Transport of carboxylate salts of varying chain lengths in crosslinked polyether membranes

Abstract

Carboxylate anions of various chain lengths are important molecules for many applications such as CO2 reduction, membrane-based bioreactors, etc. Also, carboxylate anions are ubiquitous in biological molecules such as amino acids, fatty acids, etc. Therefore, understanding the transport behavior of carboxylates of different chain lengths in polymer materials is important both as a fundamental phenomenon but also for designing materials for applications. Here, we characterized transport behavior by measuring the permeability (P), and total partition coefficient (K) for a series of polymer membranes for four model carboxylate salts—sodium salts of formate (NaOFm), acetate (NaOAc), propionate (NaOPr), and butanoate (NaOBu)—at varied upstream salt concentrations (0.1–1 M) or a series of polyethylene glycol diacrylate (PEGDA)-based membranes with 1) varying pre-polymerization water content; 2) varying uncharged side chain comonomer (polyethylene glycol methacrylate, PEGMA), and 3) varying charged comonomer)2-acrylamido-2-methyl-1-propanesulfonic acid, AMPS). Also, diffusivity values of the four salts through the membranes have been calculated based on the solution diffusion model equation (PK × D), experimentally obtained permeability, and total partition coefficients. For a majority of these membranes, NaOFm's permeability is much higher than the other three carboxylate salts (NaOAc, NaOPr, and NaOBu) seemingly due to the lower chain length and thereby smaller hydrated diameter. In terms of total partition coefficient, a size-based trend is not observed. For example, NaOBu's total partition coefficient (K) is generally the largest among the four, and at higher upstream salt concentrations (1 M), the values of the total partition coefficients of the four salts converge. From this we conclude that the carboxylate salt transport through these PEGDA-based non-porous dense membranes to be primarily driven by kinetics and not sorption.