Polymer Science and Engineering

Zenamarkos B. (PhD)

Process Engineering Program

Faculty of Chemical and Food Engineering
Bahir Dar Institute of Technology (BiT)
Bahir Dar University
August, 2019

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Polymer Synthesis and
Reaction Kinetics

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 Polymers Synthesis and Reaction Kinetics
Why Synthesis Kinetics?

• Because the kinetics determine:

- The molecular weight

- The molecular weight distribution
- (The degree of cross-linking)

Key parameters for the material

properties of a polymer!!
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 Polymers Synthesis and Reaction Kinetics
❖ Polymerization:
➢ any process in which relatively small molecules, called monomers,
combine chemically to produce a very large chainlike or network
molecule, called a polymer.

➢ The monomer molecules may be all alike, or they may represent two,
three, or more different compounds.

➢ The formation of stable covalent chemical bonds between the

monomers sets polymerization apart from other processes, such as
crystallization, in which large numbers of molecules aggregate under
the influence of weak intermolecular forces.
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 Polymers Synthesis and Reaction Kinetics

❖Monomer:

➢ a molecule of any of a class of compounds, mostly organic, that can

react with other molecules to form very large molecules, or polymers.

➢ The essential feature of a monomer is polyfunctionality, the capacity

to form chemical bonds to at least two other monomer molecules.

➢ Bifunctional monomers can form only linear, chainlike polymers, but

monomers of higher functionality yield cross-linked, network polymeric
products.

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 Polymers Synthesis and Reaction Kinetics

❖Classification of polymer synthesis:

1) According to functionality: number of bonds per monomer

2) Kinetic scheme: Addition (chain-growth) or Condensation (step-

growth)

1) Number of monomers: Homo or Hetero- polymers

2) Type of chemical reaction taking place (e.g., ester formation)

3) Process used: bulk, emulsion, suspension, solution

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 Polymers Synthesis and Reaction Kinetics

❖ Addition:
➢ rapid polymerization via initiator
• Radical initiator
• Ionic mechanism

➢Kinetics of initiation, propagation and termination

➢polymer chains are formed in a stepwise fashion by random union of monomers

to dimers, trimers and higher species throughout the monomer matrix.
➢Only one monomer added per reaction.

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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

▪ Typical case is polymerization of monomers with double bond

functionality (e.g., vinyl monomers)

▪ Polymer molecular weight = n*M (monomer)

▪ Steps of initiation, propagation and termination

▪ Initiation by free radicals, anionic or cationic groups

▪ Most common is free radical initiation.

Examples are PVC, PE, PP, PS, PAN, PTFE, etc.

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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

• The actual polymerization takes place by adding

monomers M to the radicals.

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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

• With ‘regulator’ molecule, to limit molecular weight

• With other polymer chain or internally in own chain

o Leads to branching
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I. Radical Addition Polymerization

❖Control of molecular weight:

• For high molecular weight, use low initiator concentration

• but initiation speed will be slow, so slow polymerization rate

• Type of termination can be controlled by temperature

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Industrial Processes for Radical Addition Polymerization

❖ Mass polymerization
❖ Solution polymerization
❖ Suspension polymerization
❖ Emulsion polymerization

▪ Very important is temperature control

• Most cases, polymerization is exothermic
• Double bond to single bond conversion releases 10-20 kcal/mol
• Adiabatic temperature rise of 200 to 400oC !
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Radical Polymerization in the Mass

▪ 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:

❖High pressure production of LDPE

• Temperature: 150 – 300 oC
• Pressure: 1800 – 3000 bar ! (to compress liquid ethylene)
• Peroxide initiator
• In these conditions, chain transfer is favoured,
✓ highly branched molecules result
• 40-60% crystallinity (with small crystals)
• Low density (0.92) and low melting point (110oC)

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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

❖ The monomer is dissolved in suitable solvent

• Temperature can be controlled by evaporation of solvent
• Viscosity can be kept low (stirring)
• Solvent can be recycled
• Complete conversion of monomer can be reached
• Two possibilities:
o Polymer also dissolves in solvent (e.g., PS in benzene)
✓ Initiator is suspended and excess can be filtered off
o Polymer does not dissolve and precipitates
✓ Polymer is filtered off
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 Radical Polymerization in Solution

❖ Disadvantages of solution polymerization:

• Termination by chain transfer is more likely
o Limited degree of polymerization and spread in molecular weight
o Difficult to remove all solvent
o Solvent reduces speed of polymerization

➢ Primarily used for polymers which are applied in the solvent (coatings,
adhesives)

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 Radical Polymerization in Suspension

❖ Monomer + Initiator are suspended in non-solvent (often water)

• Vigorous stirring determines particle size
• 10-25% monomer to non-solvent
• ‘mass’ polymerization in
each droplet
• Polymer beads are formed;
then filtered, washed and
dried.
• Dispersion agent is used to
prevent coagulation of
viscous droplets Schematic representation of suspension polymerization
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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

Schematic representation of the initial stages of an emulsion polymerization

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Radical Polymerization in Emulsion

❖ 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

Typical example of electron-acceptor

• Lewis acids BF3, AlCl3, TiCl4, SnCl4
• Co-catalyzing Lewis-base necessary like H2O

H+ becomes the initiator

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Cationic Addition Polymerization

❖ Example: PP- Initiation

➢ Activation energy for cationic polymerization is low, so reactions take

place at low temperature (<< 0oC !) and are not very temperature –
sensitive.

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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

• monomer must squeeze between carbonium-ion and negative counter-ion, so

type of initiator affects propagation
• More possibility for stereo-chemical control: isotactic or syndiotactic
structures
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Cationic Addition Polymerization

❖ Termination:

• Combination is not possible, due to electrostatic repulsion

What can happen:

✓ Elimination of a proton, which can act as initiator again
✓ The stronger the Lewis-acid, the less likely termination happens (and
the more likely initiation occurs)
✓ Transfer reactions, e.g., transfer to monomer

• At low temperature, termination can be slowed down, to allow reaching

interesting molecular weights

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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

Acrylonitrile > methylmetacrylate > styrene > butadiene

Example Propagation of PAN:

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Anionic Addition Polymerization

❖ Termination:
• By proton transfer with the solvent (example PAN in ammonia)

• Elimination of hydride-ion or transfer with monomer is less likely

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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

✓ Dimethyl-terephtalate + ethylene glycol

• Boiling temperature
methanol only 65oC, so
this variant easier to
enhance

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Condensation Polymerization
❖ PET:

• Aromatic ring leads to relatively high transition temperature

• Melting temperature = 260oC, Tg = 64oC
• Semi-crystalline, amorphous when cooled rapidly
• PET has high stiffness (~ 3 GPa)
• Bi-axially stretched PET has high strength, stiffness and low
permeability for gases
• Ideal for packaging (bottles)
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Condensation Polymerization
❖ Polycarbonates (PC):
• Di-ol + phosgene (in presence of NaOH)

• Example bis-phenol A

• Tough and transparent polymer

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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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