POLYMER SCIENCE:A COMPREHENSIVE

REFERENCE

POLYMER SCIENCE:A COMPREHENSIVE

REFERENCE

EDITORS-IN-CHIEF

Krzysztof MatyjaszewskiCarnegie Mellon University, Pittsburgh, PA, USA

Martin MollerRWTH Aachen University, Aachen, Germany

VOLUME 10

POLYMERS FOR A SUSTAINABLE ENVIRONMENTAND GREEN ENERGY

VOLUME EDITORS

J. E. McGrath,Virginia Polytechnic Institute and State University, Blacksburg, VA, USA

M. A. HicknerThe Pennsylvania State University, University Park, PA, USA

R. HöferEditorial Ecosiris, Düsseldorf, Germany

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The following articles are US Government work in the public domain and is not subject to copyright:Chapter 4.08 Cationic Ring-Opening Polymerization of Cyclic EthersChapter 4.17 Polymerization of Cyclic Siloxanes, Silanes, and Related MonomersChapter 7.18 Polymer Dynamics in Constrained Geometries

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CONTENTS OF VOLUME 10

Volume Editors ix

Editors-in-Chief: Biographies xi

Editors: Biographies xiii

Contributors of Volume 10 xxi

Preface xxv

Foreword xix

Volume 10 Polymers for a Sustainable Environment and Green Energy

10.01 Introduction: Polymers for a Sustainable Environment and Green Energy 1JE McGrath, MA Hickner, and R Höfer

10.02 Green Chemistry and Green Polymer Chemistry 5R Höfer and M Selig

Lipids

10.03 Lipid-Based Polymer Building Blocks and Polymers 15TW Abraham and R Höfer

Carbohydrate-Based Polymer Building Blocks & Biopolymers

10.04 Mono-, Di-, and Oligosaccharides as Precursors for Polymer Synthesis 59J-P Pascault, R Höfer, and P Fuertes

10.05 Celluloses and Polyoses/Hemicelluloses 83T Heinze and T Liebert

10.06 Nanochitins and Nanochitosans, Paving the Way to Eco-Friendly and Energy-SavingExploitation of Marine Resources 153RAA Muzzarelli

10.07 Starch-Based Biopolymers in Paper, Corrugating, and Other Industrial Applications 165D Glittenberg

10.08 Guar and Guar Derivatives 195M-P Labeau

10.09 Acacia Gum 205F Thevenet

10.10 Alginates: Properties and Applications 213G Skjåk-Bræk and KI Draget

v

10.11 Xanthan 221G Hublik

10.12 Polylactic Acid 231R Hagen

Amino Acid Based Polymer-Building Blocks and Proteins as Biopolymers

10.13 Gelatin 237TR Keenan

10.14 Processing Soy Protein Concentrate as Plastic in Polymer Blends 249F Chen and J Zhang

Lignin

10.15 Lignin as Building Unit for Polymers 255E Windeisen and G Wegener

Sustainable Use of Biomass

10.16 Natural Fibers 267M Möller and C Popescu

10.17 Natural Rubber 281L Vaysse, F Bonfils, J Sainte-Beuve, and M Cartault

10.18 Biocomposites: Long Natural Fiber-Reinforced Biopolymers 295U Riedel

Polymer Processing: Environmentally Benign & Safe

10.19 Performance Profile of Biopolymers Compared to Conventional Plastics 317H-J Endres and A Siebert-Raths

10.20 Processing of Plastics into Structural Components 355C Bonten and E Haberstroh

10.21 Processing and Performance Additives for Plastics 369R Höfer

10.22 Processing and Performance Additives for Coatings 383R Höfer

Sustainable Manufacturing, Processing and Applications for Polymers and Polymer Systems

10.23 Paper 397MM Mleziva and JH Wang

10.24 Polyurethanes 411G Avar, U Meier-Westhues, H Casselmann, and D Achten

10.25 Polysiloxanes 443F Müller and S Silber

10.26 Lubricant and Fuel Additives Based on Polyalkylmethacrylates 453CD Neveu, R Sondjaja, T Stöhr, and NJ Iroff

10.27 Aqueous Emulsion Polymers 479H Lutz, H-P Weitzel, and W Huster

10.28 Water-Based Epoxy Systems 519A Klippstein, M Cook, and S Monaghan

10.29 Powder Coatings 541G Crapper

10.30 Radiation-Curing Polymer Systems 567R Schwalm

vi Contents of Volume 10

Plastics after Use

10.31 Sustainable Management of Material and Energy Resources 581H Krähling and I Sartorius

Polymers in Energy Applications

10.32 Polymers in Energy Applications 597MA Hickner and JE McGrath

10.33 Poly(Perfluorosulfonic Acid) Membranes 601M Yandrasits and S Hamrock

10.34 Alternative Hydrocarbon Membranes by Step Growth 621B Bae, K Miyatake, and M Watanabe

10.35 Alternative Proton Exchange Membranes by Chain-Growth Polymerization 651EMW Tsang and S Holdcroft

10.36 Polymers in Membrane Electrode Assemblies 691DS Kim, C Welch, RP Hjelm, YS Kim, and MD Guiver

10.37 Morphology of Proton Exchange Membranes 721AM Osborn and RB Moore

10.38 Polymer Electrolyte Membrane Degradation 767DA Schiraldi and D Savant

10.39 Molecular and Mesoscale Modeling of Proton Exchange Membranes 777BF Habenicht and SJ Paddison

10.40 Polymers for Thin Film Capacitors: Energy Storage – Li Conducting Polymers 811K Han and Q Wang

10.41 Aromatic Poly(amides) for Reverse Osmosis 831WE Mickols

10.42 Electrolyzer Membranes 849CK Mittelsteadt and JA Staser

Contents of Volume 10 vii

VOLUME EDITORS

Volume 1 – Basic Concepts and Polymer Properties

AR Khokhlov, Moscow State University, Moscow, RussiaF Kremer, University of Leipzig, Leipzig, Germany

Volume 2 – Polymer Characterization

T Hashimoto, Japan Atomic Energy Agency, Ibaraki, JapanHW Spiess, Max Planck Institute for Polymer Research, Mainz, GermanyM Takenaka, Kyoto University, Kyoto, Japan

Volume 3 – Chain Polymerization of Vinyl Monomers

GW Coates, Cornell University, Ithaca, NY, USAM Sawamoto, Kyoto University, Kyoto, Japan

Volume 4 – Ring-Opening Polymerization and Special Polymerization Processes

S Penczek, Polish Academy of Sciences, Lodz, PolandR Grubbs, California Institute of Technology, Pasadena, CA, USA

Volume 5 – Polycondensation

H-W Schmidt, University of Bayreuth, Bayreuth, GermanyM Ueda, Engineering Tokyo Institute of Technology, Tokyo, Japan

