Lecture Notes In Chemistry 82 Wei-Fang Su Principles of Polymer Design and Synthesis Springer
Lecture Notes In Chemistry 82 Principles of Polymer Design and Synthesis Wei-Fang Su
Foreword While the ubiquity of polymers might imply that this field forms a significant portion of undergraduate and graduate courses,students typically leave their studies with only rudimentary knowledge of this important subject.This is perhaps particularly surprising given that many of these new graduates will enter careers in the consumer goods,pharmaceutical,materials,electronics,or other industries where polymers hold the key to the performance of the final product.With this in mind,it is critical that we better prepare our students for their ultimate careers.For this reason,Principles of Polymer Design and Synthesis is a welcome addition to the toolkit for young scientists and engineers,providing a solid base for learning about the incredible influence of polymers to modern life.The logical format of the book and its combination of breadth and depth will also allow it to serve as a very useful text for established professionals who are entering the broad field of polymer chemistry or researchers who want to freshen up their knowledge with some of the latest directions in polymer design and synthesis. The book introduces polymers to chemists,material scientists,and engineers with no prior experience of the area in a straightforward,rigorous,and logical manner. Intended for students who have completed undergraduate courses in organic and physical chemistry,the chapters cover the properties,synthesis,and characterization of polymeric materials.Readers will gain an appreciation for the diversity of poly- mers with examples ranging from natural proteins,rubber,and cellulose to the huge variety of synthetic materials that are used to produce fibers,plastics,and elastomers. The aim is to equip scientists and engineers with a deeper understanding of how the structure of polymers dictates their function and potential applications- whether that may be in cheap polyethylene bags or sophisticated light emitting materials for flexible displays.Not only will readers learn how to synthesize common polymers,they will also gather greater knowledge of the principles for designing materials and an appreciation for the state of the art.The value in Principles of Polymer Design and Synthesis is in giving students and researchers a flavor of the breadth of polymer science and inspiring them to delve deeper into the field and develop materials for the next great advances to impact our lives. Craig J.Hawker
Foreword While the ubiquity of polymers might imply that this field forms a significant portion of undergraduate and graduate courses, students typically leave their studies with only rudimentary knowledge of this important subject. This is perhaps particularly surprising given that many of these new graduates will enter careers in the consumer goods, pharmaceutical, materials, electronics, or other industries where polymers hold the key to the performance of the final product. With this in mind, it is critical that we better prepare our students for their ultimate careers. For this reason, Principles of Polymer Design and Synthesis is a welcome addition to the toolkit for young scientists and engineers, providing a solid base for learning about the incredible influence of polymers to modern life. The logical format of the book and its combination of breadth and depth will also allow it to serve as a very useful text for established professionals who are entering the broad field of polymer chemistry or researchers who want to freshen up their knowledge with some of the latest directions in polymer design and synthesis. The book introduces polymers to chemists, material scientists, and engineers with no prior experience of the area in a straightforward, rigorous, and logical manner. Intended for students who have completed undergraduate courses in organic and physical chemistry, the chapters cover the properties, synthesis, and characterization of polymeric materials. Readers will gain an appreciation for the diversity of polymers with examples ranging from natural proteins, rubber, and cellulose to the huge variety of synthetic materials that are used to produce fibers, plastics, and elastomers. The aim is to equip scientists