We investigate the solvent density driven changes in polymer conformation and phase behavior that occur in a supercritical fluid, with a particular emphasis on conditions near the lower critical solution temperature ͑LCST͒ phase boundary. Using continuous space Monte Carlo simulations, the mean square end-to-end distance (R) and radius of gyration (R g ) are calculated for a single chain with 20 Lennard-Jones segments in a monomeric solvent over a broad range of densities and temperatures. The chains collapse as temperature increases at constant pressure, or as density decreases at constant temperature. A minimum in R and R g occurs at a temperature slightly above the coil-to-globule transition temperature ͑C-GTT͒, where the chain adopts a quasi-ideal conformation, defined by the balance of binary attractive and repulsive interactions. Expanded ensemble simulations of finite-concentration polymer-solvent mixtures reveal that the LCST phase boundary correlates well with the single chain C-GTT. At temperatures well above the LCST, the chain expands again suggesting an upper critical solution temperature ͑UCST͒ phase boundary above the LCST.
Deep Eutectic Solvents (DESs) based upon mixtures of Acrylic Acid (AA) or Methacrylic Acid (MAA) and Choline Chloride (CCl) demonstrated superior performance than regular organic solvents and even ionic liquids for frontal polymerizations (FPs). Full recovering of CCl after FP provided an interesting green character to the process.
We have demonstrated that l-lactide (LLA) forms a eutectic mixture with ε-caprolactone (CL) in a 30:70 mol ratio with a melting point of -19 °C. Taking advantage of the liquid nature and polarity at the LLA-CL eutectic mixture, we have formulated oil-in-eutectic-mixture high-internal-phase emulsions (HIPEs) by stepwise addition of the oil phase (tetradecane) into the continuous phase (mixture of surfactant and LLA-CL eutectic mixture) at room temperature and under stirring. The oil-in-LLA-CL-eutectic-mixture HIPEs were polymerized in the presence of both the organocatalysts 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and methanesulfonic acid (MSA) and the initiator benzyl alcohol (BnOH) at 37 °C and without the addition of any extra reagent or solvent in one single pot. The catalytic selectivities of DBU and MSA for the ring-opening polymerizations of LLA and CL, respectively, allowed the synthesis of macroporous poly(l-lactide)/poly(ε-caprolactone) blend materials. The resulting materials exhibited a macroporous morphology that resembled that of the HIPE internal-phase droplets used as templates. These materials proved effective as oil absorbents for oil/water separation with not only a noticeable performance, similar to that of conventional sorbents in terms of both selectivity and recyclability, but also unprecedented safe disposability, certainly of interest for applications in the cleanup of industrial oily wastewaters and oil spills, thanks to the biodegradable features of both poly(ε-caprolactone) and poly(l-lactide).
Due to their viscosity and polarity, DESs represent a suitable internal phase for HIPEs containing styrenic monomers in addition to acrylates, thus expanding on the range of monomers forming polymerizable DES-based HIPEs.
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