Volume 6 – Macromolecular Architectures and Soft Nano-Objects

AHE Müller, University of Bayreuth, Bayreuth, GermanyKL Wooley, Texas A&M University, College Station, TX, USA

Volume 7 – Nanostructured Polymer Materials and Thin Films

E Kumacheva, University of Toronto, Toronto, CanadaTP Russell, University of Massachusetts, Amherst, MA, USA

Volume 8 – Polymers for Advanced Functional Materials

K Müllen, Max Planck Institute for Polymer Research, Mainz, GermanyCK Ober, Cornell University, Ithaca, NY, USA

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Volume 9 – Polymers in Biology and Medicine

DA Tirrell, California Institute of Technology, Pasadena, CA, USAR Langer, Massachusetts Institute of Technology, Cambridge, MA, USA

Volume 10 – Polymers for a Sustainable Environment and Green Energy

JE McGrath, Virginia Polytechnic Institute and State University, Blacksburg, VA, USAMA Hickner, The Pennsylvania State University, University Park, PA, USAR Höfer, Editorial Ecosiris, Düsseldorf, Germany

x Volume Editors

EDITORS-IN-CHIEF: BIOGRAPHIES

Krzysztof Matyjaszewski received his PhD degree in 1976 from the Polish Academy of Sciencesunder Prof. S. Penczek. Since 1985 he has been at Carnegie Mellon University where he iscurrently J. C. Warner University Professor of Natural Sciences and director of Center forMacromolecular Engineering. He is also Adjunct Professor at the University of Pittsburgh andat the Polish Academy of Sciences. He is the editor of Progress in Polymer Science and CentralEuropean Journal of Chemistry. He has coedited 14 books and coauthored more than 70 bookchapters and 700 peer-reviewed publications; he holds 41 US and more than 120 internationalpatents. His papers have been cited more than 50000 times. His research interests includecontrolled/living radical polymerization, catalysis, environmental chemistry, and advancedmaterials for optoelectronic and biomedical applications.

Dr. Matyjaszewski has received 2011 Wolf Prize, 2011 Prize of Société Chimique de France,2009 Presidential Green Chemistry Challenge Award, 2004 Prize from the Foundation of Polish

Science, and several awards from the American Chemical Society (including 2011 Hermann Mark Award, 2011 AppliedPolymer Science Award, 2007 Mark Senior Scholar Award, 2002 Polymer Chemistry Award, and 1995 Marvel CreativePolymer Chemistry Award). He is a member of US National Academy of Engineering, Polish Academy of Sciences, RussianAcademy of Sciences, and received honorary degrees from l’Institut Polytechnique, Toulouse, France; University of Athens,Greece; Russian Academy of Sciences; Lodz Polytechnic, Poland; and University of Ghent, Belgium.

Martin Möller studied chemistry at Hamburg and Freiburg. He received his PhD degree in 1981from the University of Freiburg.He was a Feodor-Lynen Research Fellow of the Alexander von Humboldt Foundation at the

Polymer Science and Engineering Department, University of Massachusetts, Amherst, USA. After hishabilitation in 1989 at Freiburg University he was professor at the universities of Twente, Enschede,The Netherlands and Ulm, Germany. Since 2002 he is professor of Textile and MacromolecularChemistry at RWTH Aachen University, and since 2003 also the director of DWI-InteractiveMaterials Research Institute at RWTH Aachen University. He has served on the editorial boardof several polymer journals. His fields of interest include polymers self-organization of macro-molecules, surface modification and activation, formation of functional nanostructures, andorganic–inorganic hybrid structures. Martin Möller has received the the Körber-Prize 2002. He isa member of the Deutsche Akademie der Technikwissenschaften (acatech) and of the Academy ofSciences of the state of North-Rhine Westphalia.

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EDITORS: BIOGRAPHIES

Alexei R. Khokhlov was born in 1954 in Moscow, Russia. He graduated from Moscow StateUniversity in 1977, received his PhD in 1979 and Doctor of Science in 1983. He is Full Professorand Head of the Chair of Physics of Polymers and Crystals. He is a Member of Russian Academyof Sciences (2000), Chairman of Polymer Council of Russian Academy of Sciences (2002) andLaureate of the Russian National Award (2007).

Friedrich Kremer is Professor of Molecular Physics, Materials Research Spectroscopy, Institute ofExperimental Physics I, University of Leipzig, Germany. His research interests include broadbanddielectric spectroscopy, time-resolved Fourier transform infrared (FTIR) spectroscopy, and experi-ments with optical tweezers. In 2005 he was awarded with the Karl Heinz Beckurts – Prize; in2011 he received the Wolfgang-Ostwald-Prize from the German Colloid Society.

Takeji Hashimoto received his MS degree in 1969 and PhD in 1971 (with Prof. R. S. Stein) fromthe University of Massachusetts. He was appointed as an assistant professor at Kyoto University,Japan, in 1971, and was promoted as a full professor in 1994. He was director of the HashimotoPolymer Phasing Project, ERATO (Exploratory Research for Advanced Technology), supported byJST (Japan Science and Technology Agency), from 1993 to 1998. He served as a group leader andinvited researcher for the project ‘Neutron Scattering and Structure-Functionality of Soft Matters’at the Advanced Science Research Center (ASRC), Japan Atomic Energy Research Institute (JAEA),Tokai, from 2003 to 2005. Since his retirement from Kyoto University in March 2005, he hasbeen a professor emeritus of Kyoto University, and served as a full-time visiting researcher atASRC, JAEA, Tokai, from 2005 to 2008 and as a group leader for the physical science and lifescience group. He has been a visiting scientist at JAEA, Tokai, since 2008 and a visiting professorat the School of Science and Technology, Kwansei-Gakuin University, Sanda, Japan, since 2009.

He has received several awards including the Society of Polymer Science Japan Award (1986), the High Polymer Physics Award(Ford Prize) from the American Physical Society (1987), the award for Young Rheologist from the Society of Rheology, Japan(1989), the Society of Fiber Science Japan Award (1990), the Osaka Science Award (1992), the Turner Alfrey Award from

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Midland Molecular Institute, Midland Section of ACS (1997), the Fraser Price Memorial Award from the University ofMassachusetts (1997), the Chemical Society of Japan Award (2003), the Japanese Society for Neutron Science Award (2004),and Society of Polymer Science Japan Award for Outstanding Achievement in Polymer Science and Technology (2006).

