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Phase Transition Kinetics of Doubly Thermoresponsive Poly(sulfobetaine)-Based Diblock Copolymer Thin Films

: Kreuzer, Lucas P.; Widmann, Tobias; Bießmann, Lorenz; Hohn, Nuri; Pantle, Johannes; Märkl, Raphael; Moulin, Jean-Francois; Hildebrand, Viet; Laschewsky, Andre; Papadakis, Christine M.; Müller-Buschbaum, Peter


Macromolecules 53 (2020), Nr.8, S.2841-2855
ISSN: 0024-9297
ISSN: 1520-5835
Deutsche Forschungsgemeinschaft DFG
Sachbeihilfe; LA 611/11-1
Zweifach und orthogonal schaltbare Blockcopolymere aus zwitterionischen und thermoresponsiven Blöcken
Fraunhofer IAP ()
block copolymer; responsive syteme; multiple stimuli; thin film; LCST; UCST

The swelling and phase transition behavior upon increasing temperature of a doubly thermoresponsive diblock copolymer thin film in steps above the characteristic cloud points (CPs) of the blocks is studied. An upper critical solution temperature (UCST)-type zwitterionic poly(sulfobetaine), poly(N,N-dimethyl-N-(3-methacrylamidopropyl)-ammoniopropane sulfonate) (PSPP, CPUCST = 31.5 °C), is combined with a lower critical solution temperature (LCST)-type nonionic poly(N-isopropyl-/methacrylamide) (PNIPMAM, CPLCST = 49.5 °C) block. Using time-of-flight neutron reflectivity (ToF-NR), we observe the swelling in D2O vapor at a constant temperature of 20 °C, followed by two subsequent temperature jumps, from 20 to 40 °C (above CPUCST) and from 40 to 60 °C (above CPLCST). The observed response of the diblock copolymer films deviates from the aqueous solution behavior, which is mainly attributed to the increased polymer concentration. Temperature-induced changes in the thin-film nanostructure are investigated with ToF grazing-incidence small-angle neutron scattering (GISANS). Alterations in the chain conformation and hydrogen bonding are probed by Fourier transform infrared (FTIR) spectroscopy. The ionic SO3– groups (in the PSPP block) and the nonionic hydrophilic amide groups (in both blocks) are found to affect the mechanisms of D2O uptake and release significantly.