ATRP in Water: Kinetic Analysis of Active and Super-Active
Catalysts for Enhanced Polymerization Control
Marco Fantin
Abdirisak A. Isse
Krzysztof Matyjaszewski
Armando Gennaro
10.1021/acs.macromol.7b00246.s001
https://acs.figshare.com/articles/journal_contribution/ATRP_in_Water_Kinetic_Analysis_of_Active_and_Super-Active_Catalysts_for_Enhanced_Polymerization_Control/4787626
Atom transfer radical
polymerization (ATRP) in water is characterized
by very high catalytic activity, i.e. the rate constant (<i>k</i><sub>act</sub>) of the “activation” reaction between
Cu<sup>I</sup> complexes and alkyl halides (RX) is very large. To
accurately study such fast reactions in water, we developed a collection
of electrochemical methods applicable for the determination of a vast
range of <i>k</i><sub>act</sub> values (>7 orders of
magnitude).
These included rate constants of extremely fast reactions with <i>k</i><sub>act</sub> > 10<sup>7</sup> mol<sup>–1</sup> dm<sup>3</sup> s<sup>–1</sup>. We studied three widely used
ATRP catalysts ([Cu<sup>I</sup>PMDETA]<sup>+</sup>, [Cu<sup>I</sup>TPMA]<sup>+</sup>, and [Cu<sup>I</sup>Me<sub>6</sub>TREN]<sup>+</sup>) and an extended series of water-soluble initiators. Accurate results
were obtained in the range 1 < <i>k</i><sub>act</sub> < 10<sup>8</sup> mol<sup>–1</sup> dm<sup>3</sup> s<sup>–1</sup>, allowing to build for the first time precise structure–reactivity
correlations for aqueous ATRP, in both pure water and water/monomer
mixtures. The results were compared to traditional ATRP systems in
organic solvents. The collected data greatly expand the available
range of investigated catalyst/initiator systems.
2017-03-24 19:08:36
mol
TREN
Cu
dm
RX
Enhanced Polymerization Control Atom transfer
k act
PMDETA
ATRP
catalyst
TPMA