Synthesis and characterization of a novel highly phosphonated water‐insoluble polymer

Abstract

A novel polymer, functionalized by tetrafluoroaryl phosphonic acid units, was prepared by free-radical polymerization of the corresponding styrene monomer. The obtained polymer was analyzed by gel permeation chromatography, differential scanning calorimetry, and spectroscopy (NMR, IR). Ion exchange capacity of the water-insoluble polymer was determined in methanol solution by titration with 0.1M NaOH. The proton conductivity of the polymer of 9.91 × 10 −7 S cm −1 as disclosed by electrochemical impedance spectroscopy renders this polymer a promising candidate for solid electrolyte applications or as a water-insoluble dopant for proton exchange membrane applications.

Design, Synthesis and Actual Applications of the Polymers Containing Acidic P–OH Fragments: Part 2—Sidechain Phosphorus-Containing Polyacids

“…In the study of Hoge et al [ 52 ], the idea of the use of styrene-derived phosphonates was further developed. Considering the high para -selectivity of nucleophilic substitution in N,N,N′,N′-tetraethyl-1-(perfluorophenyl)phosphinediamine, they synthesized vinyl monomer having 1,4-perfluorophenylene linkage between styryl and –P(O)(OH) 2 fragments ( Scheme 10 ).…”

“…Polystyrene, containing 1,4-perfluorophenylene linkage between aryl and –P(O)(OH) 2 fragments (see Scheme 10 ), under anhydrous conditions at 120 °C exhibited a conductivity of 9.91 × 10 −7 S∙cm −1 [ 52 ].…”

“… Synthesis of phosphonic acid with 1,4-perfluorophenylene linkage between styryl and –P(O)(OH) 2 fragments [ 52 ]. …”

Low humidity dependence of proton conductivity in modified zirconium(iv)-hydroxy ethylidene diphosphonates

“…22 There have been many studies on polymers functionalized with dense phosphonic acid groups. [23][24][25] However, polymers are generally flexible and swollen by water under humid conditions, making it challenging to maintain a high-density acid structure.…”

Tetrafluoroaryl Phosphonic Acid Functionalized Polyphosphazenes – Synthesis, Characterization, and Evaluation of Proton Conductivity

“…As reported in recent papers by our group, perfluoroaryl phosphonic acid provides an even higher conductivity than its non‐fluorinated counterpart at high temperatures and low humid conditions. [ 12 ] As shown by, Desmarteau et al [ 13 ] fluorinated phosphonic acid also provide a higher conductivity than sulfonic acid derivatives which are currently used in Nafion® based membranes. Polyphosphazenes bearing perfluorinated sulfonic acid groups have already been reported and exhibit higher conductivity and stability than their aliphatic derivative.…”