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高等高分子化學 Advanced Polymer Chemistry

高等高分子化學 Advanced Polymer Chemistry. 李文福 教授. References. Principles of Polymer Chemistry (second Edition) Author: A. Ravve Polymer Chemistry - an Introduction(3rd ed) Author: Malcom P. Stevens. Contents. 1. Introduction and Physical Properties of Polymers Introduction

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高等高分子化學 Advanced Polymer Chemistry

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  1. 高等高分子化學Advanced Polymer Chemistry 李文福 教授

  2. References • Principles of Polymer Chemistry (second Edition) • Author: A. Ravve • Polymer Chemistry - an Introduction(3rd ed) • Author: Malcom P. Stevens

  3. Contents 1. Introduction and Physical Properties of Polymers • Introduction • Physical Properties of Polymers • Structure and Property Relationship in Organic Polymers • Amorphous and Crystalline arrangements • Effect of Chemical structure upon Physical Properties • Solution of Polymers • Molecular weights and Molecular weight distributions • Steric Arrangement in Macromolecules

  4. 2. Free-Radical Chain-Growth Polymerization 2.1 Free-Radical Chain-Growth Polymerization Process • Kinetic Relationship in Free-Radical Polymerization • Reaction Leading to Formation of Initiating Free-Radicals 2.2 Capture of the Free Radical by the Monomers

  5. 2.3 Propagation • 2.4 Termination Reaction • 2.5 Copolymerization • 2.6 Inhibition and Retardation • 2.7 Donor-Acceptor Complexes in Copolymerization • 2.8 Polymer5ization of Complexes With Lewis Acids

  6. 2.9 Controlled/”Living” Polymerization 2.10 Atom Transfer radical Polymerization 2.11 Special Types of Controlled/ “Living” polymerization 2.12 Kinetic of Controlled/ “Living” Polymerization

  7. 3.Ionic Chain-Growth Polymerization 3.1 Chemistry of Ionic Chain-Growth Polymerization 3.2 Kinetic of ionic Chain Growth Polymerization 3.3 Cationic Polymerization • Two electron Transposition Initiation Reaction • One Electron Transposition Initiation Reaction 3.4 Anionic Polymerization of Olefins

  8. 4. Step Growth Polymerization 4.1 Mechanism and Kinetics of Step Growth Polymerization 4.2 Polyesters 4.3 Polyamides 4.4Aromatic Polyamide-Imides and Aromatic Polyester-Imides 4.5 Polyimides 4.6 Polyethers

  9. 4.7 Polyurethanes 4.8 Epoxy Resins 4.9 Phenol-Formaldehyde Resins 4.10 Silicon Polymers 4.11 High Performance Polymers 4.12 Dendrimers and Polyrotaxanes

  10. Definitions Lectures 1 and 2 • Definition：poly (很多) mer (unit) 由很多repeating unit 組成 • 最簡單的polymer：linear Polyethylene • 分子量＞10000 可稱 polymer • 分子量＜10000 稱 oligermer • Molecular weight (Mw) • Chain length • Degree of Polymerization

  11. Lectures 1 and 2 Types of Polymers • star-shaper polymer • comb-shaper polymer • ladder polymer • Semi-ladder polymer • network polymer

  12. Homopolymer：單一monomer聚合的polymer • Copolymer A+B • Rendom ABAAABABA • Alternating ABABABABAB • Block AAAAAAAABBBBBBBBAAAAAAA • Graft 接枝(多用於表面處理)

  13. Classification • Carothers • Addition polymer • Condensation polymer • Flory • Step-growth polymer • Chain-growth polymer

  14. Lecture 3 • Gel point • Thermosetting • Thermoplastic • Oligomer • Telomer Telechelic polymer • Dendrimer 樹枝狀高分子 • Rotaxanes

  15. Lecture 4 Techniques of polymerizations • Polymerization Bulk Solution Emulsion Suspension

  16. Nomenclature Lecture 4 • Nomenclature • IUPAC • Source Name

  17. Lectures 5 and 6 Structure and Property Relationships of Structure and Properties • Physical property • Force：primary force Secondary force H-bonding (polyamide) Vander waals Dipole-dipole Induced dipole (polyester)

  18. Amorphous and Crystalline Arrangements Morphology • Amorphous Vitrification(玻化) In molten state In solid state • Secondary Transition Temp. (Tg) • Primary Transition Temp. (Tm) • Crystalline

