Synthesis of hyperbranched poly(arylene ether phosphine oxide)s, HB PAEPOs, from bis(4-fluorophenyl)(4-hydroxyphenyl)phosphine oxide, 1a, in the presence of a series of core molecules with systematically altered reactivity of the aryl fluoride groups provides polymers with molecular weights, MWs, controlled by the concentration of the core molecule, and narrow polydispersity indices, PDIs. Polymers with number-average molecular weights ranging from 3270 to 8100 Da, and PDIs as low as 1.25 have been prepared. The core molecules utilized in this work consist of a series of fluorinated triarylphosphine oxides, tris(4-fluorophenyl)phosphine oxide, tris(3,4-difluorophenyl)phosphine oxide, and tris(3,4,5-trifluorophenyl)phosphine oxide, 2a, 2b, and 2c, respectively. The most highly activated core, 2c, provides the best control over the final MW and the lowest PDIs. The degree of branching, DB, for the HB PAEPOs decreases from 0.57 with no core to below 0.40 at higher concentrations of 2b and 2c.

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

Key indicatorsSingle-crystal X-ray study T = 293 K Mean '(C±C) = 0.003 A Ê R factor = 0.064 wR factor = 0.219 Data-to-parameter ratio = 22.7 For details of how these key indicators were automatically derived from the article, see