Molecular Simulation Study of the Kinetics and Mechanism of Micellization of Charged and Uncharged Block Copolymer in Aqueous Solution: Polystyrene-Block-Poly(acrylic acid) PS-b-PAA

The micellization kinetics, dynamics, and diffusional properties of poly(styrene)-block-poly(acrylic acid) copolymer chains in salt-free aqueous solution have been investigated as a function of the copolymer composition (X-PS) for the cases of un-ionized (charge density f = 0) and ionized PAA blocks (charge density f = 1), for the first time to our knowledge via atomistic molecular dynamic simulations. The micelle formation mechanism was inspected by tracking the population of unimers and clusters across the simulation trajectory; it confirmed that the asymmetric copolymer micelle formation followed a combined approach of unimer insertion and cluster fusion mechanisms, while symmetric micelle formation followed the unimer insertion method exclusively. Micelle formation took a longer time for copolymers having charged (ionized) PAA blocks (f > 0) and relatively short PS blocks (number fraction of PS repeat units in copolymer X-PS < 0.5) due to the presence of a greater number of hydrophobic groups, in agreement with the micellization kinetics observed for model copolymer micelles via DPD (Dissipative Particle Dynamics) simulation studies in literature. The conformational dynamics were studied using the relaxation of backbone dihedral angles and radius of gyration, for the core and corona blocks, respectively, showed that the PS blocks relaxed slower as compared to the soluble PAA blocks in solution due to their hydrophobic nature. The conformational relaxation time increased linearly for the PS blocks and was invariant for the PAA blocks with respect to XPS. The interaction dynamics of the PS-b-PAA copolymer micelles studied via the relaxation times of the PAA-PAA inter-chain (tau(HB,PP)) and PAA-water inter-molecular hydrogen bonds (tau(HB,PW)) showed the increase of tau(HB,PP), and the decrease of tau(HB,PW) in solution with the increase in XPS. The PAA-water H-bond relaxes slower at f = 1 than that at f = 0 due to the stronger affinity of ionized PAA units with water molecules. The diffusivity of the copolymer chains decreased exponentially with an increase in XPS value, which is in agreement with the theoretical and experimental observations described in the literature.