Effect of Counterions on the Self-Assembly of Polystyrene–Polyphosphonium Block Copolymers

Abstract

The ability to manipulate block copolymers on the nanoscale has led to many scientific and technological advances. These include nanoscale ordered bulk and thin films and also solution phase components; these are promising materials for making smaller ordered electronics, selective membranes, and also biomedical applications. The ability to manipulate block copolymer material architectures on such small scales has risen from thorough investigations into the properties that affect the architectures. Polyelectrolytes are an important class of polymers that are used to make amphiphilic block copolymers. In this context the authors synthesized polystyrene-b-polyphosphonium block copolymers with different anions coordinated to the polyphosphonium block in order to study the effect of the anion on the aqueous self-assembly of the polymers. The anions play an important role in the solubility of the monomeric materials which results in differences in the self-assembly observed through dynamic light scattering and transmission electron microscopy.

Interplay of Solvation and Size Effects Induced by the Counterions in Ionic Block Copolymers on the Basis of Hofmeister Series

“…On the other hand, one should bear in mind that the volume fraction of hydrophilic block is an essential reason for determining the morphologies of most neutral BCP systems. However, for a permanently charged block, the function of newly introduced anions alters not only the separation of anions and cationic block but also the hydrophilic volume fraction through the size of anion itself . The former is related to the solvation of the counterions, while the latter alters the volume fraction of the hydrophilic block.…”

“…However, for a permanently charged block, the function of newly introduced anions alters not only the separation of anions and cationic block but also the hydrophilic volume fraction through the size of anion itself. [63] The former is related to the solvation of the counterions, while the latter alters the volume fraction of the hydrophilic block. In this study, the hydration radius of the anion follows the order: Brˉ < Iˉ < SCNˉ < PF 6ˉ.…”

Exploring How Vitrimer-like Properties Can Be Achieved from Dissociative Exchange in Anilinium Salts

“…Synthesis of 4-vinyl benzyl bromide (VBBr) was carried out following the previous literature report and confirmed by 1 H NMR. 45,56 Synthesis of N,N-Dimethyl-4-vinyl-N-(4-vinylbenzyl)benzenaminium Bromide. Synthesis of N,N-dimethyl-4-vinyl-N-(4vinylbenzyl)benzenaminium bromide (VBABr) was carried out following the previous literature report and confirmed by 1 H NMR.…”

Flexible conductive poly(styrene‐butadiene‐styrene)/carbon nanotubes nanocomposites: Self‐assembly and broadband electrical behavior

“…Currently, block copolymers are also intensively investigated, mainly due to their ability of self‐assembly into well‐ordered structures with dimensions in the order of nanometers . From a thermodynamic point of view, the self‐assembly of a block copolymer relies on the minimization of the free energy, due to the competition between the enthalpy, related to the Flory‐Huggins interaction parameter (χ), and entropy, which depends on the degree of polymerization ( N ).…”

“…These morphologies include body centered cubic packed spheres, hexagonally packed cylinders (HEX), continuous gyroids, and alternating lamellae . Accordingly, the self‐assembly of the block copolymers can be a powerful tool to create functional materials and CPNs with tailored structures and, thereby fine‐tuning properties …”