Abstract
Hyperbranched poly(ether ether ketone)s with hydroxyl terminal groups are prepared by a one-step polycondensation of 3,5-dihydroxy-4′-(4-fluorobenzoyl)diphenylether (AB2-type monomer) through an aromatic nucleophilic substitution reaction. With the help of model compounds, 1H-NMR studies reveal that the degree of branching of the poly(ether ether ketone)s is about 52%. The possibility of entanglement among the hyperbranched polymer molecules is suggested from comparison of their glass transition temperatures with the corresponding dendrimers and the optimized structure of the hyperbranched polymers. The terminal hydroxyl groups were readily functionalized, yielding hyperbranched polymers with a variety of different functional chain ends. The nature of the chain end is shown to dramatically affect the properties of the hyperbranched polymers.
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References
Hawker, C. J., Lee, R. & Frechet, J. M. J. One-pot synthesis of hyperbranched polyester. J. Am. Chem. Soc. 113, 4583–4588 (1991).
Turner, S. R., Viot, B. I. & Mourey, T. H. All-aromatic hyperbranched polyesters with phenol and acetate and groups: Synthesis and characterization. Macromolecules 26, 4617–4623 (1993).
Malmstrom, E., Johansson, M. & Hult, A. Hyperbranched aliphatic polyester. Macromolecules 28, 1698–1703 (1995).
Ishida, Y., Jikei, M. & Kakimoto, M. Synthesis of hyperbranced aromatic polyester by carbon monoxide insertion reaction using palladium catalyst. Poly. Adv. Technol 11, 684–704 (2000).
Yang, G., Jikei, M. & Kakimoto, M. Successful terminal self-condensation of AB2 monomer to form hyperbranched aromatic polyamide. Macromolecules 31, 5964–5966 (1998).
Yang, G., Jikei, M. & Kakimoto, M. Synthesis and properties of hyperbranched aromatic polyamide. Macromolecules 32, 2215–2220 (1999).
Ishida, Y., Sun, A. C. F., Jikei, M. & Kakimoto, M. Synthesis of hyperbranced aromatic polamides starting from dendrons as ABx monomers: effect of monomer multiplicity on the degree of branching. Macromolecules 33, 2832–2838 (2000).
Miller, T. M., Neenan, T. X., Kwock., E. W. & Stein, S. M. Dendritic analogs of engineering plastics: A general one-step synthesis of dendritic polyaryl ethers. J. Am. Chem. Soc. 115, 356–357 (1993).
Hawker, C. J. & Chu, F. Hyperbranched poly(ether ketones): manipulation of structure and physical properties. Macromolecules 29, 4370–4380 (1996).
Morikawa, A. Preparation and properties of hyperbranched poly(ether ketones) with a various number of phenylene units. Macromolecules 31, 5999–6009 (1998).
Shu, C. F. & Leu, C. M. Hyperbranched poly(ether ketone) with carboxylic acid terminal groups: synthesis, characterization, and derivation. Macromolecules 32, 100–105 (1999).
Kim, Y. H. & Webster, O. W. Hyperbranched polyphenylenes. Macromolecules 25, 5561–5572 (1992).
Spindler, R. & Frechet, J. M. J. Synthesis and characterization of hyperbranched polyurethanes from blocked isocyanate monomers by step-growth polymerization. Macromolecules 26, 4809–4813 (1993).
Yamanaka, K., Jikei, M. & Kakimoto, M. Preparation and properties of hyperbranched aromatic polyimides via polyamic acid methyl ester precursor. Macromolecules 33, 6937–6944 (2000).
Yamanaka, K., Jikei, M. & Kakimoto, M. Synthesis of hyperbranched aromatic polyimides via polyamic acid methyl ester precursor. Macromolecules 33, 1111–1114 (2000).
Yamanaka, K., Jikei, M. & Kakimoto, M. Preparation of hyperbranched aromatic polyimides without linear units by end capping reaction. Macromolecules 34, 3910–3915 (2001).
Bolton, D. H. & Wooley, K. L. Synthesis and characterization of hyperbranched polycarbonates. Macromolecules 30, 1890–1896 (1997).
Kim, K., Jikei, M. & Kakimoti, M. Preparation and properties of novel hyperbranched poly(dimethylsiloxane). Polym. J. 34, 275–279 (2002).
Kim, K., Jikei, M. & Kakimoti, M. Synthesis and properties of amphiphilic hyperbranched poly(dimethylsiloxane) possessing hydrophilic and terminal group. Polym. J. 34, 755–760 (2002).
Hong, C., Jikei, M. & Kakimoto, M. Synthesis of characterization of hyperbranched polybenzoxazoles. J. Photopolym. Sci. Technol. 15, 219–222 (2002).
Hong, C. S., Jikei, M., Kikuch, R. & Kakimoto, M. Chemically amphified photosensitive polybenzoxazoles based on tert-butoxycarbonyl protevted hyperbranched poly(o-hydroxyamide)s. Macromolecules 36, 3174–3179 (2003).