and engineers with a deeper understanding of how the structure of polymers dictates their function and potential applications— whether that may be in cheap polyethylene bags or sophisticated light emitting materials for flexible displays. Not only will readers learn how to synthesize common polymers, they will also gather greater knowledge of the principles for designing materials and an appreciation for the state of the art. The value in Principles of Polymer Design and Synthesis is in giving students and researchers a flavor of the breadth of polymer science and inspiring them to delve deeper into the field and develop materials for the next great advances to impact our lives. Craig J. Hawker v
Preface Synthetic polymers are vital materials used in modern daily life from packaging, electronics,medical devices,clothing,vehicles,buildings,etc.How can a scientist or engineer synthesize and utilize polymers to solve the problems of daily life? This is the objective of this textbook to provide students with fundamental knowledge in the design and synthesis of polymers to achieve specific properties required in the applications.To have the ability to design a polymer,one has to understand the chemical structure effects on the physical and chemical charac- teristics of polymer first.Therefore,in this book,the first five chapters discuss the properties and characterization of polymers.Then,six chapters are followed to discuss the principles of polymerization reactions including step,radical chain, ionic chain,chain copolymerization,coordination,and ring opening.They cover the descriptions of how commonly known polymers are synthesized. This book is intended as an introductory textbook for one semester course in polymer chemistry or polymer synthesis at the advanced undergraduate or beginning graduate level of students in chemistry,chemical engineering,and material science and engineering with no prior training in polymer.The students who uses this book should have completed undergraduate courses in organic chemistry and physical chemistry.After going through the lectures or reading the text of this book,they will have the capability to synthesize common known polymers and comprehend the advanced polymerization reactions reported in the literature to further design and synthesize new polymers. Finally,I would like to thank the encouragement and patience obtained from my husband Cheng-Hong Su during the course of this work and the inspiration, chemical formula drawing,and proof reading from my students Chun-Chih Ho, Shih-Hsiang Lin,Tzu-Chia Huang,Shang-jung Wu,Shih-Chieh Wang,Jhin-Fong Lin,and Hsueh-Chung Liao.Thanks are also due to typing and organization of the manuscript done by Shiow-Wei Wang and drawing of figures done by Yin-Hsi Lin. vii
Preface Synthetic polymers are vital materials used in modern daily life from packaging, electronics, medical devices, clothing, vehicles, buildings, etc. How can a scientist or engineer synthesize and utilize polymers to solve the problems of daily life? This is the objective of this textbook to provide students with fundamental knowledge in the design and synthesis of polymers to achieve specific properties required in the applications. To have the ability to design a polymer, one has to understand the chemical structure effects on the physical and chemical characteristics of polymer first. Therefore, in this book, the first five chapters discuss the properties and characterization of polymers. Then, six chapters are followed to discuss the principles of polymerization reactions including step, radical chain, ionic chain, chain copolymerization, coordination, and ring opening. They cover the descriptions of how commonly known polymers are synthesized. This book is intended as an introductory textbook for one semester course in polymer chemistry or polymer synthesis at the advanced undergraduate or beginning graduate level of students in chemistry, chemical engineering, and material science and engineering with no prior training in polymer. The students who uses this book should have completed undergraduate courses in organic chemistry and physical chemistry. After going through the lectures or reading the text of this book, they will have the capability to synthesize common known polymers and comprehend the advanced polymerization reactions reported in the literature to further design and synthesize new polymers. Finally, I would like to thank the encouragement and patience obtained from my husband Cheng-Hong Su during the course of this work and the inspiration, chemical formula drawing, and proof reading from my students Chun-Chih Ho, Shih-Hsiang Lin, Tzu-Chia Huang, Shang-jung Wu, Shih-Chieh Wang, Jhin-Fong Lin, and Hsueh-Chung Liao. Thanks are also due to typing and organization of the manuscript done by Shiow-Wei Wang and drawing of figures done by Yin-Hsi Lin. vii
