Insight in the Phase Separation Peculiarities of Poly(dialkylaminoethyl methacrylate)s

The thermoresponsive and pH-sensitive behavior of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), poly(N,N-diethylaminoethyl methacrylate) (PDEAEMA), and poly(N,N-diisopropylaminoethyl methacrylate) (PDiPAEMA) is compared by use of different techniques. We employed temperature- and pH-dependent turbidimetry, fluorescence spectroscopy (of the polarity indicator 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran, 4HP, which is sometimes also abbreviated as DCM), and IR spectroscopy (of the carbonyl band). Within specific pH windows, all polymers showed phase separation at elevated temperatures (showing a lower critical solution temperature behavior, an LCST behavior). By increasing the hydrophobicity of the dialkylaminoethyl substituent, the phase separation is shifted to lower pH (at constant temperatures; pH(PDMAEMA) > pH(PDEAEMA) > pH(PDiPAEMA)) or to lower temperatures (at constant pH; T-PDMAEMA > T-PDEAEMA > T-PDiPAEMA). While PDMAEMA does not exhibit pronounced changes in polarity upon phase separation (as seen by fluorescence spectroscopy), PDEAEMA and PDiPAEMA provide a nonpolar surrounding for the 4HP uptake above their collapse. In addition, PDiPAEMA causes the sharpest transition (as seen by the 4HP probe), although the carbonyl hydration experiences a more gradual (sigmoidal) transition for all polymers (as seen by IR). These observations allow a distinction of the phase separation mechanisms. While the LCST properties of PDMAEMA are mainly caused by backbone/carbonyl interactions, its rather polar dimethylaminoethyl group does not inflict pronounced hydrophobicity, but promotes a higher water content within the phase-separated polymer. In contrast, the phase separation of PDEAEMA and PDiPAEMA is mainly influenced by the less polar dialkylaminoethyl groups, leading to drastic changes in the hydrophobicity around the cloud points. Further, the IR data suggest that the diisopropylaminoethyl groups of PDiPAEMA tend to backfold to the carbonyl groups/backbone to minimize water-polymer contact already in its soluble state. Finally, this study might lead to advanced lasing applications of the laser dye 4HP.