Introduction to Polymers

Citation

Young, R. J., & Lovell, P. A. (2011). Introduction to Polymers (3rd ed.). CRC Press.

Chapter Summary

The book is organized in four parts and 25 chapters, running to 688 pages: Part I, Concepts, Nomenclature and Synthesis of Polymers (Chapters 1–9); Part II, Characterization of Polymers (Chapters 10–15); Part III, Phase Structure and Morphology of Bulk Polymers (Chapters 16–18); and Part IV, Properties of Bulk Polymers (Chapters 19–25). The publisher's contents list gives chapter titles and their section headings without chapter numbers (numbers here follow the order of the list). Problems and further reading appear at the end of each chapter, and answers to problems are at the back.

Chapters 1–2: Concepts and Nomenclature; Principles of Polymerization

The opening chapter covers the origins of polymer science and the polymer industry, basic definitions and nomenclature, and molar mass and degree of polymerization. Chapter 2 classifies polymerization reactions, relates monomer functionality to polymer skeletal structure, and introduces the principle of equal reactivity of functional groups.

Chapters 3–5: Step Polymerization; Radical Polymerization; Ionic Polymerization

Step polymerization is treated in linear and non-linear forms. Radical polymerization covers the chemistry and kinetics of conventional free-radical polymerization, polymerization processes, reversible-deactivation ("living") radical polymerizations and non-linear radical polymerizations. Ionic polymerization covers cationic and anionic polymerization and group-transfer polymerization.

Chapters 6–9: Stereochemistry and Coordination Polymerization; Ring-Opening Polymerization; Specialized Methods of Polymer Synthesis; Copolymerization

Chapter 6 deals with tacticity, geometric isomerism in polymers from conjugated dienes, and Ziegler–Natta and metallocene catalysts. Chapter 7 covers cationic, anionic, free-radical and metathesis ring-opening routes. Chapter 8 collects solid-state topochemical polymerization, oxidative coupling, precursor routes to intractable polymers and supramolecular polymerization. Chapter 9 treats step and chain copolymerization together with block and graft copolymer synthesis.

Chapters 10–13: Theoretical Description of Polymers in Solution; Number-Average Molar Mass; Scattering Methods; Frictional Properties of Polymers in Solution

The solution thermodynamics and chain dimensions of polymers come first, followed by the methods used to measure molar mass: membrane and vapour pressure osmometry, ebulliometry and cryoscopy, end-group analysis, static and dynamic light scattering, small-angle X-ray and neutron scattering, viscometry and ultracentrifugation.

Chapters 14–15: Molar Mass Distribution; Chemical Composition and Molecular Microstructure

Chapter 14 covers fractionation, gel permeation chromatography, field-flow fractionation and mass spectroscopy. Chapter 15 introduces spectroscopy and then ultraviolet–visible, infrared, Raman, nuclear magnetic resonance and mass spectroscopy applied to composition and microstructure.

Chapters 16–18: The Amorphous State; The Crystalline State; Multicomponent Polymer Systems

The amorphous state covers the glass transition, the factors that control it and macromolecular dynamics. The crystalline state covers crystal structure determination, single crystals, semi-crystalline and liquid crystalline polymers, defects, crystallization and melting. Multicomponent systems cover polymer blends and block copolymers.

Chapters 19–21: Elastic Deformation; Viscoelasticity; Elastomers

Elastic deformation leads into viscoelasticity (mechanical models, the Boltzmann superposition principle, dynamic mechanical testing, time–temperature superposition, entanglements, non-linear behaviour) and elastomers (thermodynamic and statistical theories of rubber elasticity and stress–strain behaviour).

Chapters 22–25: Yield and Crazing; Fracture and Toughening; Polymer Composites; Electrical Properties

The final chapters cover yield criteria and crazing, fracture mechanics and toughened polymers, composite materials (matrices, reinforcements, nanocomposites) and electrical properties (dielectric properties, conduction, polymer electronics).

Key Concepts

Part I: Synthesis (Chapters 1–9)

• Molar mass and degree of polymerization: the quantities that describe polymer size (Chapter 1).
• Principle of equal reactivity: the assumption that the reactivity of a functional group does not depend on molecular size (Chapter 2).
• Step, radical, ionic and coordination polymerization: the main polymerization mechanisms (Chapters 3–6).
• Copolymerization: step and chain routes to copolymers, including block and graft types (Chapter 9).

