However, even though a radical is generated, this reaction does result in a wastage of initiator, there is no increase in the number of radicals or the amount of monomer being converted to polymer.
1. Chain transfer to initiator
However, even though a radical is generated, this reaction does result in a wastage of initiator, there is no increase in the number of radicals or the amount of monomer being converted to polymer.
2. Side reactions
Cage effects
[ ]
Most significant reaction in the cage is
[ ] = cage where radicals are held for some time before they diffuse out. Once outside the cage the radicals can react with monomer [2 f COO•]
2 f COO•
Other reactions
of secondary importance
Average lifetime of neighboring radicals is 10–10 to 10–9 seconds with kf = 107 dm3/mol/s
In the cage:
The concentration of radicals in the solvent cage ~ 10 mol/dm3
Out of cage:
CMonomer = 0.1 to 10 mol/dm3
CR1 = 10–9 to 10–7 mol/dm3
3. Recombination of primary radicals has no effect on initiator efficiency
