高等高分子化学PPT教学课件
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3.2 Kinetic of ionic Chain Growth Polymerization
3.3 Cationic Polymerization
– Two electron Transposition Initiation Reaction – One Electron Transposition Initiation Reaction
Copolymerization • 2.8 Polymer5ization of Complexes With
Lewis Acids
2.9 Controlled/”Living” Polymerization 2.10 Atom Transfer radical Polymerization 2.11 Special Types of Controlled/ “Living”
• Solutions of polymers
– Solubility parameter
• Moleculer weight and MW Determination
– Number average MW (Mn) – Weight average MW (Mw) – Mark-Houwink-Sakurada eq
• 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)
• Classification • Carothers • Addition polymer • Condensation polymer • Flory • Step-growth polymer • Chain-growth polymer
• Rheology(流變) • Relaxation • Elastic behavior • Viscous flow • Viscoelasticity
• Morphology Amorphous(Crystalline) Glassy State Rubbery State Molten Flow
– Bimolecular system (Redox System)
• Redox system rxn
• Born and Metal alkyl initiators of free radical polymerization
• Photochemical initiator (photoinitiator) • Radiation source
Morphology • Amorphous
Vitrification(玻化)
In molten state
In solid state
– Secondary Transition Temp. (Tg) – Primary Transition Temp. (Tm)
• Crystalline
Lecture 7
monomer)
• Initiators
– 實驗室通常用3種 Peroxides 過氧化物 Azo compounds Redox Systems
• Thermal decomposition of compounds
– Azo compoud and peroxides
• Azo compoud rxn的反應機構 • Peroxides rxn的反應機構
3.4 Anionic Polymerization of Olefins
4. Step Growth Polymerization
4.1 Mechanism aHale Waihona Puke Baidud Kinetics of Step Growth Polymerization
4.2 Polyesters 4.3 Polyamides 4.4Aromatic Polyamide-Imides and Aromatic
– Lyotropic (solvent)：nematic, smetic, cholesteric – Thermotropic(melt)
• 影響 physical properties
– Freedom of molecular motion – Flexibility – Density – Solubility
高等高分子化學 Advanced Polymer
Chemistry
References
• Principles of Polymer Chemistry (second Edition)
– Author: A. Ravve
• Polymer Chemistry - an Introduction(3rd ed)
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
Lecture 3
• Gel point • Thermosetting • Thermoplastic • Oligomer • Telomer
Telechelic polymer • Dendrimer 樹枝狀高分子 • Rotaxanes
Lecture 4
Techniques of polymerizations
2.2 Capture of the Free Radical by the Monomers
• 2.3 Propagation • 2.4 Termination Reaction • 2.5 Copolymerization • 2.6 Inhibition and Retardation • 2.7 Donor-Acceptor Complexes in
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
– β-ray, γ-ray:Co60 ,α-particle, Electron beam
• capture of free radical by monomer
Lecture 12
• propagation
– factors
• steric hindrance => 和取代基的大小有關 • polar effect • resonance stability
polymerization 2.12 Kinetic of Controlled/ “Living”
Polymerization
3.Ionic Chain-Growth Polymerization
3.1 Chemistry of Ionic Chain-Growth Polymerization
Tacticity
• Steric control
– Isotactic – Syndiotactic – Atactic (random)
• Effect of reaction Medium
– pH – solution viscosity – solvent – ceiling temp(Tc)
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
• Polymerization Bulk Solution Emulsion Suspension
Lecture 4
Nomenclature
• Nomenclature • IUPAC • Source Name
Lectures 5 and 6 Structure and Property Relationships of Structure and Properties
Lecture 8
• Structure影響 Tg
Chemical structure Method of measurement Molecular weight Aging effect
• 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
Lectures 1 and 2
Definitions
• 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
Polyester-Imides 4.5 Polyimides 4.6 Polyethers
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
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
• Molecular weight (Mw) • Chain length • Degree of Polymerization
Lectures 1 and 2
Types of Polymers
• star-shaper polymer • comb-shaper polymer • ladder polymer • Semi-ladder polymer • network polymer
– Author: Malcom P. Stevens
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
• Physical property • Force：primary force
Secondary force H-bonding (polyamide) Vander waals Dipole-dipole Induced dipole (polyester)