Hans Wolfgang Spiess, born in 1942, received his doctoral degree in physical chemistry in 1968from the University of Frankfurt with H. Hartmann. After a postdoctoral stay at Florida StateUniversity (with R. K. Sheline), he returned to Germany in 1970 and joined the Max PlanckInstitute for Medical Research (with K. H. Hausser), taking part in the rapid development ofnovel NMR techniques for studying molecular motion in liquids and solids. In 1978, he finishedhis habilitation in physical chemistry at the University of Mainz in the group of H. Sillescu.Subsequently, he held professorships of physical chemistry at the University of Münster (1981–82)and macromolecular chemistry at the University of Bayreuth (1983–84). In 1984, he wasappointed a director of the newly founded Max Planck Institute for Polymer Research inMainz. His research interests include the development of magnetic resonance techniques forelucidating the structure, dynamics, phase behavior, and order of synthetic macromolecules andsupramolecular systems. He applies these methods to the study of new polymer materials to

relate their microscopic and macroscopic behavior. Spiess has served as chairman of the European Polymer Federation(1991–92) and as chairman of the Capital Investment Committee of the German Science Foundation (1994–96). From 1999till 2005, he has been a member of the Scientific Council of the Federal Republic of Germany. His achievements have beenhonored by several distinctions, including the Leibniz Prize of the German Research Foundation in 1987, the EuropeanAmpere Prize, the Liebig Medal of the German Chemical Society, the Award of the Society of Polymer Science (Japan) in2002, the Walther Nernst Medal of the German Bunsen Society for Physical Chemistry in 2007, and the Paul J. FloryResearch Prize in 2010. He is doctor honoris causa of the Technical University of Cluj-Napoca, Romania (1997), and of AdamMickiewicz University, Poznan, Poland (1998).

Mikihito Takenaka received both the master’s degree in engineering in 1988 and the doctor’sdegree in engineering in 1993 with Prof. Takeji Hashimoto from Kyoto University. In 1997, hewas appointed as an assistant professor of the Department of Polymer Chemistry in KyotoUniversity. He was promoted to associate professor in 2011. His research scope includes thedynamics of phase transitions of polymer alloys and the directed self-assembling of blockcopolymer thin films.

Geoffrey W. Coates was born in 1966 in Evansville, Indiana. He received a BA degree in chemistryfrom Wabash College in 1989 and a PhD in organic chemistry from Stanford University in 1994.His thesis work, under the direction of Robert M. Waymouth, investigated the stereoselectivity ofmetallocene-based Ziegler–Natta catalysts. Following his doctoral studies, he was an NSFPostdoctoral Fellow with Robert H. Grubbs at the California Institute of Technology. Duringthe summer of 1997, he joined the faculty of Cornell University as an assistant professor ofchemistry. He was promoted to associate professor in 2001 and to professor in 2002. He wasappointed to the first Tisch University Professorship in 2008.

The research focus of the Coates Group is the development of new catalysts for the synthesisof macromolecules as well as small molecules. Professor Coates’ research concentrates ondeveloping new methods for reacting commodity feedstocks in unprecedented ways. His currentresearch centers on the development of homogeneous catalysts for olefin polymerization,heterocycle carbonylation, epoxide homo- and copolymerization, and utilization of carbondioxide in polymer synthesis.

xiv Editors: Biographies

Professor Coates is an Alfred P. Sloan Research Fellow and has received awards from the ACS (A. C. Cope Scholar Award,Affordable Green Chemistry Award, A. K. Doolittle Award, Carl S. Marvel – Creative Polymer Chemistry Award, and AkronSection Award), NSF (CAREER), MIT Technology Review Magazine (TR 100 Award), Research Corporation (InnovationAward), Arnold and Mabel Beckman Foundation (Young Investigator Award), David and Lucile Packard Foundation(Fellowship in Science and Engineering), and Dreyfus Foundation (Camille and Henry Dreyfus New Faculty and CamilleDreyfus Teacher-Scholar Awards). In 2006, he received the Stephen and Margery Russell Distinguished Teaching Award atCornell University and became a member of the American Association for the Advancement of Science. In 2011, he wasidentified by Thomson Reuters as one of the world’s top 100 chemists on the basis of the impact of his scientific research. He isa member of the editorial advisory boards of the Journal of Polymer Science, Chemical Reviews, and ChemCatChem. He is amember of the editorial board of Dalton Transactions and is an associate editor for Macromolecules.

Mitsuo Sawamoto was born in 1951 in Kyoto, Japan. He received a BS (1974), an MS (1976),and PhD degrees (1979) in polymer chemistry from Kyoto University, Japan. After a postdoc-toral research at the Institute of Polymer Science, The University of Akron, Akron, OH, USA(1980–81), he joined the faculty of Department of Polymer Chemistry, Kyoto University, Japanin 1981 as a research instructor and is currently Professor of Department of Polymer Chemistry,Graduate School of Engineering, Kyoto University, Japan since 1994.

He served as President of the Society of Polymer Science, Japan from 2008–10, and iscurrently an executive member of the Science Council of Japan, a titular member of IUPACPolymer Division, and one of the Editors of the Journal of Polymer Science, Part A, PolymerChemistry. He is also the principal investigator of a research project “Sequence-RegulatedMacromolecules” (2006–10; Grant-in-Aid for Scientific Research: Creation of Novel AcademicDisciplines) and the project leader of the Kyoto University Global Center of Excellence (GCOE)

Project “Integrated Materials Science” (2007–11), both granted by the Ministry of Education, Science, Culture, and Sports,Japan via the Japan Society for Promotion of Science.

With over 350 original papers and over 30 reviews, he has received, among others, Award of the Society of Polymer Science,Japan (1992), Divisional Research Award of the Chemical Society of Japan (1999), and Arthur K. Doolittle Award of PMSEDivision, the American Chemical Society (2002). His research interest includes development of novel precision polymeriza-tions and catalysis (living cationic polymerization with Lewis-acid catalysts (1984) and living radical polymerization withtransition metal complex catalysts (since 1995)), the synthesis of designed functional polymers, the nature of polymerizationintermediates, and most recently the sequence regulation in chain growth polymerization for single-chain functional macro-molecules of carbon-based backbones.

The first paper on his living radical polymerization has been cited thus far over 1600 times and is ranked number two in themost cited papers published in Macromolecules; a comprehensive review on this discovery published in Chemical Reviews hasnow been cited over 1200 times and has been selected as one of the ACS 2007 Highly Cited Papers (within top 1%) in the latestten years (1998–2007); and he was ranked number one in Japan and number three in the world among the most cited scientistsin organic and polymer chemistry for the period of 1997–2001.

