Fluoride‐terminated hyperbranched poly(arylene ether phosphine oxide)s via nucleophilic aromatic substitution

Abstract

A series of ABx‐type triarylphosphine oxide monomers, bis‐(4‐fluorophenyl)‐(4‐hydroxyphenyl)phosphine oxide (4a), bis‐(3,4‐difluorophenyl)‐(4‐hydroxyphenyl)phosphine oxide (4b), and 4‐hydroxyphenyl‐bis‐(3,4,5‐trifluorophenyl)phosphine oxide (4c) were prepared, characterized, and polymerized under nucleophilic aromatic substitution conditions [N‐methylpyrrolidone (NMP), K2CO3] to provide the corresponding hyperbranched poly(arylene ether phosphine oxide)s with number‐average molecular weights ranging from 9200 to 14,600 Da. NMR spectroscopic analysis indicated the presence of highly branched products with an approximate degree of branching of 0.57. The polymers were soluble in a variety of typical organic solvents and displayed excellent thermal stability. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1456–1467, 2002

Synthesis and Characterization of Hyperbranched Poly(arylene ether)s from a New Activated Trifluoro B3 Monomer Adopting an A2 + B3 Approach

“…phenyl quinoxaline)s, [16][17][18] poly(phenylene oxide)s, [19,20] poly(arylene ether imide)s, [21][22][23] poly(arylene ether ketone imide)s, [24,25] and poly(arylene ether phosphine oxide)s. [26,27] However, AB x monomers are usually not always commercially available and their synthesis sometimes involves multistep organic synthesis. As a consequence several groups have attempted a facile A 2 þ B 3 approach toward hyperbranched polymers.…”

Branched poly(arylene ether ketone)s with tailored thermal properties: Effects of AB/AB2 ratio, core (B3) percentage, and reaction temperature

“…For example, 5d was more stable than 5n, with 5% weight losses in air occurring at 480 and 464 C, respectively, These results were not unexpected as the TPO group has been shown to increase the thermo-oxidative stability of many poly(arylene ether)s [15,[27][28][29][30]. However, it is surprising to note that higher TPO content did not provide higher thermal stability of the respective branched polymers here.…”

“…N-Methylpyrrolidinone, (NMP), was dried over CaH 2 and distilled prior to use. The AB 2 monomer, bis(4-fluorophenyl)-(4-hydroxyphenyl)phosphine oxide, 2, [15] and core molecule, tris-(3,4,5-trifluorophenyl)phosphine oxide, 4, [16] were prepared according to literature procedures.…”

Aromatic Hyperbranched Polymers: Synthesis and Application

“…A series of AB 2 monomers, namely bis-(4-fluorophenyl)-(4-hydroxyphenyl) phosphine oxide (1-26, Scheme 10), bis-(3,4-difluorophenyl)-(4-hydroxyphenyl) phosphine oxide (1-28, Scheme 10), and 4-hydroxyphenyl-bis-(3,4,5-trifluorophenyl)phosphine oxide (1-29, Scheme 10), were synthesized and characterized by Bernal et al [166]. The AB x monomers were self-condensed to form hb-PAEPOs according to the procedure reported by Hawker and Chu [65].…”