| termination
or transfer reactions |
absence of termination or transfer
reactions, especially for
styrenes and dienes (truly “living” polymerization) |
some degree of termination and transfer reactions |
| synthesis of high MW polymers with low Đ (<1.1) |
extremely high MW polymers (>2 ×
106 g mol–1) exhibiting Đ < 1.1 |
moderate to high MW polymers (<106 g mol–1) exhibiting Đ < 1.1 (except
acrylates)– Emulsion RAFT produces very high MW polymers (up
to 106 g mol–1, Đ ∼ 1.3–1.4) |
| experimental
conditions (purification of reagents,
polymerization conditions) |
demanding |
simple |
| extensive purification procedures for monomers,
solvents, initiators,
etc. Polymerization is performed under high vacuum or Ar conditions
at low or moderate temperatures |
mild experimental conditions,
no requirements on extensive
purification of the reagents |
| type of vinyl
monomers |
styrenes, dienes, meth(acrylates), vinylpyridines;
functional
groups must be excluded or protected |
styrenes, meth(acrylates),
(meth)acrylamides, vinylpyridines,
and a broad choice of functional monomers |
| type of polymerization (in bulk, solution etc.) |
solution,
bulk |
bulk, solution, and emulsion polymerizations |
| purity of polymers |
complete elimination
of Li compound, depending on the termination
agent, by reprecipitation |
multipurification steps for
the removal of controlling agents
(metal residuals or CTA agents) |
| macromolecular
architectures |
access to a wide library of well-defined
(model) macromolecular
architectures (linear block polymers, multiblocks, stars, grafts,
cyclics, branched, dendrimers) through multifunctional initiators
or appropriate coupling reactions (e.g., chlorosilanes) |
access to a wide library of well-defined macromolecular architectures
(linear block polymers, multiblocks, stars, grafts, cyclics, brush,
branched, hybrid materials) through multifunctional initiators |
| functionalized polymers |
direct method
for chain-end and in-chain functionalization |
postpolymerization
modifications, limited access to in-chain
functionalization |
| large-scale industrial
applications |
thermoplastic elastomers (TPEs), rubber
industry (SBR) |
currently limited large-scale industrial
use due to the high
cost of controlling agents, difficulty in elimination of metal or
thio-containing end groups |