Stanislaw Penczek is Professor of Polymer Chemistry at the Polish Academy of Sciences (Centreof Molecular and Macromolecular Studies in Lodz). He teaches at the Graduate School of theJagiellonian University (Krakow) as an honorary professor. He has mostly contributed to thekinetics, thermodynamics, and mechanisms of the ring-opening polymerization, publishing over300 papers in related areas. He was one of the first to observe living and controlled polymeriza-tions in cationic and anionic ROP, including reversibility of deactivation of propagating species.Among other honors from Belgium, Japan, and Germany (the Warburg Prize), he is a member ofthe Polish Academy of Sciences and foreign member of German (Nordrhein) Academy, Dr h.c. ofthe Pierre and Marie Curie University in Paris and Dr h.c. of the Russian Academy of Sciences. Hewas a member of the International Union of Pure and Applied Chemistry (IUPAC) Bureau fortwo terms, and former president of European Polymer Federation.

Editors: Biographies xv

Robert (Bob) Howard Grubbs’ main interests in organometallic chemistry and synthetic chem-istry are catalysts, notably Grubbs’ catalyst for olefin metathesis and ring-opening metathesispolymerization with cyclic olefins such as norbornene. He also contributed to the development ofso-called ‘living polymerization’.

Grubbs has received many awards including Alfred P. Sloan Fellow (1974–76), Camille andHenry Dreyfus Teacher-Scholar Award (1975–78), Alexander von Humboldt Fellowship (1975),ACS Benjamin Franklin Medal in Chemistry (2000), ACS Herman F. Mark Polymer ChemistryAward (2000), ACS Herbert C. Brown Award for Creative Research in Synthetic Methods (2001),the Tolman Medal (2002), and the Nobel Prize in Chemistry (2005). He was elected to theNational Academy of Sciences in 1989 and a fellowship in the American Academy of Arts andSciences in 1994.

Hans-Werner Schmidt studied chemistry at the University of Mainz (Germany) and ETH Zürich(Switzerland). He received his diploma in chemistry and Dr. rer. nat. degree in macromolecularchemistry with Prof. Helmut Ringsdorf at the University of Mainz. After a stay at the DuPontCentral Research in Wilmington, Delaware (USA), he moved to the University of Marburg toobtain his habilitation. From 1989 to 1994, he was Assistant and Associate Professor of Materialswith tenure at the Materials Department, College of Engineering at the University of California,Santa Barbara. Since 1994, he has been Full Professor for Macromolecular Chemistry at theUniversity of Bayreuth. He is director of the Bayreuth Institute of Macromolecular Research andfounding member of the Bayreuth Centre for Colloids and Interfaces. Since 2009, he has beenVice President of the University of Bayreuth for research and since 2004 chairman of the ‘EliteStudy Program Macromolecular Science’ (Elite Network Bavaria).

His research interest is focused on the synthesis and development of novel organic functionalmaterials in the area of emerging technologies. This includes multifunctional polymers, molecular glasses, and supramolecularpolymer additives and gelators. Combinatorial methods to efficiently synthesize and screen materials properties of polymerand supramolecular materials and functions of devices are an additional aspect.

Mitsuru Ueda received his BS and MS degrees in polymer chemistry from Chiba University in1970 and 1972, respectively, and a PhD degree from Tokyo Institute of Technology in 1978. Hejoined Yamagata University in 1972 and was promoted to a professor in 1989. He moved toTokyo Institute of Technology in 1999. His current research interests are the development of newsynthetic methods for condensation polymers, polymer solar cells, fuel-cell membranes, photo-sensitive materials for microelectronics, and new advanced resist materials.

Axel H. E. Müller obtained his PhD in 1977 from Johannes Gutenberg University in Mainz,Germany, for the work on the kinetics of anionic polymerization with G. V. Schulz. Since 1999,he has been professor and chair of macromolecular chemistry at the University of Bayreuth. In2004, he received the IUPAC MACRO Distinguished Polymer Scientist Award and since 2011, hehas been a Fellow of the Polymer Chemistry Division of the American Chemical Society. He issenior editor of the journal Polymer. His research interests focus on the design of well-definedpolymer structures by controlled/living polymerization techniques and on self-organized nanos-tructures and hybrids obtained from them. He has coedited five books and published over 400research papers.

xvi Editors: Biographies

Karen L. Wooley holds the W. T. Doherty-Welch Chair in the Department of Chemistry at TexasA&M University, with a joint appointment in the Department of Chemical Engineering. Shereceived a BS in chemistry from Oregon State University in 1988 and then studied under thedirection of Professor Jean M. J. Fréchet at Cornell University, obtaining a PhD in polymer/organic chemistry in 1993. She began an academic career as an assistant professor of chemistry atWashington University in St. Louis, Missouri; was promoted in 1999 to full professor with tenure;and was installed as a James S. McDonnell Distinguished University Professor in Arts & Sciencesin 2006. In 2009, she relocated to Texas A&M University. Research areas include the synthesis andcharacterization of degradable polymers, unique macromolecular architectures and complexpolymer assemblies, and the design and development of well-defined nanostructured materials,for which she has received several awards, including an Arthur C. Cope Scholar Award, aHerman F. Mark Scholar Award, and awards from the National Science Foundation, the Office

of Naval Research, and the Army Research Office. Karen serves as an editor for the Journal of Polymer Science, Part A: PolymerChemistry. She directs an NHLBI-supported Program of Excellence in Nanotechnology and also serves on the Scientific AdvisoryPanel for the NIH Nanomedicine Development Centers and on the International Scientific Advisory Board for the DutchBioMedical Materials Program.

Professor Eugenia Kumacheva is a Canada Research Chair in Advanced Polymer Materials. Hercurrent research interests are in polymer micro- and nanostructured materials, hybrid materials,biomaterials, inorganic nanoscale materials, and microfluidics.

Thomas Russell is Silvio O. Conte Distinguished Professor, Polymer Science and EngineeringDepartment; Director, Energy Frontier Research Center (EFRC), Polymer-Based Materials forHarvesting Solar Energy. His research interests are polymer-based nanoscopic structures,polymer-based nanoparticle assemblies, electrohydrodynamic instabilities in thin polymerfilms, surface and interfacial properties of polymers, polymer morphology; kinetics of phasetransitions, and supercritical fluid/polymer interactions.

Professor Christopher K. Ober received his BSc in honours chemistry (co-op) from theUniversity of Waterloo, Ontario, in 1978. He received his PhD in polymer science and engineer-ing from the University of Massachusetts (Amherst) in 1982. From 1982 until 1986, he was asenior staff member at the Xerox Research Centre of Canada where he worked on markingmaterials. Ober joined Cornell University as an assistant professor in the Department ofMaterials Science and Engineering in 1986. He recently served as Interim Dean of the Collegeof Engineering. He has pioneered new methods in photolithography and studies the biologymaterials interface. His awards include the 2009 Gutenberg Research Award from the Universityof Mainz, the 1st Annual FLEXI Award in the Education Category (for flexible electronics)awarded in 2009, the 2007 Humboldt Research Prize, the 2006 ACS Award in AppliedPolymer Science, and the Photopolymer Science and Technology Award in 2004. He was electedan ACS Fellow in the 2009 Inaugural Class.

