175	(3)
Synthesis of 3D Hybrids by Surface-Initiated Self-Condensing Vinyl (Co)polymerization	178	(3)
Theoretical Considerations	181	(1)
Other Systems	182	(5)
Part II Characterization	187	(142)
The Analysis and Characterization of Polymer Brushes: From Flat Surfaces to Nanoparticles	189	(24)
Rigoberto C. Advincula
Introduction	190	(3)
Polymer Brushes	190	(2)
SIP on Flat Surfaces and Particle Substrates	192	(1)
Characterization of Ultrathin Polymer Films and Polymer Brushes	193	(5)
Spectroscopy and Optical Techniques	194	(1)
Microscopy	195	(1)
Other Methods	196	(2)
Investigating Polymer Brush Systems	198	(6)
Characterization of the Step-by-Step Procedure	198	(1)
Investigating the Different Regimes of Polymer Brush Conformation on Surfaces	199	(1)
Investigating Phase Segregation and Formation of Patterns	200	(1)
Polymerization Mechanism	201	(3)
Patterning Using Nonlithographic Methods	204	(1)
The Importance of Characterizing Particles and Nanoparticles	204	(1)
Characterization and Analysis Methods for Polymer Brushes on Particles	205	(8)
In-Situ Investigations on Particles	206	(2)
Degrafted Polymers from Particles	208	(5)
Characterization of Polymer Brushes on Nanoparticle Surfaces	213	(18)
Thomas A. P. Seery
Mark Jordi
Rosette Guino
Dale Huber
Introduction	213	(2)
Experimental	215	(6)
Materials	215	(1)
Instrumentation	215	(1)
Pyrolysis GC-MS	216	(1)
Infrared Monitoring of Polymer Formation	216	(1)
Synthesis of Alkanethiol-Stabilized Gold Nanoparticles	217	(1)
Synthesis of Stober Silica Nanoparticles	218	(1)
Synthesis of NCSEOS	218	(1)
Synthesis of BCH, NCSEOS, and TMEOS-Coated Nanoparticles	218	(1)
Synthesis of TMEOS Silica-Polymer Mixture	219	(1)
Synthesis of Silica-Poly(norbornene) Nanocomposites	219	(1)
Isolation of Grafted Polymer Chains	220	(1)
Polymer Stability Test	220	(1)
Results and Discussion	221	(10)
Spherical Polyelectrolyte Brushes	231	(18)
Matthias Ballauff
Introduction	231	(3)
Synthesis and Characterization	234	(2)
Determination of Core Radius R, Contour Length LC, and Grafting Density σ	234	(1)
Titration Curve	235	(1)
Experimental Verification of Theoretical Predictions	236	(4)
Confinement of the Counterions	237	(1)
Correlation of the Counterions to the Macroion	238	(2)
Flow Behavior	240	(2)
Applications	242	(7)
Interaction with Charged Surfaces	242	(1)
Interaction with Proteins in Solution	243	(6)
Weak Polyelectrolyte Brushes: Complex Formation and Multilayer Build-up with Oppositely Charged Polyelectrolytes	249	(24)
Rupert Konradi
Haining Zhang
Markus Biesalski
Jurgen Ruhe
Introduction	249	(2)
Synthesis and Data Evaluation	251	(2)
Synthesis	251	(1)
Multiple-Angle Nulling Ellipsometry	252	(1)
Swelling Behavior of Weak Polyelectrolyte Brushes in Aqueous Environments	253	(12)
The Influence of pH Value	254	(1)
Interaction with Monovalent Cations	254	(3)
Interaction with Divalent Cations	257	(6)
Interaction with a Trivalent Cation: Aluminum	263	(1)
A Classification	264	(1)
Interaction Between Polyelectrolyte Brushes and Oppositely Charged Polyelectrolytes in Solution	265	(8)
The Formation of Surface-Attached PEL-PEL Complexes	265	(3)
The Formation of PEL Multilayer Assemblies	268	(5)
Structure and Properties of High-Density Polymer Brushes	273	(14)
Yoshinobu Tsujii
Muhammad Ejaz
Shinpei Yamamoto
Kohji Ohno
Kenji Urayama
Takeshi Fukuda
Introduction	273	(1)
Controlled Synthesis of High-Density Polymer Brush by ATRP	274	(3)
Structure and Properties of High-Density PMMA Brushes	277	(5)
Swollen Brushes	277	(2)
Dry Brushes	279	(3)
Application of High-Density Polymer Brushes	282	(5)
Behavior of Surface-Anchored Poly(acrylic acid) Brushes with Grafting Density Gradients on Solid Substrates	287	(30)
Tao Wu
Jan Genzer
Peng Gong
Igal Szleifer
Petr Vlcek
Vladimir Subr
Glossary	287	(1)
Introduction	288	(4)
Experimental Section	292	(4)
Formation of the Gradient of the Polymerization Initiator	292	(1)
Preparation of PtBA and Hydrolysis into PAA	293	(1)
Polymer Characterization	294	(2)
Theory Section	296	(4)
Experimental Results	300	(4)
Discussion	304	(13)
Surface Hydrolysis of PtBA	304	(2)
Dependence of H on Ionic Strength	306	(2)
Dependence of H on the PAA Grafting Density	308	(2)
Molecular Insight from Calculations	310	(7)
Kinetics of Polymer Brush Formation With and Without Segmental Adsorption	317	(12)
Lynn S. Penn
Heqing Huang
Roderic P. Quirk
Tae H. Cheong