Contents 1 Introduction.......。.. 1 l.1 Types of Polymers.························ 3 l2 Types of Polymerization...·.·············… l.3 Nomenclature of Polymers........·············· 4 l.4 Polymer Recycling.····.····················· 7 1.5 7 References...··············· F 2 Polymer Size and Polymer Solutions.,.....,....·.....··. 9 2.1 The Molecular Weight of Polymer.................... 9 2.2 Polymer Solutions...............·.·.···· 12 2.3 Measurement of Molecular Weight.················· 16 2.4 Problems..·.…。···…······ 24 References...................。····· 25 3 Structure Morphology Flow of Polymer................... 27 3.1 Chemical and Molecular Structure of Polymer............ 27 3.2 Crystal Structure of Homopolymer.....··.·.···.···· 31 3.3 Crystal Structure of Copolymer...................... 33 3.4 Liquid Crystalline Polymer...·..·····.....····· 37 3.5 Crosslinked Polymer.....·· 43 3.6 Polymer Blend.....·..·············· 44 3.7 Polymer Flow Under Shear Force..·.·.,··.·········· 46 3.8 Polymer Flow Under Thermal Stress................... 52 3.9 Problems.····……· 56 References...。..…。.·.·…······· 58 4 Chemical and Physical Properties of Polymers··.··..··.···· 61 4.1 Chemical Property of Polymer....................... 61 4.2 Mechanical Property of Polymer,·..··.··...········· 66 4.3 Thermal Property of Polymer...........······· 68 4.4 Electrical Property of Polymer..........·..·...···.·. 72 年
Contents 1 Introduction ........................................ 1 1.1 Types of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1.2 Types of Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1.3 Nomenclature of Polymers. . . . . . . . . . . . . . . . . . . . . . . . . . 4 1.4 Polymer Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.5 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2 Polymer Size and Polymer Solutions ...................... 9 2.1 The Molecular Weight of Polymer . . . . . . . . . . . . . . . . . . . . 9 2.2 Polymer Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 2.3 Measurement of Molecular Weight . . . . . . . . . . . . . . . . . . . . 16 2.4 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 3 Structure Morphology Flow of Polymer . . . . . . . . . . . . . . . . . . . 27 3.1 Chemical and Molecular Structure of Polymer . . . . . . . . . . . . 27 3.2 Crystal Structure of Homopolymer . . . . . . . . . . . . . . . . . . . . 31 3.3 Crystal Structure of Copolymer . . . . . . . . . . . . . . . . . . . . . . 33 3.4 Liquid Crystalline Polymer . . . . . . . . . . . . . . . . . . . . . . . . . 37 3.5 Crosslinked Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 3.6 Polymer Blend . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 3.7 Polymer Flow Under Shear Force. . . . . . . . . . . . . . . . . . . . . 46 3.8 Polymer Flow Under Thermal Stress. . . . . . . . . . . . . . . . . . . 52 3.9 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 4 Chemical and Physical Properties of Polymers . . . . . . . . . . . . . . 61 4.1 Chemical Property of Polymer . . . . . . . . . . . . . . . . . . . . . . . 61 4.2 Mechanical Property of Polymer . . . . . . . . . . . . . . . . . . . . . 66 4.3 Thermal Property of Polymer. . . . . . . . . . . . . . . . . . . . . . . . 68 4.4 Electrical Property of Polymer . . . . . . . . . . . . . . . . . . . . . . . 72 ix