Editors: Biographies xvii

Professor Dr. Klaus Müllen obtained his PhD degree from the University of Basel, Switzerland, in1972 where he undertook research with Professor F. Gerson on EPR spectroscopy of twistedπ-systems. In 1972, he joined the group of Professor J.F.M. Oth at the Swiss Federal Institute ofTechnology in Zürich where he worked in the field of dynamic NMR spectroscopy and electro-chemistry. He received his habilitation from the ETH Zurich in 1977. In 1979, he became aprofessor in the Department of Organic Chemistry, University of Cologne, and accepted an offerof a chair in organic chemistry at the University of Mainz in 1983. In 1988, he joined the Max-Planck-Society and in 1989 as one of the directors of the Max-Planck Institute for PolymerResearch. His current research topics include new polymer-forming reactions, multidimensionalpolymers with complex shape-persistent architectures, dyes, chemistry and physics of singlemolecules, polymers for electronic and optoelectronic devices, materials for lithium or hydrogenstorage, biosynthetic hybrids, and nanocomposites. In recent years, he has especially focused on

the chemistry and physics of carbon-rich materials such as carbon nanotubes, graphenes, and nanographenes. He has receivednumerous prestigious awards such as the International Award of the Polymer Society of Japan (2009), the ACS Award forPolymer Chemistry (2011), the ERC Advanced Grant (2011), and the Tsungming Tu Award (2011). Since 2006, he acts asAssociate Editor of the Journal of the American Chemical Society and in 2008 and 2009 he served as President of the GermanChemical Society.

David A. Tirrell is the Ross McCollum-William H. Corcoran Professor of chemistry and chemicalengineering at the California Institute of Technology. After earning the BS degree in chemistry atMIT in 1974, he enrolled in the Department of Polymer Science and Engineering at the Universityof Massachusetts, where he was awarded the PhD degree in 1978 for work done under thesupervision of Otto Vogl. After a brief stay with Takeo Saegusa at Kyoto University, he accepted anassistant professorship in the Department of Chemistry at Carnegie Mellon University in the fallof 1978. He returned to Amherst in 1984 and served as director of the Materials ResearchLaboratory at the University of Massachusetts before moving to Caltech in 1998. He chairedthe Division of Chemistry and Chemical Engineering at Caltech from 1999 until 2009. Hiscontributions to chemistry and chemical engineering have been recognized by his election tothe National Academy of Sciences, the National Academy of Engineering, the Institute ofMedicine, and the American Academy of Arts and Sciences.

Robert S. Langer is the David H. Koch Institute Professor (there are 14 Institute Professors at MIT;being an Institute Professor is the highest honor that can be awarded to a faculty member). Dr.Langer has written nearly 1130 articles. He also has approximately 800 issued and pendingpatents worldwide. Dr. Langer’s patents have been licensed or sublicensed to over 220 pharma-ceutical, chemical, biotechnology, and medical device companies. He is the most cited engineerin history. He served as a member of the United States Food and Drug Administration (FDA)’sSCIENCE Board, the FDA’s highest advisory board, from 1995 to 2002 and as its Chairman from1999 to 2002.

Dr. Langer has received over 180 major awards including the 2006 United States NationalMedal of Science; the Charles Stark Draper Prize, equivalent of the Nobel Prize for engineers;the 2008 Millennium Prize, the world’s largest technology prize; and the 2012 Priestley Medal,the highest award of the American Chemical Society. He is the also the only engineer to receive

the Gairdner Foundation International Award; 72 recipients of this award have subsequently received a Nobel Prize. Amongnumerous other awards Langer has received are the Dickson Prize for Science (2002); Heinz Award for Technology, Economyand Employment (2003); the Harvey Prize (2003); the John Fritz Award (2003) (given previously to inventors such as ThomasEdison and Orville Wright); the General Motors Kettering Prize for Cancer Research (2004); the Dan David Prize in MaterialsScience (2005); the Albany Medical Center Prize in Medicine and Biomedical Research (2005), the largest prize in the UnitedStates for medical research; induction into the National Inventors Hall of Fame (2006); the Max Planck Research Award (2008);and the Prince of Asturias Award for Technical and Scientific Research (2008). In 1998, he received the Lemelson-MIT Prize, the

xviii Editors: Biographies

world’s largest prize for invention for being ‘one of history’s most prolific inventors in medicine’. In 1989, Dr. Langer waselected to the Institute of Medicine of the National Academy of Sciences, and in 1992, he was elected to both the NationalAcademy of Engineering and the National Academy of Sciences. He is one of very few people ever elected to all three UnitedStates National Academies and the youngest in history (at age 43) to ever receive this distinction.

Forbes Magazine (1999) and Bio World (1990) have named Dr. Langer as one of the 25 most important individuals inbiotechnology in the world. Discover Magazine (2002) named him as one of the 20 most important people in this area. ForbesMagazine (2002) selected Dr. Langer as one of the 15 innovators worldwide who will reinvent our future. Time Magazine andCNN (2001) named Dr. Langer as one of the 100 most important people in America and one of the 18 top people in science ormedicine in America (America’s Best). Parade Magazine (2004) selected Dr. Langer as one of six ‘Heroes whose research maysave your life’. Dr. Langer has received honorary doctorates from Harvard University, the Mt. Sinai School of Medicine, YaleUniversity, the ETH (Switzerland), the Technion (Israel), the Hebrew University of Jerusalem (Israel), the Universite Catholiquede Louvain (Belgium), Rensselaer Polytechnic Institute, Willamette University, the University of Liverpool (England), BatesCollege, the University of Nottingham (England), Albany Medical College, Pennsylvania State University, NorthwesternUniversity, Uppsala University (Sweden), and the University of California–San Francisco Medal. He received his bachelor’sdegree from Cornell University in 1970 and his ScD from the Massachusetts Institute of Technology in 1974 (both degrees inChemical Engineering).

