Polymerization: Process were monomers are linked in chains.

Polymer: Molecule made up of repeating structural units (monomers). Etileno.

Homopolymers: Single repeating unit

Step reactions: Bifunctional or polyfunctional polymers

Chain reactions: Require presence of an initiator

Copolymers: two or more repeating units

Step polymerization: Requires at least a reactive functional group on each end of

monomer to react with other monomers. Molecular weight builds up slowly.
Conversion is no good measure for progress of reaction. Will proceed even if all
the monomer has been consumed. The progress must be measured with
parameter “p” (fraction of functional groups that have reacted).

Degree of polymerization (average number of units per chain):

Flory-Schulz distribution:

Chain polymerization: 1Requires initiator, adds one repeating unit at a time.

Molecular weight builds up fast once a chain is initiated (polystyrene).

Free-Radical Polymerization

 2Initiation: Adding a small amount of chemical that decomposed to form free

radicals.
 Monofunctionals:

3Multifunctional (form different radicals)

 4Propagation:

(Assuming equal reactivity)

 Chain transfer (Transfer of a radical from a growing polymer chain):
1. 5Transfer to a monomer:

2. 6Transfer to another species:

3. 7Transfer of the radical to the solvent:

R’s produced in chain reactions are taken to be same. However, in some

cases, the transfer agent may be too large or unreactive. Choice of
solvent for polymerization is important.
 Termination (to form dead polymer):
1. 8Addition of two growing polymers:

2. 9By disproportionation:
Developing the Rate Laws for the Net Rate of Reaction
Begin by considering rate of formation of initiator radical, which is

f= Fraction of initiator free radicals successful in initiating chaining. (0.2-

0.7)
Use PSSH for the initiator. Total loss of R1 radicals is found by adding
them in each reaction (sumatoria). PSSH allows to modify rate low to
find closed form solutions for polymerization reactions.
10Total free-radical concentration:

11Rate of disappearance of monomer:

12Rate of formation of dead polymers:

Modelling a Batch Polymerization Reactor

Monomer balance:

Initiator balance:

Concentration profile:
Probability of propagation: