Synthesis and characterization of fluorinated poly(aryl ether ketone)s containing 1,4-naphthalene moieties

Abstract

The new monomer 2,2‐bis[4‐(4‐{4‐fluorobenzoyl}‐1‐naphthoxy)phenyl]hexafluoropropane (2) was synthesized in a two‐step reaction sequence. 2,2‐his[4‐(1‐naphthoxy)phenyl]‐hexafluoropropane (1) was prepared using the Ullmann ether synthesis reaction of 4,4‐(hex‐afluoroisopropylidiene)diphenol with 1‐bromonaphthalene. Friedel‐Crafts acylation of 1 with 4‐fluorobenzoyl chloride in methylene chloride containing dimethylsulfone selectively afforded 2 in 82% yield. The polycondensation of 2 with various bisphenols in DMAc in the presence of an excess of potassium carbonate as a condensation reagent was carried out at 165°C to quantitatively afford the corresponding fluorinated poly(aryl ether ketone)s containing 1,4‐naphthalene moieties. Thermal analysis of the polymers showed them to have Tgs ranging from 194 to 230°C and to be thermally stable in air up with initial weight losses at about 500°C. In addition, these novel polymers exhibited excellent solubility in organic solvents including NMP, DMAc, and chloroform. © 1997 John Wiley & Sons, Inc.

Naphthalene-based poly(arylene ether ketone) anion exchange membranes

“…Among the various types of fuel 20 cells, polymer electrolyte membrane fuel cells (PEMFC) have attracted considerable attention for a variety of power generation applications, such as automotive transportation. The PEMFC is an energy system that can convert hydrogen fuel (or CH 3 OH) and oxygen (or air) directly to electricity, with water as the primary 25 byproduct. 1−5 However, the requirement for high cost precious metal (Pt) electrodes has limited their commercialization to some extent.…”

“…The final step was amination of the brominated polymers was conducted in the membrane form. The aminated polymers had 25 poor solubility in organic solvents, and consequently, no NMR results can be presented. …”

“…In this study, both theoretical IEC values that were deduced from the 1 H NMR of PAEK-Br-X and the IEC values that were determined using the standard back-titration technique are given in Table 2. In order to make a wider comparison with other 25 reported work, we also list a series of data of monofunctionalized quaternized non-naphthalene-based PEEK AEMs (PEEK-Q-X). 21 NAPAEK-Q-X membranes could have obviously higher IEC values than those of PEEK-Q-X, because of their higher content of quaternary ammonium groups.…”

“…The NAPAEK-Q-100 15 membrane had the highest conductivity of 0.074 S cm −1 at 100 o C. Similar to proton exchange membranes, NAPAEK-Q-X AEMs with pendant quaternary ammonium groups can provide better hydrophilic/hydrophobic phase separation compared with polymers with functionalization directly on the main chain, which 20 would enhance the conductivity of the ionomers. Table 2, compares two side-chain-type AEMs with the NAPAEK-Q-X membranes; the former has a similar structure, but without naphthalene The ion conductivities of NAPAEK-Q-X are higher than those of PEEK-Q-X membranes, due to the higher IEC 25 values. Membranes utilized for direct methanol fuel cell (DMFC) must both possess high ion conductivity and be effective barriers to limit methanol crossover.…”

Fabrication of Aromatic‐Aliphatic Aminoketone Polymers with Terminal Fluorine Groups

“…[9] Oligomeric or polymeric building blocks for the target molecules should be readily available via the nucleophilic aromatic substitution reaction [9][10][11][12][13][14][15] of secondary aliphatic diamines with 4,4 0 -difluorobenzophenone (DFB). This simple method would be in analogy to the well-established syntheses of poly(ether ketone)s (PEK) [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] or poly(ether sulfone)s (PES) [34][35][36][37][38] , both based on DFB (Scheme 1). Surprisingly, no reports on the target PAK were available in spite of the fact that related synthetic routes are known, e.g., to produce N-substituted Michler's Ketone derivatives.…”