2017_Book_PolymerChemistry.pdf - Sebastian Koltzenburg Michael Maskos Oskar Nuyken Polymer Chemistry Polymer Chemistry Sebastian Koltzenburg Michael

2017_Book_PolymerChemistry.pdf - Sebastian Koltzenburg...

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Unformatted text preview: Sebastian Koltzenburg Michael Maskos Oskar Nuyken Polymer Chemistry Polymer Chemistry Sebastian Koltzenburg Michael Maskos Oskar Nuyken Polymer Chemistry Sebastian Koltzenburg Functional Biopolymers BASF SE, GMM/B - B001 Ludwigshafen, Germany Oskar Nuyken Garching, Germany Michael Maskos Fraunhofer ICT-IMM Mainz, Germany Translated by Karl Hughes Forewords by Rolf Mülhaupt and Krzysztof Matyjaszewski ISBN 978-3-662-49277-2    ISBN 978-3-662-49279-6 (eBook) DOI 10.1007/978-3-662-49279-6 Library of Congress Control Number: 2016943641 © Springer-Verlag Berlin Heidelberg 2017 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made. Cover illustration: With kind permission by Gurit Printed on acid-free paper This Springer imprint is published by Springer Nature The registered company is Springer-Verlag GmbH Germany The registered company address is: Heidelberger Platz 3, 14197 Berlin, Germany v Foreword Today, synthetic polymers can be found everywhere and are used in nearly every device. All computer chips used in our desktops, laptops, smartphones, or tablets are enabled by polymers used as photoresistors in microlithographic processes or as organic light-­ emitting diodes. Cutting-edge biomedical applications require polymers for tissue or bone engineering, drug delivery, and tubing and containers for intravenous delivery of medications. The interior of every automobile is almost entirely made from polymers, and they are also used for automobile body parts and under-the-hood applications. New lightweight and strong nanocomposite polymeric materials have enabled energy-­efficient Dreamliner and A380 aircrafts. The construction industry uses polymers as insulating materials, sealants, adhesives, and coatings. Many new applications require smart polymers that respond to external stimuli, which can be used in sensors, shape memory materials, and self-healing systems. Thus, polymers are perhaps the most important materials in our society today, and their annual production exceeds 200 million tons. Although approximately 50% of chemists in the USA, Japan, and Western Europe work with polymers, polymer education has not yet reached the appropriate level, and many of those chemists neither take advantage of the unique properties of polymeric materials nor fully comprehend the synthetic pathways to control precisely macromolecular architecture. Polymer Chemistry by Koltzenburg, Maskos, and Nuyken covers all aspects of polymer science, starting with fundamental polymer physical chemistry and physics, including all classical and modern synthetic techniques, and ending by reviewing various applications including more specialized uses in energy, environment, biomaterials, and other advanced fields. The authors present the material in 22 chapters in a very lucid and attractive way and identify the most important references for each chapter. This textbook is expected to be very helpful for all beginners in polymer science and also for more experienced polymer scientist. I read the book with great interest and believe that it will become an excellent introductory polymer science textbook for senior undergraduate and graduate students. Krzysztof Matyjaszewski J.C. Warner University Professor of Natural Sciences Carnegie Mellon University, Pittsburgh, PA, USA Fall 2015 Foreword to the German Edition Small molecules such as drugs and food ingredients prolong human life, whereas macromolecules as versatile structural and functional materials are essential for a high quality of life, making “high tech” products available to all mankind. Originally developed as substitutes for natural materials such as ivory, silk, and natural rubber, highly versatile modern synthetic polymers can readily be tailored and processed to meet the diverse needs of our society and our modern technologies. Nowadays polymeric materials and systems are indispensable in modern life. The wide spectrum of polymer applications spans from food packaging to construction, textiles, automotive and aerospace engineering, rubbers, paints, adhesives, and system-integrated functional polymers indispensable in electronics, flexible microsystems, and energy and medical technologies. Their unique versatility in terms of tailored property profiles, ease of processing, application range, and recycling, coupled with their outstanding resource, ecological, energy, and cost efficiency, is not met by any other class of materials. Today polymeric materials play an important role in sustainable development. The success of polymer development and the high demand for polymer products by the rapidly growing world population are reflected by the surging polymer production capacity, which today exceeds 300 million tons per annum. Following the Stone Age, the Bronze Age, and the Iron Age, in the twenty-first century we are now living in the Polymer Age. Anyone interested in sustainable development become increasingly confronted with synthetic and natural macromolecules and their applications. In almost every facet of modern technology and in innovative problem solutions, the development of engineering plastics and functional polymers plays a key role. In order to convert macromolecules into useful materials and sustainable products it is essential to understand the basic correlations between molecular polymer design, polymer technology, processing, applications, and sustainability. Unlike most conventional textbooks with a rather narrow focus on traditional chemistry and physics, this textbook clearly goes beyond the limits of the individual disciplines and presents a fascinating view of the challenges and prospects of modern interdisciplinary polymer sciences and engineering and their impact on modern technologies. It is obvious that all three authors bring to bear their profound experiences in teaching and research covering the broad field of polymer science and engineering. Furthermore, they are highly skilled in didactics and have succeeded in pointing out the relevance of tailoring polymers with respect to polymer applications. This team of three authors has successfully merged their complementary