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A new LCST-type thermoresponsive polyelectrolyte P[P4,4,4,4][SS], poly(tetrabutyl phosphonium styrene sulfonate), was introduced to PMEO2MA (poly(2-(2-methoxyethoxy)ethyl methacrylate)) via RAFT polymerization, in order to explore the transition behavior of the block copolymer PMEO2MA-b-P[P4,4,4,4][SS] with two distinct LCST-type segments. A relatively sharp LCST-type phase transition with only one transition point is observed in the turbidity curves, while the whole phase transition is completely different from the micro perspective. The phase transition temperature range is relatively broad, according to the unsynchronized changes of different protons of the two blocks in the temperature-variable 1H NMR analysis. From PCMW analysis, it is found that there exists an obvious two-step phase transition behavior, especially in the region of the C–H groups. Accordingly, we divided the whole transition process into two subregions: 20–40 °C and 40–55 °C in 2Dcos analysis. At the first stage of 20–40 °C, the CH3 groups mainly belonging to the backbones of PMEO2MA blocks have the earliest response to the heating and drive the first step of the dehydration process of PMEO2MA-b-P[P4,4,4,4][SS], resulting in the formation of an intermediate micelle state composed of the collapsed PMEO2MA core and hydrophilic P[P4,4,4,4][SS] corona. In particular, the conformational changes and the more compact structures due to the interaction between the C=O groups and P[P4,4,4,4][SS] segments (ν(C=O…D2O-PILs)) were observed using IR analysis. With the continual increase of the temperature, when the second temperature range of 40–55 °C is reached, the P[P4,4,4,4][SS] segments start to collapse and expel the water molecules, driven by the anions of the poly(ionic liquid)s, with the phosphonium cations being distributed over the relatively hydrophilic outside. [ABSTRACT FROM AUTHOR]

The assembly properties, thermal phase behavior and microdynamics of well-defined P(MEO2MA-co-OEGMA)-b-P4VP, (poly(2-(2-methoxyethoxy)ethylmethacrylate)-co-poly(oligo(ethylene glycol) methacrylate))-b-poly(4-vinyl pyridine), in aqueous solution during heating are investigated in detail by dynamic light scattering (DLS), turbidity measurements, temperature-variable 1H NMR and FTIR spectroscopy in combination with two-dimensional correlation spectroscopy (2Dcos) and the perturbation correlation moving window (PCMW) technique. It is observed that the chain length of the relatively hydrophobic P4VP segment strongly affects the temperature-induced phase transition behavior of the block copolymers: the copolymers with shorter P4VP7/10 segments exhibit an abrupt phase transition process, while the copolymer with longer P4VP19 blocks presents a relatively gradual transition behavior. Moreover, the two systems with different P4VP segment lengths have different morphologies in aqueous solution: a single-chain globule for shorter P4VP7/10 systems and a core–shell micelle consisting of a relatively hydrophobic P4VP core and a hydrophilic POEGMA-based shell for the longer P4VP19 system. Analysis of spectral results clearly illustrates that the dehydration of the C=O groups at the linkages between backbones and pendant chains predominates the sharp phase transition of P(MEO2MA-co-OEGMA)-b-P4VP10, while the dehydration of hydrophobic C–H groups on the side chains in P(MEO2MA-co-OEGMA)-b-P4VP19 leads to the continuous increase of the hydrodynamic diameter (Dh) upon heating. [ABSTRACT FROM AUTHOR]