Part II: Characterization (Chapters 10–15)

• Number-average molar mass: measured by osmometry, end-group analysis and related methods (Chapter 11).
• Molar mass distribution: fractionation and gel permeation chromatography (Chapter 14).
• Light and X-ray/neutron scattering: scattering routes to molecular properties (Chapter 12).
• Spectroscopy: composition and microstructure from UV–visible, infrared, Raman, NMR and mass spectroscopy (Chapter 15).

Parts III–IV: Structure and properties (Chapters 16–25)

• Glass transition and crystallinity: the main features of the amorphous and crystalline states (Chapters 16–17).
• Viscoelasticity: time- and temperature-dependent mechanical behaviour (Chapter 20).
• Elastomer deformation: thermodynamic and statistical theories of rubber elasticity (Chapter 21).
• Yield, crazing and fracture: the failure of polymers (Chapters 22–23).

Critical Analysis

Strengths

• A complete arc from molecule to material. The four parts follow polymers from their synthesis through characterization and phase structure to bulk properties, and the publisher says the third edition was reorganized to give a coherent platform for teaching and learning contemporary polymer science.
• Contemporary topics in the contents. The publisher highlights reversible-deactivation radical polymerization, dendrimers, hyperbranched and block copolymers, diffusion and field-flow fractionation, multicomponent systems, nanocomposites and electrical properties among the additions to the third edition.
• Self-contained and derived. According to the publisher, the text is largely self-contained, fully derives most equations and cross-references topics between chapters. Each chapter has a list of further reading and problem sets, particularly numerical ones.
• Reviewed as both an undergraduate and an entry-level postgraduate text. A review quoted by the publisher (Chemistry World, 2012) calls the second edition the recommended text for a second-year undergraduate course, says the reviewer would recommend the third for that course and for a fourth-year Masters course on advanced polymer synthesis, and recommends it as an entry-level text for postgraduates with limited experience of polymers.

Limitations

• Long and quantitative. At 688 pages and 25 chapters, with most equations derived in the text and sections on subjects such as the Boltzmann superposition principle and the statistical theory of elastomer deformation, the book is more than a single course covers and expects comfort with physical chemistry and mathematics.
• No chapter on processing, degradation or recycling. None of the chapter or section headings addresses polymer processing, degradation or recycling, and none is devoted to natural polymers, so a reader with these interests will need other sources.
• Age of the edition. The third edition appeared in 2011; developments in polymer synthesis, characterization and materials since then are not in the contents list.

Where It Fits in the Course

Young and Lovell is a physical and quantitative treatment of polymers: Parts III and IV, ten of its 25 chapters, deal with the structure and properties of bulk polymers. Carraher's Introduction to Polymer Chemistry is described as an introductory text on how polymers are made, how their structure and size are measured, and how chemistry translates into the properties of plastics, fibres, rubbers and natural macromolecules, with applications, case studies and exercises; it is a gentler first course that makes a good preparation for Young and Lovell. Allcock's Introduction to Materials Chemistry places polymers among ceramics, metals and semiconductors, and is the choice for a reader who wants that wider materials context first.

For more specialised reading, West's Solid State Chemistry and its Applications treats the structure and properties of inorganic solids, the inorganic counterpart to Young and Lovell's polymer solids, and Müller's Crystal Structure Refinement is a practical guide to refining molecular crystal structures from diffraction data, a more specialised subject than the section on crystal structure determination in Chapter 17.

How to Use This Book

The book is aimed at chemistry and materials students from the second year onwards and at postgraduates new to polymers. Readers should be comfortable with organic reaction mechanisms and basic thermodynamics; the publisher notes that polymerization mechanisms are shown with electron movements, and the equations are derived in the text.

A practical plan:

• Core: Part I, Chapters 1–5 and 9, for concepts, step, radical and ionic polymerization and copolymers; then Chapters 11, 14 and 15 for molar mass and spectroscopy; then Chapters 16, 17, 19 and 20 for glass transition, crystallinity, elasticity and viscoelasticity.
• Follow-on or optional: the remaining synthesis chapters (6–8), solution theory and scattering (10, 12, 13), multicomponent systems (18), and elastomers, yield and fracture, composites and electrical properties (21–25).
• For an advanced synthesis course: the newer material the publisher lists for Part I, such as reversible-deactivation radical polymerization (Chapter 4) and free-radical ring-opening polymerization (Chapter 7).

Work the numerical problems after each chapter and check them against the answers at the back; use the further-reading lists to move beyond a chapter.