??????? Advanced Polymer Chemistry

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???????Advanced Polymer Chemistry

• ??? ??

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References

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

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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

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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

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• 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

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• 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

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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

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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

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• 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

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Definitions
Lectures 1 and 2

• Definitionpoly (??) mer (unit)
  ???repeating unit ??
• ????polymerlinear Polyethylene
• ???gt10000 ?? polymer
• ???lt10000 ? oligermer
• Molecular weight (Mw)
• Chain length
• Degree of Polymerization

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Types of Polymers
Lectures 1 and 2

• star-shaper polymer
• comb-shaper polymer
• ladder polymer
• Semi-ladder polymer
• network polymer

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• Homopolymer??monomer???polymer
• Copolymer AB
• Rendom ABAAABABA
• Alternating ABABABABAB
• Block AAAAAAAABBBBBBBBAAAAAAA
• Graft ??(???????)

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

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Lecture 3

• Gel point
• Thermosetting
• Thermoplastic
• Oligomer
• Telomer Telechelic polymer
• Dendrimer ??????
• Rotaxanes

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Techniques of polymerizations
Lecture 4

• Polymerization
• Bulk
• Solution
• Emulsion
• Suspension

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Nomenclature
Lecture 4

• Nomenclature
• IUPAC
• Source Name

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Structure and Property Relationships of Structure
and Properties
Lectures 5 and 6

• Physical property
• Forceprimary force
• Secondary force
• H-bonding (polyamide)
• Vander waals
• Dipole-dipole
• Induced dipole (polyester)

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Amorphous and Crystalline Arrangements

• Morphology
• Amorphous
• Vitrification(??)
• In molten state
• In solid state
• Secondary Transition Temp. (Tg)
• Primary Transition Temp. (Tm)
• Crystalline

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Lecture 7

• Rheology(??)
• Relaxation
• Elastic behavior
• Viscous flow
• Viscoelasticity

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• Morphology
• Amorphous(Crystalline)
• ?Glassy State
• ?Rubbery State
• ?Molten
• ?Flow

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Lecture 8

• Structure?? Tg
• Chemical structure
• Method of measurement
• Molecular weight
• Aging effect

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• Rsize ? Tg?
• R?? Tg?
• Branched substituional group ?????
• Polarity? Tg?,H-bonding Tg ?
• Chain-stiffening effect
• Stereochemistry

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Lecture 9

• Tm????
• ?????
• ??orientation(??,??)
• Liquid crystallinity
• Pure liquid isotropic ??
• Crystalline material anisotropic ??
• Polymer liquid crystal
• Lyotropic (solvent)nematic, smetic, cholesteric
• Thermotropic(melt)

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• ?? physical properties
• Freedom of molecular motion
• Flexibility
• Density
• Solubility

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• Solutions of polymers
• Solubility parameter

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

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Free-Radical Polymerization
Lectures 10 and 11

• Free-radical polmerization(?????thermopastic)
• ? condensation ?????????90
• ??Free-radical?????????(vinyl monomer)

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• Initiators
• ??????3?
• Peroxides ????
• Azo compounds
• Redox Systems

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• Thermal decomposition of compounds
• Azo compoud and peroxides
• Azo compoud rxn?????
• Peroxides rxn?????
• Bimolecular system (Redox System)
• Redox system rxn

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• Born and Metal alkyl initiators of free radical
  polymerization
• Photochemical initiator (photoinitiator)
• Radiation source
• ß-ray, ?-rayCo60 ,a-particle, Electron beam
• capture of free radical by monomer

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Lecture 12

• propagation
• factors
• steric hindrance gt ?????????
• polar effect
• resonance stability

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Tacticity

• Steric control
• Isotactic
• Syndiotactic
• Atactic (random)

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

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Lectures 1 3 and 14

• Thermochemisity of chain polymerization
• Activation energy (E)
• Kinetic chain length (?)
• Autoacceleration ?????
• Polymerization of monomers with multiple double
  bonds
• Ring forming polymerization unconjugated diene

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• Termination rxn
• A second order radical radical rxn
• A second radical molecule rxn
• A first order loss radical activity ?chain
  transfer
• Chain transfer agentmercaptan (thiol) ????

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

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• Resonance stabilization
• Degradative chain transferring
• Inhibition and retardation
• Donoracceptor complex
• ?alternating copolymer in polymerization

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Lecture 15

• Steric control in free radical Polymerization
• Canal complex
• Lamellae polymerization
• Template polymerization

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Living polymer and controlled/living
Polymerization
Lecture 16

• 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

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Ionic Chain-Growth Polymerization
Lectures 1 7

• Chemistry of Ionic chain growth Polymerization
• Cationic
• Anionic
• Polymerization Modes
• Electrophilic addition
• Nucleophilic addition

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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

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Cationic Polymerization
Lecture 1 8

• Initiating Systems
• Lewis Acid/Bronsted Acid
• Bronsted Acid by themselves
• Stable Cationic Salts
• Organometallic Compounds
• Some Cationic Forming Substances

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Step-Growth Polymerization and Step-Growth
Polymers
Lecture 19

• Mechanism and Kinetics of Step-Growth
  Polymerization
• Reactions of Functional Groups
• Kinetic Considerations