skills, own experiences, and different points of view. In 22 chapters the authors have impressively managed to present a comprehensive view of the extensive and rapidly developing fields of polymer sciences and technology in an appealing and easy-to-read format. In addition to covering the fundamentals of polymer chemistry and physics, the book describes the synthetic methods and polymer analytics as well as the technological aspects which are essential for tailoring polymeric materials, including multicomponent and multiphase polymer systems. Moreover, illustrated by carefully selected examples of specific applications, this text book gives an excellent view on the hot topics in polymer sciences as well as on environmental aspects of polymers, recycling, bio-based polymers, and modern research trends. The result of this remarkable and successful three-author co-production Foreword to the German Edition vii is a methodically well-conceived and easy-to-read textbook that serves as a desk book reference for polymer scientists, engineers, educators, and students. This textbook represents a valuable source of information for those who are already familiar with science. Because of its clear and didactic style, this textbook represents an excellent choice of reading for those who are approaching the subject of polymer sciences and engineering for the first time. The length of the book is more than adequate to cope with the complexity and breadth of this highly diversified and interdisciplinary field. Despite its high density of valuable information, this textbook reads well and I am firmly convinced that it is certain to become one of the key reference textbooks in the field of polymer sciences. Rolf Mülhaupt Freiburg June 2013 Acknowledgement The success of the German edition, the encouragement of colleagues in many countries, and the honor of winning the 2015 prize (Literaturpreis der Chemischen Industrie) from the Organization of German Chemical Industry (Verband der Chemischen Industrie VCI) persuaded us to translate our textbook into English to make it more available to a broader international audience. The authors would like to thank the team of translators from the language department of the TU Munich, led by Mr Karl Hughes, for their dependable cooperation and continuous willingness to discuss suggestions for alteration. The contribution of Dr Stephen Pask has been particularly valuable, both in terms of language and his specialist knowledge. Thanks to his expertise and tireless unflagging commitment and innumerable discussions in which Karl Hughes and his team were constantly involved, we now have an English text which, we believe, contains numerous improvements compared to the German edition. We would like to thank Dr Kyriakos A. Eslahian, Dr Thomas Lang, and Jonas Schramm for translating and redrawing the figures and for suggesting and making corrections where necessary. We would like to express our special gratitude to Christoph Bantz who read the final version of the entire document and provided patient and constructive ­criticism. We also owe thanks to many interested and critical readers of the German edition who have contacted us to point out typos and mistakes. In this respect we would specifically like to name our colleagues Prof Dr André Laschewsky, University of Potsdam and Prof Dr Ulrich Ziener, University of Ulm. A special thank you goes to our sponsors for this translation project: the “Fonds der Chemischen Industrie” and the group of macromolecular chemistry of the Gesellschaft Deutscher Chemiker (GDCh). Thanks are also expressed to Springer-Verlag, especially Ms Merlet Bencke-­Braunbeck and Dr Tobias Wassermann, for their support during this project. Finally, as with the German edition, we have enjoyed continued encouragement and support from our families, for which we can never thank them enough! Sebastian Koltzenburg Michael Maskos Oskar Nuyken January 2016 ix Contents 1 Introduction and Basic Concepts.........................................................................................   1 2 Polymers in Solution....................................................................................................................  17 3 Polymer Analysis: Molar Mass Determination............................................................  39 4 Polymers in Solid State...............................................................................................................  93 5 Partially Crystalline Polymers............................................................................................... 105 6 Amorphous Polymers.................................................................................................................. 119 7 Polymers as Materials................................................................................................................. 141 8 Step-Growth Polymerization................................................................................................. 163 9 Radical Polymerization.............................................................................................................. 205 10 Ionic Polymerization.................................................................................................................... 245 11 Coordination Polymerization................................................................................................. 293 12 Ring-Opening Polymerization............................................................................................... 321 13 Copolymerization.......................................................................................................................... 349 14 Important Polymers Produced by Chain-Growth Polymerization................ 381 15 Chemistry with Polymers.......................................................................................................... 407 16 Industrially Relevant Polymerization Processes....................................................... 425 17 The Basics of Plastics Processing......................................................................................... 439 18 Elastomers.......................................................................................................................................... 477 19 Functional Polymers.................................................................................................................... 