Kinetically Controlled Patterning of Highly Cross-Linked Phosphonium Photopolymers Using Simple Anion Exchange

Abstract

A phosphonium salt possessing three methacrylate groups has been incorporated into a photopolymeric system to generate highly cross-linked polyelectrolyte networks. Emergent chemical and physical properties in the polymers were observed and attributed to the tandem increase in cross-link density and ion-content upon incorporation of the self-cross-linking cation. Anion-exchange with bis(trifluoromethylsulfonyl)imide or dodecylbenzenesulfonate resulted in significant differences in wettability and ion-exchange behavior. The passivating effects of dodecylbenzenesulfonate were utilized to selectively pattern fluorescein dye into the polymer network, highlighting a new patterning procedure using ionic-bond forming reactions.

Convenient synthetic route to tetraarylphosphonium polyelectrolytes via palladium‐catalyzed P–C coupling of aryl triflates and diphenylphosphine

“…Polyelectrolytes have been attracting tremendous interest in recent decades due to the growing range of applications available based on their intriguing and unique properties . Phosphonium‐derivatized polyelectrolytes in particular have been investigated for application in diverse applications ranging from their use as antimicrobial agents and biodelivery vectors, to materials and energy applications such as alkaline fuel cell membranes, redox‐active films, ordered optically active materials and optoelectronic devices …”

Photopolymerization of Ionic Liquids – A Mutually Beneficial Approach for Materials Fabrication

“…One issue with these formulations is the replacement of IL with neutral crosslinker, which is needed to provide the coating with mechanical integrity. This use of a crosslinkable phosphonium ionic liquid would allow for the fabrication of highly crosslinked, non‐swellable PILs with nearly 100 % IL content . Materials comprised of highly crosslinked ILs possess very low swellability and are thus excellent candidates for anion‐exchange printing applications.…”

“…This use of a crosslinkable phosphonium ionic liquid would allow for the fabrication of highly crosslinked, non-swellable PILs with nearly 100 % IL content. [65] Materials comprised of highly crosslinked ILs possess very low swellability and are thus excellent candidates for anion-exchange printing applications. For example, a PDMS stamp coated with dodecylbenzenesulphonate (DBS) was pressed on to a highly crosslinked PIL film, resulting in a transfer of DBS to a PIL surface ( Figure 3).…”

Living anionic polymerization of 4‐diphenylphosphino styrene for ABC triblock copolymers

“…Incorporating phosphorus‐containing sequences into macromolecular architectures advantageously provides diverse oxidation states (phosphates, phosphines, phosphine oxides and phosphoniums), high alkylation and metal catalysis efficiency, thermal and base stability and tailored structures and morphologies . Literature precedence exists for phosphorus‐containing monomers exhibiting vinylbenzyl‐, acrylate‐ and methacrylate‐polymerizable units, facilitating synthetic methods involving conventional and controlled free radical polymerizations . However, DPPS does not contain a benzylic carbon adjacent to the phosphorus atom, thus eliminating the low temperature reverse Menschutkin (nucleophilic) degradation pathways.…”