Introduction	317	(3)
Experimental	320	(3)
Synthesis and Characterization of Amine Chain-End Functionalized Polystyrene	320	(1)
Introduction of Active Sites to Surface of Solid	320	(1)
Tethering Reactions in Good Solvent	320	(1)
Tethering Reactions in Poor Solvent	321	(1)
Monitoring the Tethering Reactions	321	(2)
Results and Discussion	323	(6)
Results in Absence of Segmental Adsorption	323	(2)
Results in the Presence of Segmental Adsorption	325	(4)
Part III Applications	329	(142)
Applications of Polymer Brushes and Other Surface-Attached Polymers	331	(40)
Kenneth C. Caster
Introduction	331	(1)
Surface Modification and Functionalization	332	(4)
Polymerization Methodologies for Surface-Attached Polymers	332	(4)
Property Control	336	(1)
Impact on Types of Materials	336	(1)
Applications	336	(15)
Adhesion	337	(4)
Tribology	341	(1)
Stabilization and Compatiblization	341	(2)
Surface Coatings	343	(2)
Stimuli-Responsive and Switchable Surfaces	345	(1)
Separations	346	(3)
Nanofabrication	349	(1)
Surfaces for Electronics	350	(1)
Other Uses	351	(1)
Future Prospects	351	(20)
Appendix	353	(18)
Polymer Brushes: Towards Applications	371	(10)
Gregory L. Whiting
Tamer Farhan
Wilhelm T. S. Huck
Introduction	371	(1)
Experimental	372	(2)
Materials	372	(1)
Characterization	373	(1)
Synthesis of Triphenylamine Acrylate (TPAA) Monomer	373	(1)
Synthesis and Deposition of Trichlorosilane ATRP Initiator	373	(1)
Surface-Initiated Polymerizations	373	(1)
Results and Discussion	374	(7)
Kinetics of Surface-Initiated ATRP of MMA from Silicon	374	(1)
Surface-Initiated ATRP from Polymeric Substrates	375	(2)
Synthesis of Conjugated Polymer Brushes from ITO	377	(4)
Polymerization, Nanopatterning and Characterization of Surface-Confined, Stimulus-Responsive Polymer Brushes	381	(22)
Marian Kaholek
Woo-Kyung Lee
Bruce LaMattina
Kenneth C. Caster
Stefan Zauscher
Introduction	381	(1)
Experimental	382	(4)
Materials	382	(1)
Substrates	383	(1)
Preparation of Initiator Monolayers	383	(1)
Nanopatterning of Initiator	383	(1)
NIPAAM Polymerization	384	(1)
Polymer Characterization	385	(1)
Results and Discussion	386	(17)
Surface-Initiated Bulk Polymerization	386	(4)
Phase Behavior and Mechanical Characterization	390	(3)
Surface Force Measurements	393	(3)
Nano-Patterning	396	(7)
Mixed Polymer Brushes: Switching of Surface Behavior and Chemical Patterning at the Nanoscale	403	(24)
Sergiy Minko
Marcus Muller
Valeriy Luchnikov
Mikhail Motornov
Denys Usov
Leonid Ionov
Manfred Stamm
Introduction	403	(1)
Theory of Mixed Polymer Brushes	404	(5)
Synthesis of Mixed Brushes	409	(3)
The ``Grafting To'' Method	409	(2)
The ``Grafting From'' Method	411	(1)
Experimental Study of Phase Segregation in Mixed Brushes	412	(5)
Adaptive Responsive Behavior: Regulation of Wetting and Adhesion	417	(3)
Patterning of Mixed Brushes	420	(7)
Local Chain Organization of Switchable Binary Polymer Brushes in Selective Solvents	427	(14)
Melbs C. LeMieux
Denys Usov
Sergiy Minko
Manfred Stamm
Vladimir V. Tsukruk
Introduction	427	(4)
Polymer Surface Modification	427	(1)
Polymer Brushes	428	(1)
Binary Polymer Brushes	429	(2)
Experimental	431	(2)
Materials and Synthesis	431	(1)
Methods	432	(1)
Results and Discussion	433	(8)
Dry State Analysis	433	(1)
Morphology in Solvent	434	(3)
Mechanical Response in Solvent	437	(4)
Motion of Nano-Objects Induced by a Switchable Polymer Carpet	441	(8)
Svetlana Prokhorova
Alexey Kopyshev
Ayothi Ramakrishnan
Jurgen Ruhe
Introduction	441	(2)
Materials	443	(1)
Results and Discussion	444	(5)
Photochemical Strategies for the Preparation and Microstructuring of Densely Grafted Polymer Brushes on Planar Surfaces	449	(22)
Oswald Prucker
Rupert Konradi
Martin Schimmel
Jorg Habicht
In-Jun Park
Jurgen Ruhe
Introduction	449	(4)
Topological and Chemical Patterning of Surfaces	449	(2)
Photochemical Pathways for Grafting Polymers onto Surfaces: A Literature Survey	451	(2)
General Features of Surface-Initiated Polymerization from Monolayers of Azo Initiators	453	(2)
Photolithographic Procedures for the Generation of Microstructured Polymer Brushes on Planar Surfaces	455	(10)
Photoablation of Polymer Brushes	455	(5)
Photoablation/Photodecomposition of the Initiator Layer followed by Thermal Polymerization	460	(2)
Patterning by Photopolymerization	462	(3)
Multifunctional Patterns	465	(1)
Applications of Photostructured Polymer Brushes	466	(5)
Index	471