Polyelectrolyte Complexes as Desiccants: Thirsty Saloplastics

Desiccants or drying agents are used extensively to remove water from liquids and gases. Many organic reactions, from the laboratory to the industrial scale, are sensitive to even trace amounts of water. A new class of desiccants made from complexed polyelectrolytes, PECs, is described here, exploiting the affinity of charged polymer repeat units for water. The enthalpy of hydration of dry PECs was used for the first time as a quantitative measure of PEC water affinity. Several combinations of positive, Pol+, and negative, Pol–, polymers were used to prepare PECs. All of these displayed significant exothermic (favorable) enthalpies of hydration, measured at room temperature using solution calorimetry. A PEC made from poly(diallyldimethylammonium) and poly(styrene sulfonate) was extruded into convenient shapes. This PEC was used to dry three common solvents, acetonitrile, tetrahydrofuran, and toluene, representing a range of polarities. Added water was radiolabeled with tritium to provide accurate and sensitive detection of residual water after treatment. This PEC was almost as efficient as the comparison desiccants, molecular sieve 3A and calcium sulfate, after 3 days of static drying but could be regenerated at a lower temperature (120 °C) and shed far fewer dust particles

Antifouling Coatings from Glassy Polyelectrolyte Complex Films

Coatings that prevent or decrease fouling are sought for many applications, including those that inhibit the attachment of organisms in aquatic environments. To date, antifouling coatings have mostly followed design criteria assembled over decades: surfaces should be well/strongly hydrated, possess low net charge, and maintain a hydrophilic character when exposed to the location of use. Thus, polymers based on ethylene glycol or zwitterionic repeat units have been shown to be highly effective. Unfortunately, hydrated materials can be quite soft, limiting their use in some environments. In a major paradigm shift, this work describes glassy antifouling films made from certain complexes of positive and negative polyelectrolytes. The dense network of electrostatic interactions yields tough materials below the glass transition temperature, Tg, in normal use, while the highly ionic character of these polyelectrolyte complexes ensures strong hydration. The proximity of equal numbers of opposite charges within these complexes mimics zwitterionic structures. Films, assembled layer-by-layer from aqueous solutions, contained sulfonated poly(ether ether ketone), SPEEK, a rigid polyelectrolyte that binds strongly to a selection of quaternary ammonium polycations. Layer-by-layer buildup of SPEEK and polycations was linear, indicating strong complexes between polyelectrolytes. Calorimetry also showed that complex formation was exothermic. Surfaces coated with these films in the 100 nm thickness range completely resisted adhesion of the common flagellate green algae, Chlamydomonas reinhardtii, which were removed from surfaces at a minimum applied flow rate of 0.8 cm s–1. The total surface charge density of adsorbed cations, determined with a sensitive radioisotopic label, was very low, around 10% of a monolayer, which minimized adsorption driven by counterion release from the surface. The viscoelastic properties of the complexes, which were stable even in concentrated salt solutions, were explored using rheology of bulk samples. When fully hydrated, their Tg values were observed to be above 75 °C

Ion Content of Polyelectrolyte Complex Coacervates and the Donnan Equilibrium

Oppositely charged polyelectrolytes in solution spontaneously associate into hydrated complexes or coacervates, PECs. The morphology, stability, and properties of PECs depend strongly on their ion content, which moderates the “sticky” reversible interactions between Pol+ and Pol– oppositely charged repeat units. Here, it is shown that the distribution of ions between a PEC and the aqueous solution in which it is immersed is accurately predicted by the Donnan equilibrium. For ideal, stoichiometric mixing of polyelectrolytes, corresponding to an enthalpy of complexation ΔHPEC → 0, the salt, MA, concentration inside the PEC, [MA]PEC, is equal to the solution salt concentration, [MA]s. Isothermal calorimetry measurements along a Hofmeister series show that if mixing is exothermic, [MA]PEC < [MA]s, while for endothermic association of Pol+ and Pol–, [MA]PEC > [MA]s. A set of simple self-consistent expressions illustrate PEC salt response without consideration of net Coulombic or electrostatic forces between charged species. ΔHPEC exactly predicts deviations from ideal Donnan equilibria, which are connected to the equilibria between associated or intrinsic pairs of Pol+Pol– and extrinsic Pol+A– and Pol–M+ pairs, where counterions compensate polyelectrolyte charges. The equilibrium constant Kpair for Pol+Pol– pair formation is shown to be proportional to the volume charge density of the hydrated, ion-free complex. Kpair may also be used to estimate the critical salt concentration at which polyelectrolytes completely dissociate

Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate

The linear viscoelastic response, LVR, of a hydrated polyelectrolyte complex coacervate, PEC, was evaluated over a range of frequencies, temperatures, and salt concentrations. The PEC was a nearly stoichiometric blend of a quaternary ammonium poly([3-(methacrylamido)propyl]trimethylammonium chloride), PMAPTAC, and poly(2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt), PAMPS, an aliphatic sulfonate, selected because they remain fully charged over the conditions of use. Narrow molecular weight distribution polyelectrolytes were prepared using fractionation techniques. A partially deuterated version of PMAPTAC was incorporated to determine its coil radius of gyration, Rg, within PECs using small-angle neutron scattering. Chain dimensions were determined to be Gaussian with a Kuhn length of 2.37 nm, which remained constant from 25 to 65 °C. The LVR for a series of matched molecular weight PECs, mostly above the entanglement threshold, exhibited crossovers of modulus versus frequency classically attributed to the reptation time, relaxation between entanglements, and the relaxation of a Kuhn length of units (the “monomer” time). The scaling for zero shear viscosity, η0, versus chain length, N, was η0 ∼ N3.1, in agreement with “sticky reptation” theory. The lifetime and activation energy, Ep, of a pair between polyanion and polycation repeat units, Pol+Pol–, were determined from diffusion coefficients of salt ions within the PEC. The activation energy for LVR of salt-free PECs was 2Ep, showing that the key mechanism limiting the dynamics of undoped PECs is pair exchange. An FTIR technique was used to distinguish whether SCN– acts as a counterion or a co-ion within PECs. Doping of PECs with NaSCN breaks Pol+Pol– pairing efficiently, which decreases effective cross-linking and decreases viscosity. An equation was derived that quantitatively predicts this effect

Anilinium Salts in Polymer Networks for Materials with Mechanical Stability and Mild Thermally Induced Dynamic Properties

Dynamic nucleophilic exchange of quaternary anilinium salts has been incorporated into rehealable and malleable polymeric materials that can be activated under mild (60 °C) thermal stimulus. The mechanism of dynamic exchange between quaternary anilinium salt and free aniline was assessed in small-molecule model experiments. The dynamic exchange was found to be dissociative in nature, due to the indirect SN2 mechanism, where initially the bromide anion attacks the anilinium salt to generate an alkyl bromide which undergoes subsequent attack by a free aniline group. A quaternary anilinium-based cross-linker was synthesized to act as dynamic linkages in the polymer network. Cross-linked polymeric materials showed thermoresponsive rehealing and malleability properties at 60 °C along with being resistant to irreversible creep under ambient conditions. The use of anilinium salts enables dynamic exchange to occur with significantly milder thermal stimulus than other comparable materials, while maintaining mechanical stability