Free Radical Polymerization - Initiation


Thermal initiators:

  • Most common kind of FR initiator.
  • Unimolecular decomposition.
  • First order kinetics.
  • Most common examples: peroxides or azo compounds.

Peroxides:

Peroxide initiators

Azo compounds:

Azo initiators

(Temperatures are for 10 hour half-lives.)


Redox initiators:

  • Usually 2 component.
  • Rarely used.
  • Example: Fenton's reagent

Fenton's reagent


Self-initiation:

  • Only proven to occur with styrene.
  • Mechanism involves preliminary dimer formation (via Diels-Alder reaction of two monomers, followed by hydrogen atom transfer to a third monomer).

Styrene autopolymerization


Photochemical:

  • One or two component.
  • Used for thin films.
  • Examples:

Photochemical initiator

Photochemical initiator


Ionizing radiation:

  • X-ray, gamma-ray.
  • Random destruction leads to radical formation.
  • Used only in very special cases.

Radiation FR initiation