James E. McGrath received his BS in chemistry from Siena College in New York (1956) and hisMS (1964) and PhD (1967) in polymer science from the University of Akron, where he workedon emulsion and anionic polymerization of synthetic rubbers, ozone cracking, and triblockcopolymer thermoplastic elastomers. After 19 years in industry (Rayonier (cellulose), Goodyear(synthetic rubbers), and Union Carbide (engineering thermoplastics, polyolefins)), he joined theChemistry Department at Virginia Tech in 1975. He is now Ethyl Chair and a UniversityDistinguished Professor. He was director of the first group of NSF Science and TechnologyCenters from 1989 to 2000 on Structural Adhesives and Composites and focused onhigh-temperature polymers including polyimides, polysulfones, and toughened epoxy polymericmatrix resins for carbon fiber composites. He has many contributions to the anionic andring-opening polymerization of dienes, epoxides, and organosiloxanes. His current focus is onpolymeric materials for carbon fibers and membranes, including fuel cells, reverse osmosis water

purification and gas separation systems. He has 50 patents and over 500 publications and has received numerous awards,including election to the National Academy of Engineers (1994), The International SPE award, the Plastics Hall of Fame, andthe ACS awards in Applied Polymer Science (2002) and Polymer Chemistry (2008). He has graduated more than 100 PhDchemists and engineers and remains one of the leaders in polymer science and engineering, with a current group (2011) of 13students and postdoctoral fellows.

Michael A. Hickner received a BS in chemical engineering from Michigan Tech in 1999 and MEngin 2002 and PhD in chemical engineering from Virginia Tech in 2003. In graduate school, heworked under the direction of James E. McGrath and also spent time in the fuel cell group at LosAlamos National Laboratory developing novel aromatic proton exchange membranes for bothhydrogen and direct methanol fuel cells. Before joining the Department of Materials Science andEngineering at Penn State in July 2007, he was a postdoctoral researcher and subsequentlybecame a staff member at Sandia National Laboratories in Albuquerque, NM, where he con-ducted experimental investigations and modeling studies of liquid water transport in fuel cellsand porous media and properties of ion-containing membranes, electrochemical reactors, andnanoporous membranes for water treatment applications. His research group at Penn State isfocused on the synthesis and properties of ion-containing polymers, measurement of water–polymer interactions using spectroscopic techniques, and the study of self- and directed assembly

of polymeric nanostructures for fast transport. He has ongoing projects in new polymer synthesis, fuel cells, batteries, watertreatment membranes, and organic photovoltaic materials. He is currently an assistant professor and the Virginia S. andPhilip L. Walker Jr. Faculty Fellow in the Materials Science Department at Penn State. Hickner’s work has been recognized by a

Editors: Biographies xix

Powe Junior Faculty Enhancement Award (2008), Young Investigator Awards from ONR and ARO (2008), a 3M Non-tenuredFaculty Grant (2009), and a Presidential Early Career Award for Scientists and Engineers from President Obama in 2009. He hasfive US and international patents and over 60 peer-reviewed publications since 2001 that have been cited more than 2900 timesas of 2011.

Rainer Höfer graduated in Inorganic Chemistry with Professor Oskar Glemser at theGeorg-August Universität zu Göttingen in 1973 with work on sulfur–nitrogen–fluorine chemis-try. He spent three years at the Technical University of Oran (ENSEP), Algeria, as Maître deConférences and Directeur de l’Institut de Chimie before joining Henkel in Düsseldorf. WithHenkel KGaA and then as Vice President Research & Technology with Cognis GmbH inMonheim, he has assumed global research and development, application technology, technicalsales service, strategic business development, and technology scouting responsibilities in oleo-chemistry, polymer chemistry, and surfactant chemistry for the polymerization, coatings, graphicarts, adhesives, engineering plastics, agrochemical, synthetic lubricants, mining, and pulpand paper markets. He is founder of Editorial Ecosiris with consultancy and publishing activitiesin the domains of green chemistry, renewable resources, sustainable development, andinterculturation.

xx Editors: Biographies

CONTRIBUTORS OF VOLUME 10

TW AbrahamCargill, Inc., Wayzata, MN, USA

D AchtenBayer MaterialScience AG, Leverkusen, Germany

G AvarBayer MaterialScience AG, Leverkusen, Germany

B BaeUniversity of Yamanashi, Yamanashi, Japan

F BonfilsCIRAD, UMR IATE, Montpellier, France

C BontenUniversity of Stuttgart, Stuttgart, Germany

M CartaultANVIS SD France S. A. S., Decize, France

H CasselmannBayer MaterialScience AG, Leverkusen, Germany

F ChenWashington State University, Pullman, WA, USA; andPacific Northwest National Laboratory, Richland, WA,USA

M CookAir Products & Chemicals Inc., Utrecht, The Netherlands

G CrapperAkzo Nobel Powder Coatings Limited, Gateshead, UK

KI DragetNorwegian University of Science and Technology(NTNU), Trondheim, Norway

H-J EndresInstitute for Bioplastics and Biocomposites (IfBB),Hanover, Germany

P FuertesRoquette Frères, Lestrem, France

D GlittenbergCargill Deutschland GmbH, Krefeld, Germany

MD GuiverNational Research Council, Ottawa, ON, Canada; andHanyang University, Seoul, Republic of Korea

BF HabenichtUniversity of Tennessee, Knoxville, TN, USA

E HaberstrohRWTH Aachen University, Aachen, Germany

R HagenUhde Inventa-Fischer GmbH, Berlin, Germany

S Hamrock3M Fuel Cell Components Program, St. Paul, MN, USA

K HanThe Pennsylvania State University, University Park, PA,USA

T HeinzeFriedrich Schiller University of Jena, Jena, Germany

R HöferEditorial Ecosiris, Düsseldorf, Germany

MA HicknerThe Pennsylvania State University, University Park, PA,USA

RP HjelmLos Alamos National Laboratory, Los Alamos, NM, USA

S HoldcroftSimon Fraser University, Burnaby, BC, Canada; andInstitute for Fuel Cell Innovation, Vancouver, BC, Canada

G HublikJungbunzlauer, Wulzeshofen, Austria

W HusterWacker Chemie AG, Burghausen, Germany

NJ IroffEvonik Oil Additives Inc, Horsham, PA, USA

TR KeenanGelita USA, Inc., Sioux City, IA, USA

xxi

DS KimLos Alamos National Laboratory, Los Alamos, NM, USA

YS KimLos Alamos National Laboratory, Los Alamos, NM, USA

A KlippsteinAir Products & Chemicals Inc., Utrecht, The Netherlands

H Krählingtecpol GmbH, Hannover, Germany

M-P LabeauRhodia Inc, Bristol, PA, USA

T LiebertFriedrich Schiller University of Jena, Jena, Germany

H LutzWacker Chemie AG, Burghausen, Germany

JE McGrathVirginia Polytechnic Institute and State University,Blacksburg, VA, USA

