Efficient and reversible absorption of SO 2 in six new deep eutectic solvents (DESs) composed of levulinic acid (LA) and quaternary ammonium salts (choline chloride, CC; choline acetyl chloride, CAC; tetraethylammonium chloride, TEAC; tetraethylammonium bromide, TEAB; tetrabutylammonium chloride, TBAC; tetrabutylammonium bromide, TBAB) was systematically investigated. The molar ratio of LA to quaternary ammonium salt was fixed at 3 : 1. The results showed that all DESs possessed satisfactory performance for SO 2 absorption, with the maximum absorption capacity of 0.625 g SO 2 per g DES of LA-TEAC at 293.15 K under ambient pressure. The absorbed SO 2 was easily released by bubbling N 2 at 323.15 K and the regenerated DES was recycled five times without obvious loss of absorption performance. The solubility of SO 2 in DES of LA-CC at T = 293. 15, 303.15, 313.15, and 323.15 K under subatmospheric pressures was also determined. The relative thermodynamic parameters, i.e., absorption enthalpy, absorption entropy, and absorption Gibbs free energy, were further calculated, giving results with small negative values. The influence of water content on the SO 2 absorption was also investigated. According to NMR and FTIR analyses, the absorption of SO 2 in DES was a physical process. Moreover, all the DESs exhibited high selectivity for SO 2 /CO 2 . The present DESs are promising absorbents for SO 2 because of their high absorption capacity and good reversibility.
Reprocessable acrylate vitrimer needs
to enhance its strength to
expand the application in photo-three-dimensional (photo-3D) printing.
However, the methods for improving mechanical properties by the addition
of nanofillers or a multifunctional resin into acrylate vitrimers
are inappropriate for photo-3D printing due to the low curing speed
of photopolymerization induced by weakening light transmittance or
reduction of dimensional accuracy caused by large shrinkage. At present,
we demonstrate a new strategy for developing a kind of mechanically
robust and reprocessable 3D printing thermosets by combining hydrogen
bonds and exchangeable β-hydroxyl esters into acrylate vitrimers.
To realize this purpose, diacrylate prepolymer containing β-hydroxyl
esters was first synthesized from glycidyl methacrylate and suberic
acid. Then, the resin formulations for 3D printing comprising the
synthesized diacrylate prepolymer together with acrylamide generate
exchanged β-hydroxyl ester and pendent amide in cross-linked
networks. Here, hydrogen bonds resulting from the amide group as sacrificial
bonds dissipate vast mechanical energy under an external load. With
the inclusion of 20 wt % acrylamide, the average tensile strength
and Young’s modulus are up to 40.1 and 871 MPa, which increased
by about 4.4 and 3.85 times, respectively. The network rearrangement
of cross-linked vitrimers can be achieved through the dynamic ester
exchange reactions with gradual disappearance of hydrogen bonds at
elevated temperatures, imparting reprocessability into the printed
structures. Various photo-3D printing or UV irradiation shapes were
successfully produced, and these dissolved in ethylene glycol could
be remolded again.
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