Amorphous and Crystalline Arrangements
3.3 Cationic Polymerization
– Two electron Transposition Initiation Reaction – One Electron Transposition Initiation Reaction
Copolymerization • 2.8 Polymer5ization of Complexes With
Lewis Acids
2.9 Controlled/”Living” Polymerization 2.10 Atom Transfer radical Polymerization 2.11 Special Types of Controlled/ “Living”
• Solutions of polymers
– Solubility parameter
• Moleculer weight and MW Determination
– Number average MW (Mn) – Weight average MW (Mw) – Mark-Houwink-Sakurada eq
• 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)
• Classification • Carothers • Addition polymer • Condensation polymer • Flory • Step-growth polymer • Chain-growth polymer
• Rheology(流變) • Relaxation • Elastic behavior • Viscous flow • Viscoelasticity
• Morphology Amorphous(Crystalline) Glassy State Rubbery State Molten Flow
– Bimolecular system (Redox System)
• Redox system rxn
• Born and Metal alkyl initiators of free radical polymerization
• Photochemical initiator (photoinitiator) • Radiation source
Morphology • Amorphous
Vitrification(玻化)
In molten state
In solid state
– Secondary Transition Temp. (Tg) – Primary Transition Temp. (Tm)
• Crystalline
Lecture 7
monomer)
• Initiators
– 實驗室通常用3種 Peroxides 過氧化物 Azo compounds Redox Systems
• Thermal decomposition of compounds
– Azo compoud and peroxides
• Azo compoud rxn的反應機構 • Peroxides rxn的反應機構
3.4 Anionic Polymerization of Olefins
4. Step Growth Polymerization
4.1 Mechanism aHale Waihona Puke Baidud Kinetics of Step Growth Polymerization
4.2 Polyesters 4.3 Polyamides 4.4Aromatic Polyamide-Imides and Aromatic
– Lyotropic (solvent)：nematic, smetic, cholesteric – Thermotropic(melt)
• 影響 physical properties
– Freedom of molecular motion – Flexibility – Density – Solubility
高等高分子化學 Advanced Polymer
Chemistry
References
• Principles of Polymer Chemistry (second Edition)
– Author: A. Ravve
• Polymer Chemistry - an Introduction(3rd ed)
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
Lecture 3
• Gel point • Thermosetting • Thermoplastic • Oligomer • Telomer
Telechelic polymer • Dendrimer 樹枝狀高分子 • Rotaxanes
Lecture 4
Techniques of polymerizations
2.2 Capture of the Free Radical by the Monomers
• 2.3 Propagation • 2.4 Termination Reaction • 2.5 Copolymerization • 2.6 Inhibition and Retardation • 2.7 Donor-Acceptor Complexes in
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
– β-ray, γ-ray:Co60 ,α-particle, Electron beam
• capture of free radical by monomer
Lecture 12
• propagation
– factors
• steric hindrance => 和取代基的大小有關 • polar effect • resonance stability
polymerization 2.12 Kinetic of Controlled/ “Living”
Polymerization
3.Ionic Chain-Growth Polymerization
3.1 Chemistry of Ionic Chain-Growth Polymerization
Tacticity
• Steric control
– Isotactic – Syndiotactic – Atactic (random)
• Effect of reaction Medium
– pH – solution viscosity – solvent – ceiling temp(Tc)
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
• Polymerization Bulk Solution Emulsion Suspension
Lecture 4
Nomenclature
• Nomenclature • IUPAC • Source Name
Lectures 5 and 6 Structure and Property Relationships of Structure and Properties
Lecture 8
• Structure影響 Tg
Chemical structure Method of measurement Molecular weight Aging effect
• 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
Lectures 1 and 2
Definitions
• 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
Polyester-Imides 4.5 Polyimides 4.6 Polyethers
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
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
• Molecular weight (Mw) • Chain length • Degree of Polymerization
Lectures 1 and 2
Types of Polymers
• star-shaper polymer • comb-shaper polymer • ladder polymer • Semi-ladder polymer • network polymer
– Author: Malcom P. Stevens
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
• Physical property • Force：primary force
Secondary force H-bonding (polyamide) Vander waals Dipole-dipole Induced dipole (polyester)
Amorphous and Crystalline Arrangements