U Meier-WesthuesBayer MaterialScience AG, Leverkusen, Germany

WE MickolsConocoPhillips Company, Bartlesville, OK, USA

CK MittelsteadtGiner Electrochemical Systems, Newton, MA, USA

K MiyatakeUniversity of Yamanashi, Yamanashi, Japan

MM MlezivaKimberly-Clark Corporation, Neenah, WI, USA

M MöllerDWI an der RWTH Aachen e.V., Aachen, Germany

S MonaghanAir Products & Chemicals Inc., Utrecht, The Netherlands

RB MooreVirginia Polytechnic Institute and State University,Blacksburg, VA, USA

F MüllerEvonik Industries AG, Essen, Germany

RAA MuzzarelliUniversity of Ancona, Ancona, Italy

CD NeveuEvonik Oil Additives GmbH, Darmstadt, Germany

AM OsbornVirginia Polytechnic Institute and State University,Blacksburg, VA, USA

SJ PaddisonUniversity of Tennessee, Knoxville, TN, USA

J-P PascaultUniversité de Lyon, INSA de Lyon, Lyon, France

C PopescuDWI an der RWTH Aachen e.V., Aachen, Germany; andUniversity ‘Aurel Vlaicu’, Arad, Romania

U RiedelJohnson Controls GmbH, Burscheid, Germany

J Sainte-BeuveCIRAD, UMR IATE, Montpellier, France

I SartoriusPlastics Europe Deutschland e.V., Frankfurt/M., Germany

D SavantCase Western Reserve University, Cleveland, OH, USA

DA SchiraldiCase Western Reserve University, Cleveland, OH, USA

R SchwalmBASF SE, Ludwigshafen, Germany

M SeligWacker Chemie AG, Burghausen, Germany

A Siebert-RathsInstitute for Bioplastics and Biocomposites (IfBB),Hanover, Germany

S SilberEvonik Industries AG, Essen, Germany

G Skjåk-BrækNorwegian University of Science and Technology(NTNU), Trondheim, Norway

R SondjajaEvonik Oil Additives GmbH, Darmstadt, Germany

JA StaserGiner Electrochemical Systems, Newton, MA, USA

T StöhrEvonik Oil Additives GmbH, Darmstadt, Germany

F ThevenetNexira, Rouen, France

EMW TsangSimon Fraser University, Burnaby, BC, Canada

L VaysseCIRAD, UMR IATE, Montpellier, France; and UMRIATE, Kasetsart University, Bangkok, Thailand

JH WangKimberly-Clark Corporation, Neenah, WI, USA

Q WangThe Pennsylvania State University, University Park, PA,USA

xxii Contributors of Volume 10

M WatanabeUniversity of Yamanashi, Yamanashi, Japan

G WegenerTechnische Universität München, München, Germany

H-P WeitzelWacker Chemie AG, Burghausen, Germany

C WelchLos Alamos National Laboratory, Los Alamos, NM, USA

E WindeisenTechnische Universität München, München, Germany

M Yandrasits3M Fuel Cell Components Program, St. Paul, MN, USA

J ZhangWashington State University, Pullman, WA, USA

Contributors of Volume 10 xxiii

PREFACE

Comprehensive Polymer Science was published in 1989 as a set of seven volumes and then supplemented by twoadditional volumes. This excellent print collection comprehensively covered the entire field of polymer scienceat that time. Much of the information is currently still as valuable as it was then, although some aspects are seendifferently now. Those differences are important in order to understand the enormous development polymerscience has taken since 1989. When we developed the concept for an entirely new edition of Polymer Science:A Comprehensive Reference, we intended not only to update and replace the original edition of ComprehensivePolymer Science, (we are pleased to announce that it will be soon available in electronic format) but also tofocus on a widely observed transition of polymer science, from exploring only macromolecules, polymericmaterials, and polymerization processes to become part of a comprehensive study on molecular soft matterscience enabling advancements in other related disciplines.

In 1989, polymer science had just started a second stage of development after completing the scientificand technological evolution of its fundamental principles. This second stage has been driven by thecontinuously increasing understanding of the complexity in the structural organization of polymermaterials and the challenge to understand and to master the fundamental underlying structure formationon exceedingly large length scales. Material functions based on molecular organization have been thefocus of outstanding and highly recognized achievements, for example, new concepts for macromoleculararchitectures, self-assembling properties, electronically conductive polymers, ultrathin films, and hybridstructures or bioconjugates.

We are once again at the beginning of another step forward in the development of polymer science. Basedon an increasing understanding of molecular processes, for example, advancements in mastering molecularself-assembly and the interfacing of bottom-up and top-down approaches to molecular organization, thetremendous progress in understanding the molecular basis of biological processes, and the growing ability todescribe more and more complex systems with the rigorous approaches of physics, the traditional bound-aries between these fields of science are being torn down. At the same time, the differentiation betweenmaterials and living organisms is becoming more and more indistinct, that is, machines are becomingbiological and biology is becoming engineered. Already a new field of biofunctional materials is emerging,where ‘biofunctional’ represents the ability to activate and control a biological response. As a consequence,polymer science is facing a shift in paradigm from having been focused on itself, toward creating an enablingscience that provides an understanding of a much broader base of ‘molecular soft matter science’ that reachesout and provides important contributions toward biology and information- and energy-related technologies.This development is seen in the increased worldwide interest in bioinspired materials engineering biomi-metic materials and in the creation of smart nanostructures, as well as polymeric electronic and photonicdevices.

The great progress that has been made in many areas of polymer science since 1989 is reflected in, and aidedby, three major developments: (1) the advancements in precision polymerization and synthetic combination ofwell-defined (bio)macromolecular building blocks, for example, controlled polymerization processes, and newmacromolecular architectures; (2) the progress in characterization methods spanning an enormous increase inlength- and timescales, for example, single molecule imaging and spectroscopy that provides an improvedinsight on slow and cooperative relaxation and ordering; and (3) significant improvement in the under-standing of complex macromolecular systems like polyelectrolytes and block and graft copolymers amplified

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by the dramatically enhanced power of computational simulations. In addition, much interest has beenfocused on polymers and materials coming from biological sources, or those designed to serve specificfunctions in a biological system, which is partly driven by environmental and sustainability aspects, but alsoby the rising interest in smart biomimetic and bioactive materials. Besides the emergence of new biomaterialsand biohybrid macromolecules, this also leads to a new interest in waterborne polymers and polymer synthesisin aqueous systems, for example, enzymatic polymerization.

The organization and outline of the ten volumes of this edition of Polymer Science: A ComprehensiveReference has been chosen to give consideration to these developments, but also to link the fundamentalsof polymer science, as developed over almost 100 years, with the challenges of the ever more complexsystems, and introduce connections that will dominate the future development of a polymer-based mole-cular soft matter science. Besides the classic print edition, this new edition of Polymer Science: A ComprehensiveReference is also provided as an e-version, enabled with efficient cross-referencing and multimedia. Weinvited the top world experts in polymer science to serve as volume editors and this ‘dream team’ hasprepared a ten-volume set with 269 chapters covering both the fundamentals and the most recent advancesin polymer science. Volumes 1–5 are directed toward the fundamentals of polymer science, that is, polymerphysics and physical chemistry, advanced characterization methods, and polymer synthesis. In spite of thebreadth of information collected in these five volumes, it has not been possible to cover all aspects ofpolymer science. In some cases, the reader must refer to the chapters in volumes 6–10 that address topicaldevelopments with a stronger material focus.