Contents 4.5 Optical Property of Polymer.....·...,.············· 76 4.6 Processability of Polymer.......................... 83 4.7 Problems.····………·…· 86 References...。。。。。。··················· 87 5 Characterization of Polymer......,...,··....·········· 89 5.1 Instruments and Testing Methods for Polymer Characterization........·· 89 5.2 Characterization of Chemical Structures of Polymers....... 90 5.2.1 Chemical Reaction Method................... 90 5.2.2 Infrared Spectroscopy·.·.·.················ 90 5.2.3 Raman Spectroscopy...····················· 92 5.2.4 UV-Visible Spectroscopy.....·.···.·········· 93 5.2.5 Nuclear Magnetic Resonance Spectroscopy.······· 95 5.2.6 Electron Spin Resonance..... 98 5.3 Characterization of Morphology and Physical Structure of Polymer...········· 100 5.3.1 Transmission Electron Microscopy.............. 100 5.3.2X-Ray Scattering................·.··.··· 102 5.3.3 Atomic Force Microscopy.............. 103 5.4 Characterization of Thermal Properties of Polymers 104 5.4.1 Differential Thermal Analysis and Differential Scanning Calorimetry....................... 104 5.4.2 Thermomechanical Analysis 106 5.4.3 Thermogravimetric Analysis...,.··.·········· 107 5.4.4 Flammability Test........................... 108 5.5 Problems.···……· 109 References.....。..····· 110 6 Step Polymerization.......·..··.··········… 111 6.1 Chemical Reactions and Reaction Mechanisms of Step Polymerization.....···.·.················· 111 6.1.1 Carbonyl Addition:Elimination Reaction Mechanism..............··..······ 113 6.1.2 Carbonyl Addition:Substitution Reaction Mechanism........................ 115 6.1.3 Nucleophilic Substitution Reaction Mechanism.···· 116 6.1.4 Double-Bond Addition Reaction Mechanism.·.···· 116 6.1.5 Free-Radical Coupling...................... 117 6.1.6 Aromatic Electrophilic-Substitution Reaction Mechanism........,.·.······.·· 117 6.2 Reaction Kinetics of Step Polymerization,.....·.....··. 117 6.3 Molecular Weight Control in Step Polymerization.···.···· 119 6.4 Molecular Weight Distribution.........··..··..······ 122 6.5 Network Formation from Step Polymerization.....··...·. 124
4.5 Optical Property of Polymer . . . . . . . . . . . . . . . . . . . . . . . . 76 4.6 Processability of Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . 83 4.7 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 5 Characterization of Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 5.1 Instruments and Testing Methods for Polymer Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 5.2 Characterization of Chemical Structures of Polymers . . . . . . . 90 5.2.1 Chemical Reaction Method . . . . . . . . . . . . . . . . . . . 90 5.2.2 Infrared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . 90 5.2.3 Raman Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . 92 5.2.4 UV-Visible Spectroscopy. . . . . . . . . . . . . . . . . . . . . 93 5.2.5 Nuclear Magnetic Resonance Spectroscopy . . . . . . . . 95 5.2.6 Electron Spin Resonance . . . . . . . . . . . . . . . . . . . . . 98 5.3 Characterization of Morphology and Physical Structure of Polymer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 5.3.1 Transmission Electron Microscopy . . . . . . . . . . . . . . 100 5.3.2 X-Ray Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . 102 5.3.3 Atomic Force Microscopy . . . . . . . . . . . . . . . . . . . . 103 5.4 Characterization of Thermal Properties of Polymers . . . . . . . . 104 5.4.1 Differential Thermal Analysis and Differential Scanning Calorimetry . . . . . . . . . . . . . . . . . . . . . . . 104 5.4.2 Thermomechanical Analysis . . . . . . . . . . . . . . . . . . 106 5.4.3 Thermogravimetric Analysis . . . . . . . . . . . . . . . . . . 107 5.4.4 Flammability Test. . . . . . . . . . . . . . . . . . . . . . . . . . 108 5.5 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 6 Step Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 6.1 Chemical Reactions and Reaction Mechanisms of Step Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 6.1.1 Carbonyl Addition: Elimination Reaction Mechanism. . . . . . . . . . . . . . . . . . . . . . . . 113 6.1.2 Carbonyl Addition: Substitution Reaction Mechanism. . . . . . . . . . . . . . . . . . . . . . . . 115 6.1.3 Nucleophilic Substitution Reaction Mechanism . . . . . 116 6.1.4 Double-Bond Addition Reaction Mechanism . . . . . . . 116 6.1.5 Free-Radical Coupling . . . . . . . . . . . . . . . . . . . . . . 117 6.1.6 Aromatic Electrophilic-Substitution Reaction Mechanism. . . . . . . . . . . . . . . . . . . . . . . . 117 6.2 Reaction Kinetics of Step Polymerization . . . . . . . . . . . . . . . 117 6.3 Molecular Weight Control in Step Polymerization . . . . . . . . . 119 6.4 Molecular Weight Distribution . . . . . . . . . . . . . . . . . . . . . . . 122 6.5 Network Formation from Step Polymerization . . . . . . . . . . . . 124 x Contents