493 x Contents 20 Liquid Crystalline Polymers.................................................................................................... 515 21 Polymers and the Environment............................................................................................ 533 22 Current Trends in Polymer Science..................................................................................... 551 Supplementary Information Index......................................................................................................................................................... 577 1 Introduction and Basic Concepts 1.1 Polymers: Unique Materials – 2 1.2 Definition of Terminology and Basic Concepts – 4 1.2.1 Fundamentals – 4 1.2.2 Polyreactions – 5 1.2.3 Nomenclature of Polymers – 7 1.3 Polymer Architectures – 8 1.3.1 Linear and Branched Macromolecules – 8 1.3.2 Isomerism in Polymers – 10 1.3.3 Copolymers – 14 References – 16 © Springer-Verlag Berlin Heidelberg 2017 S. Koltzenburg et al., Polymer Chemistry, DOI 10.1007/978-3-662-49279-6_1 1 2 1 Chapter 1 · Introduction and Basic Concepts Among the many areas of chemistry, polymer science is a comparatively new field. The empirical use of polymeric materials made from natural substances has been documented for centuries; however, only the pioneering work of the late Hermann Staudinger (1926), a Nobel laureate, in the 1920s provided the basis for a systematic understanding of this class of materials. In the decades since then, polymer science has developed to become both technically demanding and industrially extremely important. In particular, polymer science is characterized by its interdisciplinary nature: 55 Most technologically relevant macromolecules1 are based on a carbon backbone and thus belong in the realm of organic chemistry. 55 Approximately half of all polymers produced today are synthesized using organo-­ metallic catalysts. 55 A description of the behavior of both solid polymers and their solutions is now based on well-established physical and physicochemical theories. 55 Because macromolecules are often used in the area of classical materials, processing and molding of polymers is an essential step in the production of finished products. Thus, engineering science is also important. In medical technologies, polymers are used in highly specialized applications, such as artificial heart valves, eye lenses, or as materials for medical devices. Last but not least, as well as the vast and significant use of synthetic polymers, macromolecules are of crucial biological importance. Undoubtedly the most important polymer in the world—without which human existence would not be possible—is DNA. Without its polymeric nature, DNA could not fulfill its essential role as the memory molecule of living systems. If the molecules were not linked to a polymeric strand, DNA would be nothing more than a mixture of four different bases with no defined structure and therefore without biological function. In addition to the millions of tons of natural rubber processed annually, further examples of biopolymers essential to life include proteins that catalyze chemical reactions as enzymes, form membranes, or act as antibodies differentiating between friend and foe. This chapter deals with the basic concepts and definitions of polymer science and especially the most important question that a natural scientist can ask: “Why?” In particular, why should one take an interest in this field? It is shown that polymers constitute a class of materials that not only make an essential contribution to the existence of life in the form of biological macromolecules, but without which, thanks to their myriad technical applications, our modern daily life would be no longer conceivable. 1.1 Polymers: Unique Materials Even if we restrict ourselves to the field of non-biogenic, traditional materials, macromolecules are a material class of unparalleled versatility. However, the range of properties covered by polymeric materials is much broader than that of traditional materials. Thus, for example: 1 Originally, a distinction was made between macromolecular substances and polymers. This differentiation has become unnecessary. In this book, these terms are used congruently. 1.1 · Polymers: Unique Materials 3 55 Glass fiber reinforced plastics can have tensile strengths that rival, e.g., steel, whereas other polymers such as polyurethane foams can be used as soft cushions or mattresses. 55 Most plastics are electrical insulators, but highly conjugated polymers have also been synthesized with specific conductivities of the same order of magnitude of those of highly conductive metals (Naarmann and Theophilou 1987). 55 The density of porous polymeric materials can be varied across a very wide range. In particular, from polymer foams such as Styrofoam®, extremely lightweight articles can be produced.2 55 The melting point of polymers can also be greatly modified by varying the macromolecular architecture. Some polymers can be physically described as highly viscous melts even at room temperature, whereas other polymers have melting points of several hundred degrees Celsius, and can be heated to red heat or sintered. Of course, the temperature range of the melting or softening point is critical for the temperature at which a material can be used or processed. On the one hand, a high melting point allows a high service temperature but requires a lot of energy to process the molten material into the final shape. For many materials in everyday life, which are only used at room temperature, a low melting point is an advantage because they can be processed much more resource-efficiently than materials with a high melting point. Here, too, the unrivaled variability that polymers offer is often a decisive and advantageous factor. Because of their great versatility and their resulting unique material properties, synthetic polymeric materials have become indispensable in our daily lives. Many familiar applications can only be realized using macromolecular materials: 55 The electrical and electronics industries in their current form are difficult to envisage without polymers. This statement includes seemingly trivial applications such as the sheathing for electric cables—no other non-polymeric substance clas...
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