The progress in polymer science is revealed in essentially all chapters of this edition of Polymer Science:A Comprehensive Reference. In Volume 1, edited by Khokhlov and Kremer, this is reflected in the improvedunderstanding of the properties of polymers in solution, in bulk, and in confined situations such as inthin films. Volume 2, edited by Spiess, Hashimoto, and Takenaka, addresses new characterizationtechniques that were not covered in the first edition, or did not even exist in 1989, such as high-resolution optical microscopy, scanning probe microscopy, and other procedures for surface and interfacecharacterization. Volume 3, edited by Coates and Sawamoto, presents the great progress achieved inprecise synthetic polymerization techniques for vinyl monomers to control macromolecular architecture:the development of metallocene and post-metallocene catalysis for olefin polymerization, new ionicpolymerization procedures, atom transfer radical polymerization, nitroxide-mediated polymerization,and reversible addition-fragmentation chain transfer systems as the most often used controlled/livingradical polymerization methods. Volume 4, edited by Penczek and Grubbs, is devoted to kinetics,mechanisms, and applications of ring-opening polymerization of heterocyclic monomers and cycloolefins(ROMP), as well as to various less common polymerization techniques. Polycondensation and non-chainpolymerizations, including dendrimer synthesis and various ‘click’ procedures, are covered in Volume 5,edited by Schmidt and Ueda. Volume 6, edited by Müller and Wooley, focuses on several aspects ofcontrolled macromolecular architectures and soft nanoobjects including hybrids and bioconjugates. Manyof the achievements would have not been possible without new characterization techniques like atomicforce microscopy (AFM) that allowed direct imaging of single molecules and nanoobjects with a precisiononly recently available. An entirely new aspect in polymer science is based on the combination ofbottom-up methods such as molecularly programmed self-assembly with top-down structuring such aslithography and surface templating, as presented in Volume 7, edited by Kumacheva and Russell. Itencompasses polymer and nanoparticle assembly in bulk and under confined conditions or influenced byan external field, including thin films, inorganic–organic hybrids, or nanofibers. Volume 8, edited byMuellen and Ober, expands these concepts, focusing on applications in advanced technologies, forexample, in electronic industry and centers, in combination with the top-down approach and functionalproperties like conductivity. Another type of functionality that is rapidly increasing in importance inpolymer science is introduced in volume 9, edited by Langer and Tirrell. This deals with various aspects ofpolymers in biology and medicine, including the response of living cells and tissue to the contact withbiofunctional particles and surfaces. Volume 10, edited by Höfer, Hickner, and McGrath, is devoted to thescope and potential provided by environmentally benign and green polymers, as well as energy-relatedpolymers. It discusses new technologies needed for a sustainable economy in our world of limitedresources. Common to all approaches in this edition of Polymer Science: A Comprehensive Reference is themastering of an increasing complexity of the polymer material structure needed for a change in focus

xxvi Preface

from commodities to materials for various advanced applications, related to energy, environment, andbiomedicine.

We hope that this new edition of Polymer Science: A Comprehensive Reference will provide the readers withstate-of-the-art coverage of all important and modern aspects of polymer science. We would like to thank allvolume editors, contributing authors, and Elsevier personnel for their efforts, not only in completing theproject in a timely fashion but also in ensuring the outstanding quality of the final product.

Krzysztof MatyjaszewskiMartin Möller

Preface xxvii

FOREWORD

Polymer science has experienced a most impressive expansion in depth, breadth, and diversity throughdevelopments in its core domains as well as at the interfaces of polymer chemistry and physics with materialsscience, supramolecular chemistry, nanoscience, biophysics, and biology. These developments are reflected inthe evolution from the original edition of Comprehensive Polymer Science to the present edition Polymer Science: AComprehensive Reference. None of these areas can nowadays be envisaged without considering the contributionsof polymer science to their own progress. At the same time and with increasing impact, scientists from the otherfields contribute new findings and concepts to polymer science and many novel and topical approaches arerooted in the areas mentioned above.

The extension of the concepts and features of supramolecular chemistry from discrete species topolymolecular entities has opened novel perspectives in materials science. It defines a field of supramole-cular materials that rests on the explicit implementation of intermolecular interactions and recognitionprocesses for controlling the buildup, the architecture, and the properties of polymolecular assemblies asthey emerge from their components through self-organization. Such spontaneous but directed self-assemblyis of major interest for the supramolecular design, synthesis, and engineering of novel materials presentingnovel properties.

Our own connection with polymer science stems from the introduction and progressive establishmentof a supramolecular polymer chemistry built on entities generated by polyassociation between molecular‘monomeric’ components through dynamic noncovalent interactions with molecular recognition betweenthe components. The more recent development of dynamic covalent chemistry led to the investigation ofdynamic covalent polymers formed by polycondensation through reversible reactions between subunitsbearing suitable functional groups. The dynamic features of both these molecular and supramolecularpolymers characterize dynamic polymers, dynamers, on both levels. Dynamers may be defined asconstitutional dynamic polymers, that is, polymeric entities whose monomeric components are linkedthrough reversible connections and have therefore the capacity to modify their constitution by exchangeand reshuffling of their components. They may undergo constitutional variation by incorporation,decorporation, and exchange of components. These dynamic properties confer to dynamers the abilityto undergo adaptation and driven evolution in response to physical stimuli or chemical effectors.Dynamers are thus constitutional dynamic materials resulting from the application of the principles ofconstitutional dynamic chemistry to polymer science. As such, they open wide perspectives towardadaptive materials and technologies.

By the nature and the size of its objects, polymer science plays a very important role in nanoscience andnanotechnology, both areas experiencing a profound mutual fertilization. Polymer science has also beensubject to major developments at the interface with biology, by the incorporation of biological componentsinto synthetic polymers, as well as by applying its own principles to the understanding of the features ofbiological macromolecules.

An extremely rich variety of novel architectures, processes, and properties have resulted and may be expectedto further emerge from the blending of polymer science with the other areas of materials chemistry and physics,with ongoing developments in chemistry as well as with the investigation of complex molecular behavior inbiological sciences.

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Polymer Science: A Comprehensive Reference provides complete and up-to-date coverage of the most impor-tant contemporary aspects and fundamental concepts of polymer science. It will become the indispensablereference not only for polymer scientists but also for all researchers in disciplines related to macromolecularsystems.

Jean-Marie LehnISIS - Université de Strasbourg, Strasbourg, France

xxx Foreword