Networked Nanogels from Self‐Assembly of End‐Functionalized Polymers at the Vapor/Liquid Interface: Molecular Dynamics Simulations

Abstract

Polymers confined at a vapor/liquid interface are particularly interesting and important as the immiscibility degree of polymers in the vapor phase is typically much less than in the liquid phase. With the help of molecular dynamics simulations, the self‐assembled monolayers of end‐functionalized polymers at the vapor/liquid interface are analyzed as a function of surface coverage, end‐attraction strength, and simulation temperature. Typical self‐assembled structures of end‐functionalized polymers such as rod‐like, branch‐like aggregates and scaffold‐like network gels have been successfully observed. Moreover, large end‐attraction interactions result into more ordered and stable networked gel configuration by providing enough scaffold crossing points in the networked framework. However, high temperature increases the diffusion coefficient of the polymers, meanwhile destroys networked structure. The potential of mean force demonstrates that the van der Waals interactions between polymer chains generate the aggregation of polymer backbones with side‐to‐side pattern, while the end‐group interactions lead to the aggregation of end‐groups of the polymers with end‐to‐end pattern. However, the end‐group interactions majorly mediate the formation of networked gels at the vapor/liquid interface. Our studies provide a deeper understanding of the formation of networked gels at vapor/liquid interface, and they can also guide the robust target‐specified design of nanostructured network materials.

Engulfing Behavior of Nanoparticles into Thermoresponsive Microgels: A Mesoscopic Simulation Study

“…The identical interaction applies as well for the interaction between a solvent particle and a subparticle in the nanoparticle. For the interaction between a crossed pair of monomer and subparticle, the similar short-ranged 12–6 LJ potential is adopted while the cutoff distance and the interaction energy parameter ε ij ′ ranging from 0.65ε 0 to 1.0ε 0 are adopted for assessing different adsorption strengths. , …”

“…and the interaction energy parameter ε ij ′ ranging from 0.65ε 0 to 1.0ε 0 are adopted for assessing different adsorption strengths. 35,36 Finally, the monomer−solvent interaction contains two contributions, namely the same short-ranged 12−6 LJ as in eq 3 plus the Morse potential with two different involved parameters ΔA pw = 12.4 and α pw = −26.8. The interaction parameters for the model system are all summarized in Table S2.…”