Macromol. Chem. Phys. 2001, 202, 263–269 263 Hyperbranched Poly(ether ketone) Analogues with Heterocyclic Triazine Moiety: Synthesis and Peripheral Functionalization Song Yun Cho, Youngkyu Chang, Jin Seok Kim, Sang Cheon Lee, Chulhee Kim* Department of Polymer Science and Engineering, Hyperstructured Organic Materials Research Center, Inha University, Inchon 402-751, Korea E-mail: chk@inha.ac.kr Introduction The control of the molecular architecture of synthetic macromolecules has always been a challenging area of research. Recently the well-defined structures of dendri- mers have attracted much attention due to their novel properties. [1–3] However, the stepwise divergent or con- vergent synthetic methods required for the preparation of dendrimers has limited their usage. Interests in hyper- branched polymers, as a polydisperse analogue of dendri- mers, grew again after Kim and Webster reported on the hyperbranched polyphenylenes in 1990. [4] Although the structure of these hyperbranched polymers is not as con- trolled as that of dendrimers in terms of the degree of branching and polydispersity, they can be constructed by a direct “one-pot” polymerization of AB x monomers, [5] and made to be highly functionalized at the ends of the peripheral branches. [6] Hawker and Chu have studied the hyperbranched poly(ether ketone)s synthesized from various AB x type monomers and their end-group functionalization from aryl hydroxyl to octyloxy, p-(ethoxycarbonyl)phenoxy, benzophenone, and acetate groups. [7] They investigated the solubility and glass transition behavior of hyper- branched polymers as a function of peripheral groups. Wooley et al. also reported on the functionalization of the peripheral groups of hyperbranched polyethers. [8] Our research was aimed at developing a methodology for the systematic synthesis of hyperbranched polymers with a common structural feature, namely, the heterocyc- lic 1,3,5-s-triazine unit. As a part of this ongoing effort, we have previously reported on the hyperbranched poly- ethynylenes based on 1,3,5-s-triazine moiety. [9] The selec- tive reactivity of three chlorine atoms in cyanuric chlor- ide toward a variety of nucleophiles was found to provide synthetic versatility for AB 2 molecules and their one-pot polymerized, hyperbranched polymers which contain 1,3,5-s-triazine units. Linear triazine polymers possess excellent thermal stability, high T g , and good solubility in Full Paper: Hyperbranched poly(ether ketone) with 1,3,5-s-triazine moiety was prepared by a one-pot poly- merization of an AB 2 type monomer, 2,4-bis(4-hydroxy- phenyl)-6-(4-(4-(4-fluorobenzoyl)phenoxy)phenyl)-1,3,5- s-triazine, which was synthesized from cyanuric chloride. The selective reactivity of three chlorine atoms on cyanu- ric chloride toward nucleophiles provides a very efficient route for the systematic synthesis of AB 2 type triazine monomers and their hyperbranched polymers. The result- ing polymers exhibited a glass transition at 264 8C without any indication of crystallinity. The modification of the peripheral hydroxyl groups on the hyperbranched poly- mers by methoxy, oligoethyleneoxy, or stearyl moieties brought about remarkable changes in their solubility and glass transition temperatures. The amphiphilic nature of the 2-[2-(2-(2-methoxyethoxy)ethoxy)ethoxy]ethoxy-ter- minated poly(ether ketone) analogue in an aqueous phase was investigated by using fluorescence techniques and dynamic light scattering. It was found that the analogue forms a self-aggregation at a critical aggregation concen- tration of 12.6 mg/L. The mean diameter of the aggregates was 320 nm. The steady-state fluorescence anisotropy value (r) of 1,6-diphenyl-1,3,5-hexatriene (DPH) in the hydrophobic domain was 0.240. Macromol. Chem. Phys. 2001, 202, No. 2 i WILEY-VCH Verlag GmbH, D-69451 Weinheim2001 1022-1352/2001/0201–0263$17.50+.50/0