Randomly cross-linked amphiphilic copolymer networks of n-butyl acrylate and N,N-dimethylacrylamide: synthesis and characterization
Authors: Ioannou Anastasia I. , Apostolides Demetris E. , Patrickios Costas S. 
Published: May 2024

Abstract
Five randomly cross-linked amphiphilic copolymer networks (ACPN) were prepared via the free radical cross-linking copolymerization of the hydrophobic n-butyl acrylate (BuA) and the hydrophilic N,N-dimethylacrylamide (DMAAm), in the presence of a small amount (5 mol% with respect to the sum of BuA plus DMAAm monomers) of the hydrophobic 1,6-hexanediol diacrylate (HexDA) cross-linker, initiated by 4,4ʹ-azobis(4-cyanovaleric acid) in 1,4-dioxane at a 10 % w/v total monomer concentration. The five ACPNs differed in their BuA content, fixed at 10, 30, 50, 70 and 90 mol%. The two homopolymer networks, BuA and DMAAm, were also prepared using the same polymerization method. Thus, this study involved a total of seven polymer networks, forming a homologous series with BuA contents ranging from 0 to 100 mol%. These networks were characterized in terms of their degrees of swelling in tetrahydrofuran (THF) and water, their mechanical properties in water, and their adhesion to human skin. The degrees of swelling (DS) of the networks in THF were higher than those in water because THF is a non-selective solvent, whereas water is selective for the hydrophilic DMAAm units. The DSs in THF increased with the network content in the less polar BuA units, while the opposite was true for the DSs in water which decreased with the content in the hydrophobic BuA units from 11 (0 mol% BuA) down to 1.1 (100 mol% BuA). A maximum in the elastic modulus was observed for the hydrogel with 50 mol% BuA, reflecting the opposing effects of polymer composition in soft polymer (polyBuA) content and hydrogel water content. In contrast, the tensile strain at break increased monotonically with the hydrogel BuA content, reaching a remarkable ∼900 % for the hydrogel with 90 mol% BuA. Finally, the adhesion of the ACPNs, both in their dried and hydrated states, onto human skin was explored. The adhesion of the hydrated samples onto skin was stronger than that of the dried ones. The hydrated ACPN with 30 mol% BuA exhibited the strongest adhesion onto skin, attributable to the best combination of a rather high content in polar DMAAm units (70 mol%), and a rather low aqueous DS (∼2.5), with the low DS value causing only a small dilution in the DMAAm units participating in the polar interactions with skin. The present work demonstrates that, even in this synthetically simple ACPN system, the multiple effects of ACPN composition on a certain property, in some cases opposing and in some other cooperating, lead to a rather complicated behavior. In particular, as the BuA content increases, some properties display maxima (elastic modulus, stress at break and fracture energy of hydrated ACPNs, and adhesion of hydrated ACPNs onto skin) while some other properties exhibit monotonic increases (strain at break of hydrated ACPNs, and adhesion of dried ACPNs onto skin). Thus, the optimal ACPN for a particular application will highly depend on the property best-serving the particular application, e.g., the ACPNs with 30, 50 and 90 mol% BuA for strongest wet adhesion to skin, stiffest hydrogel response, and highest hydrogel extensibility and toughness, respectively.