In theory, a miniemulsion should be an ideal environment for “living” radical polymerization
via the reversible addition−fragmentation chain transfer process (RAFT). Compartmentalization
minimizes radical−radical termination events, and droplet nucleation eliminates the mass transfer
limitation found in conventional “living” emulsion polymerizations. In practice, however, several
phenomena were observed when using the RAFT technique, indicating a deviation from this idealized
theory when the miniemulsion was stabilized by an ionic surfactant. Inefficient droplet nucleation, a
steadily rising polydispersity over the reaction, and the appearance of a separate organic phase after
initiation were all indications of particle instability. A distinct difference between standard polymerizations
and those that involve highly active RAFT agents is the fact that in RAFT polymerization there is a time
interval early in the reaction where oligomers dominate the molecular weight distribution. The presence
of large quantities of oligomers is postulated to be the culprit behind the destabilization observed through
a detrimental interaction with the ionic surfactant of the miniemulsion. Conductivity measurements
verified the increase of free surfactant in the aqueous phase over the course of reaction. Despite this,
results showed clear indication of “living” character with a linear evolution of molecular weight until
roughly 40% monomer conversion, after which the molecular weight showed contributions from initiator-derived chains.
The polymerization of styrene in latex particles by means of
pulsed high-energy electrons
has been studied. Using a sequence of electron beam pulses,
periodic initiation is accomplished, similar
to that used in pulsed laser polymerization. The larger
penetration depth of electron beams offers
advantages as compared to laser light in heterogeneous systems since
samples do not need to be optically
transparent. Therefore pulsed electron beam irradiations are more
suitable to study polymerizations
homogeneously irradiated in emulsion. From the molar mass
distribution of the formed polymer, the
monomer concentration in the particles can be determined.
Polystyrene particles swollen with styrene
were used. A typical dose per pulse was 1.5 Gy. The monomer
concentration in 46 nm diameter particles
was found to be 6 mol dm-3. Cationic and
anionic polymerization of styrene was suppressed by the
presence of water.
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