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Polymer Science and Engineering - Part II
Polymer Science and Engineering - Part II
Polymer Science and Engineering - Part II
Zenamarkos B. (PhD)
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Polymer Synthesis and
Reaction Kinetics
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Polymers Synthesis and Reaction Kinetics
Why Synthesis Kinetics?
➢ The monomer molecules may be all alike, or they may represent two,
three, or more different compounds.
❖Monomer:
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Polymers Synthesis and Reaction Kinetics
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Polymers Synthesis and Reaction Kinetics
❖ Addition:
➢ rapid polymerization via initiator
• Radical initiator
• Ionic mechanism
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Polymers Synthesis and Reaction Kinetics
❖ Condensation:
▪ relatively slow chain growth by step wise reaction of monomers and
oligomers, whilst releasing small molecules
▪ the molar mass of the chains increase by the successive linkage of
monomer molecules.
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I. Radical Addition Polymerization
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I. Radical Addition Polymerization
Initiation
•Decomposition of initiator to yield initiator radicals.
•Decomposition: thermally or photo-chemically
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I. Radical Addition Polymerization
Initiation
Initiator Wastage Reactions
• Removal of radicals from the polymerization.
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I. Radical Addition Polymerization
Start Reaction
• Addition of monomer to the initiator radical.
• The initiation reaction is much slower than the start reaction and determines
therefore the speed of radical formation.
✓ Typical values for f for most free radical polymerizations range from 0.3 to 0.8
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I. Radical Addition Polymerization
Propagation
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I. Radical Addition Polymerization
Termination
• The polymerization of a chain can be stopped by different mechanisms:
✓ coupling (or combination)
✓ disproportionation
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I. Radical Addition Polymerization
Termination
❖ Other reaction phenomena: Chain transfer
• With solvent: new radical can start new chain
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Industrial Processes for Radical Addition Polymerization
❖ Mass polymerization
❖ Solution polymerization
❖ Suspension polymerization
❖ Emulsion polymerization
▪ Monomer (fluid), initiator and regulator are mixed under controlled T & P
• 0.1-1wt% initiator
• Continuous stirring (heat control)
• Two possibilities:
o Polymer is soluble in monomer (e.g., PS, PMMA)
✓ Viscosity rises rapidly
✓ Strong exotherm (even risk of explosion)
o Polymer is insoluble in monomer (e.g., PVC)
✓ Viscosity rises but less rapidly
▪ After reaction, polymer melt is separated, cooled and granulated.
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Radical Polymerization in the Mass
❖Advantages of mass polymerization:
▪ ‘‘simple’’
▪ Good purity/quality of polymer
▪ Low residual content of initiator
❖ Disadvantages:
▪ Residual monomer is difficult to remove
▪ Difficult temperature control
▪ Viscous mixture is difficult to stir:
✓ inhomogeneous temperature and composition
✓ large spread in molecular weight
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Radical Polymerization in the Mass
Examples:
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Radical Polymerization in the Mass
Examples:
❖ Production of PS
• Mass polymerization at 250oC
• 5-25% ethylbenzene is added to lower viscosity
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Radical Polymerization in the Mass
Examples:
❖ Production of PVC
• Vinylchloride is mass polymerized at 40 – 70oC and 5-12 bar
• Product in powder form (Tg = 81oC)
• Not soluble in monomer
• Temperature control by evaporation of liquid vinylchloride in
reactor
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Radical Polymerization in Solution
➢ Primarily used for polymers which are applied in the solvent (coatings,
adhesives)
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Radical Polymerization in Suspension
❖ Advantages:
• Water as cheap dispersion medium
• Low viscosity, very good heat control
• High purity, already in form of beads
• Narrow molecular weight distribution; good mechanical properties
❖ Disadvantages:
• High level of stirring needed
• Difficult to control particle size
• Dispersion agent stays in polymer bead
• Batch process to prevent contamination of vessel by coagulated beads
✓ Cleaning needed
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Radical Polymerization in Suspension
Example:
❖ Production of PVC
• Stirred autoclave
• 15 bar pressure to liquefy vinylchloride
• VC, initiator, suspension stabilizer are suspended in water
• 200 m3, 100 ton
• Stirring, heating (50 – 80oC)
• Unreacted VC is vaporized by pressure drop
• Porous beads which can absorb plasticiser
• In each bead solid PVC is formed (not soluble in VC, Tg = 87 oC)
• Centrifuging, washing, drying
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Radical Polymerization in Emulsion
❖ (Non-water soluble) monomer is
Micelle swollen
emulsified in water with surfactant with monomer
Spherical micelle
(‘soap’) + initiator
• Surfactant prevents coagulation
• Also soap micelles present
• 99% of monomer is emulsified (1 – 10 µm
droplets) Monomer droplet Water
stabilized by surfactant
• 1% of monomer sits in micelles
• Only 0.05% in water phase
• Initiator is soluble in water
Hydrophilic Hydrophobic
head tail
Surfactant
molecule
❖ Start of reaction:
• Heating to create radical initiator
• Radicals migrate to emulsified droplets and start polymerization
• But the largest part of the radicals enters the surfactant micelles
• Polymer chains are formed in the micelles
• Then, monomer diffuses from the monomer droplets to the micelles
• Typically, one growing polymer chain per micelle
• Termination by other entering radical; re-start by third radical, etc.
• End-phase of polymerization is latex
• De-activation of surfactant
• Coagulation, filtration, washing, drying
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Radical Polymerization in Emulsion
❖ Advantages:
• Low viscosity, good heat control
• Very high conversion (100%)
• Molecular weight, rate of polymerization and latex particles size are function
of surfactant concentration
• Initiator typically not soluble in monomer; higher initiator concentration can
increase speed of polymerization, but will not lead to more termination
• Termination by combination is less likely
❖ Disadvantages
• Surfactant difficult to remove (alternative is to produce latex, e.g., for rubbers)
• Residual surfactant can lower properties
• Relatively expensive
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Cationic Addition Polymerization
❖ Initiation:
• Initiation by positively charged species (electron-acceptor)
• Electrophilic addition
• Growing carbon - chain ends with Carbonium-ion
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Cationic Addition Polymerization
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Cationic Addition Polymerization
❖ Propagation:
• A chain reaction ensues
• Cationic polymerization only works well for carbonium-ion which can be
stabilized.
Example:
polyisobutene
❖ Termination:
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Anionic Addition Polymerization
❖ Initiation:
• Initiation by negatively charged species (electron-donor)
• Nucleophilic addition
• Growing Carbon-chain ends with Carban-ion
• Positive counter-ion
Catalysts/initiators used:
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Anionic Addition Polymerization
❖ Propagation:
• Propagation is promoted, the more the carban-ion is stabilized
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Anionic Addition Polymerization
❖ Termination:
• By proton transfer with the solvent (example PAN in ammonia)
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Condensation Polymerization
• ‘Step-wise’ polymerization
• Much slower than addition polymerization
• A small molecule like water is released
• Monomers with 2 functional groups are required to form linear chains
(thermoplastics)
• More functional groups lead to networks (thermosets)
• There is no real termination -> oligomers can in principle react further
o MW increases as a function of time, but slower and slower the less
monomer is present
• Removal of small molecule helps to enhance reaction
• Mn typically limited to 20, 000 to 30, 000
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Condensation Polymerization
❖ Saturated polyesters (Linear):
• Like: (Carboxylic) acid + alcohol → ester + water
• Well-known example: PET = Poly Ethylene Terephtalate
o Two variants:
✓ Terephtalic acid + ethylene glycol
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Condensation Polymerization
❖ PET:
• Example bis-phenol A
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Condensation Polymerization
❖ Polycarbonate:
• High Tm: 225oC (aromatic groups)
• Tg = 149oC
• Amorphous and transparent
• Thermoplastic (linear chains)
• High toughness and dimensionally stable
• Temperature range -110oC to 140oC
• Lower resistance to chemicals
• Applications:
o Glass replacement, tough glazing
o Safety helmets, car lights
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