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Controlling the Polymer Microstructure in Anionic Polymerization by Compartmentalization
Author(s) -
Rieger Elisabeth,
Blankenburg Jan,
Grune Eduard,
Wagner Manfred,
Landfester Katharina,
Wurm Frederik R.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201710417
Subject(s) - copolymer , monomer , dilution , polymer chemistry , polymer , compartmentalization (fire protection) , polymerization , emulsion , emulsion polymerization , cyclohexane , phase (matter) , kinetics , chemical engineering , chemistry , materials science , thermodynamics , organic chemistry , physics , quantum mechanics , engineering , enzyme
An ideal random anionic copolymerization is forced to produce gradient structures by physical separation of two monomers in emulsion compartments. One monomer (M) is preferably soluble in the droplets, while the other one (D) prefers the continuous phase of a DMSO‐in‐cyclohexane emulsion. The living anionic copolymerization of two activated aziridines is thus confined to the DMSO compartments as polymerization occurs selectively in the droplets. Dilution of the continuous phase adjusts the local concentration of monomer D in the droplets and thus the gradient of the resulting copolymer. The copolymerizations in emulsion are monitored by real‐time 1 H NMR kinetics, proving a change of the reactivity ratios of the two monomers upon dilution of the continuous phase from ideal random to adjustable gradients by simple dilution.