  19. Lecture 7 • Rheology(流變) • Relaxation • Elastic behavior • Viscous flow • Viscoelasticity

  20. Morphology Amorphous(Crystalline) Glassy State Rubbery State Molten Flow

  21. Lecture 8 • Structure影響 Tg Chemical structure Method of measurement Molecular weight Aging effect

  22. R：size 大 Tg大 • R：越長 Tg小 • Branched substituional group 可塑化效應 • Polarity大 Tg高，H-bonding Tg 高 • Chain-stiffening effect • Stereochemistry

  23. Lecture 9 • Tm點的產生 • 冷卻時間長 • 利用orientation(配向，延伸) • Liquid crystallinity • Pure liquid – isotropic 同向 • Crystalline material – anisotropic 異向 • Polymer liquid crystal • Lyotropic (solvent)：nematic, smetic, cholesteric • Thermotropic(melt)

  24. 影響 physical properties • Freedom of molecular motion • Flexibility • Density • Solubility

  25. Solutions of polymers • Solubility parameter

  26. Moleculer weight and MW Determination • Number average MW (Mn) • Weight average MW (Mw) • Mark-Houwink-Sakurada eq

  27. Lectures 10 and 11 Free-Radical Polymerization • Free-radical polmerization(大部分屬於thermopastic) • 以 condensation 聚合高分子大約佔有90% • 可以Free-radical聚合者大部分有雙鍵(vinyl monomer)

  28. Initiators • 實驗室通常用3種 Peroxides 過氧化物 Azo compounds Redox Systems

  29. Thermal decomposition of compounds • Azo compoud and peroxides • Azo compoud rxn的反應機構 • Peroxides rxn的反應機構 • Bimolecular system (Redox System) • Redox system rxn

  30. Born and Metal alkyl initiators of free radical polymerization • Photochemical initiator (photoinitiator) • Radiation source • β-ray, γ-ray:Co60 ,α-particle, Electron beam • capture of free radical by monomer

  31. Lecture 12 • propagation • factors • steric hindrance => 和取代基的大小有關 • polar effect • resonance stability

  32. Tacticity • Steric control • Isotactic • Syndiotactic • Atactic (random)

  33. Effect of reaction Medium • pH • solution viscosity • solvent • ceiling temp(Tc)

  34. Lectures 1 3 and 14 • Thermochemisity of chain polymerization • Activation energy (E) • Kinetic chain length (ν) • Autoacceleration 自加速反應 • Polymerization of monomers with multiple double bonds • Ring forming polymerization – unconjugated diene

  35. Termination rxn • A second order radical – radical rxn • A second radical – molecule rxn • A first order loss radical activity chain transfer • Chain transfer agent：mercaptan (thiol) 鏈調整劑

  36. Copolymerization • Define reactivity ratio (r) • Q-e scheme

  37. Resonance – stabilization • Degradative chain transferring • Inhibition and retardation • Donor—acceptor complex alternating copolymer in polymerization

  38. Lecture 15 • Steric control in free radical Polymerization • Canal complex • Lamellae polymerization • Template polymerization

  39. Lecture 16 Living polymer and controlled/living Polymerization • Controlled/living Polymerization • Deactivations of growing radical • Reversible deactivations of growing radical with non-radical species • Reversible addition-Fragmentation Chain transfer (RAFT) • The kinetics of controlled/living polymerization

  40. Lectures 1 7 Ionic Chain-Growth Polymerization • Chemistry of Ionic chain growth Polymerization • Cationic • Anionic • Polymerization Modes • Electrophilic addition • Nucleophilic addition

  41. Kinetic of Ionic Chain-Growth Polymerization • Cationic Initiation Process • Cationic Propagation Process • Cationic Termination • By Transfer • By spontaneous Termination • By rearrangement of the Kinetic Chain

  42. Lecture 1 8 Cationic Polymerization • Initiating Systems: • Lewis Acid/Bronsted Acid • Bronsted Acid by themselves • Stable Cationic Salts • Organometallic Compounds • Some Cationic Forming Substances

  43. Lecture 19 Step-Growth Polymerization and Step-Growth Polymers • Mechanism and Kinetics of Step-Growth Polymerization • Reactions of Functional Groups • Kinetic Considerations

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