Molecular dynamics simulation of associative polymers: Understanding linear viscoelasticity from the sticky Rouse model

Polymers bearing associative groups (APs) are characterized by their fantastic viscoelastic behaviors. In a work recently published by our group [Jiang et al., Macromolecules 53, 3438-3451 (2020)], a single chain sticky Rouse model (SRM) is proposed to describe the linear viscoelasticity of APs without the entanglement effect. In this work, equilibrium molecular dynamics simulation of an unentangled melt of an AP with uniformly distributed stickers is carried out, and the dynamic properties are simultaneously analyzed from the SRM. A chain model with capped stickers is proposed so that a well-defined association chemistry is promised in the simulation system. The relative effective frictional coefficient of stickers, which is the key parameter in the SRM, is extracted from the chain center-of-mass diffusion, and it is found to be consistent with the dynamics of associative reaction in the fully gelated network. Based on this, a linear relaxation modulus and segmental diffusion functions are predicted from the SRM without fitting parameters, and these are found to quantitatively agree with the simulation results, showing the effectiveness of the SRM in connecting the dynamic properties at different molecular levels. The change in relaxation modes and the definition of the effective chain center are found to be crucial in the scenario of the SRM. Finally, the above analysis from the SRM is successfully extended to the simulation system with asymmetric chains. All these simulation results strongly support the SRM as a molecular model for the linear rheology of AP.

Automated summary

The study introduced a single chain sticky Rouse model (SRM) to describe the linear viscoelasticity of polymers bearing associative groups (APs). The dynamic properties of APs were analyzed through equilibrium molecular dynamics simulation, and the SRM was found to effectively connect different molecular levels of dynamic properties. The analysis was successfully extended to simulation systems with asymmetric chains, supporting the SRM as a molecular model for the linear rheology of AP.