Compatibilization of Polymer Blends by Ionic Bonding

Chemically dissimilar polymers are rarely miscible due to a specific entropy of mixing that scales as 1/N, where N is the degree of polymerization. As a consequence, the compatibilization of immiscible polymer blends presents a major challenge to plastics recycling efforts. We demonstrate that when the chain ends of two highly immiscible polymers are functionalized with reacting acid and base groups, ionic junctions form in situ by proton transfer, leading to the stabilization of interfaces and the suppression of macroscopic phase separation. Due to the dynamic nature of proton transfer, the microstructure can be tuned via ionic bond energy (h) and segregation strength (χN). In this work, a library of ionically end-functionalized polystyrene (PS) and polydimethylsiloxane (PDMS) is used to demonstrate the importance of end-group acidity/basicity and molecular weight on compatibilization. Well-ordered lamellae result from blending polymers with strong acid and base units, while less ordered, more swollen microphases occur in systems with weak acid and base end groups or larger molar mass. Heating the ionic blends results in reverse proton transfer and destruction of the close-contact ion pairs. As a result, domains are swollen with the resulting unbonded homopolymers, which in sufficient amounts, leads to macrophase separation. Moreover, external salt ions screen the electrostatic attractions and disturb ionic compatibilization. The self-consistent field theory (SCFT) of this system reveals that the ionic interactions can be tuned to create a broad range of morphologies, from microphases to macrophases.