Jikei, M., Mori, R., Kawauchi, S. & Kakimoto, M. Synthesis and properties of hyperbranched poly(triphenylamine)s prepared by palladium catalyzed C-N coupling reaction. Polym. J. 34, 550–557 (2002).
Takeuchi, M., Jikei, M. & Kakimoto, M. Preparation of hyperbranched aromatic poly(ether sulfone)s possessing sulfonic acid terminal groups for polymer electrolyte. Chem. Lett. 32, 242–243 (2003).
Jikei, M., Chon, S.-H., Kakimoto, M., Kawauchi, S., Imase, T. & Watanabe, J. Synthesis of hyperbranched aromatic polyamides from aromatic diamines and trimesic acid. Macromoleules 32, 2061–2064 (1999).
Hao, J., Jikei, M. & Kakimoto, M. Synthesis and comparison of hyperbranched aromatic polyimides having the same repeating unit by AB2 self-polycondensation and A2+B3 polycondensation. Macromoleules 36, 3519–3528 (2003).
Sinananwanich, W., Higashihara, T. & Ueda, M. Synthesis of a hyperbranched polymer with perfect branching based on piperidine-4-one. Macromolecules 42, 994–1001 (2009).
Sagawa, Y., Higashihara, T. & Ueda, M. Hyperbranched polymers with controlled degree of branching 0 to 100%. J. Am. Chem. Soc. 132, 11000–11001 (2010).
Tian, W., Fan, X., Kong, J., Liu, Y. & Hung, Y. Novel supramolecular system of amphiphilic hyperbranched polymer with β-cyclodextrine and hyperbranched topography cavites: Synthesis and selective encapsulation. Polymer (Guildf) 51, 2556–2564 (2010).
Kaneko, R., Jikei, M. & Kakimoto, M. Preparation and properties of composite materials composed aromatic polyamides and vinyl polymers. High Perform. Polym. 14, 41–51 (2002).
Kaneko, R., Suzuki, E., Jikei, M. & Kakimoto, M. Preparation and properties of hyperbranched aromatic polyamide-silica composites by sol-gel method. High Perform. Polym. 14, 105–114 (2002).
Gao, H., Yorifuji, D., Wakita, J., Jiang, Z. H. & Ando, S. In situ preparation of nano ZnO/hyperbranched polyimide hybrid film and their optical properties. Polymer (Guildf) 51, 3173–3180 (2010).
Kakimoto, M., Grunzinger, S. J. & Hayakawa, T. Hyperbranched poly(ether sulfone)s: preparation and application to ion-exchange membranes. Polym. J. 42, 697–705 (2010).
Kaneko, R., Jikei, M. & Kakimoto, M. Preparation and properties of photosensitive polymers based on hyperbranched aromatic polyamides. High Perform. Polym. 14, 53–62 (2002).
Xie, J., Deng, X., Cao, Z., Shen, Q., Zhang, W. & Shi, W. Synthesis and second-order nonlinear optical properties of hyperbranched polymers containing pendant azobenzene chromophores. Polymer (Guildf) 48, 5988–5993 (2007).
Wen, G. A., Xin, Y., Zhu, X. R., Zeng, W. J., Zhu, R., Feng, J. C., Cao, Y., Zhao, L., Wang, L. H., Wei, W., Peng, B. & Hung, W. Hyperbranched triazine-containing polyfluorene: Efficient blue emitters for polymer light-emitting diodes (PLEDs). Polymer (Guildf) 48, 1824–1829 (2007).
Taniguchi, Y., Shirai, K., Saitoh, H., Yamaguchi, T. & Tubokawa, N. Postgrafting of vinyl polymers onto hyperbranched poly(amino-amido)-grafted nano-sized silica surface. Polymer (Guildf) 46, 2541–2547 (2005).
Oh, J. H., Jang, J. & Lee, S. H. Curing behavior of tetrafunctional epoxy resin/hyperbranched polymer system. Polymer (Guildf) 42, 8339–8347 (2001).
Morikawa, A. & Ono, K. Preparation of poly(ether ether ketone) dendrimers by the divergent Method. Polym. J. 32, 234–242 (2000).
Morikawa, A. & Ono, K. Preparation of poly[(ether)-(ether ether ketone)]dendrimers by the convergent method. Polym. J. 32, 255–262 (2000).
Ishizu, K., Shibuya, T. & Mori, A. Synthesis and characterization of hyperbranched poly(ethyl methacrylate) by quasi-living radical polymerization of photofunctional inimer. Polym. Int. 51, 424–428 (2002).
Jikei, M., Uchida, D., Haruta, Y., Takahashi, Y. & Matsumoto, K. Synthesis and properties of hyperbranched poly(ether sulfone)s prepared by self-polycondensation of novel AB2 monomer. J. Polym. Sci. Part A, Polym. Chem. 50, 3830–3839 (2012).
Hawker, C. J. & Frechet, J. M. Monodispersed dendritic polyesters with removable chain ends; a versatile approach to globular macromolecules with chemically reversible polarities. J. Chem. Soc. Perkin. Trans. 1, 2459–2469 (1992).
Morikawa, A., Kakimoto, M. & Imai, Y. Convergent synthesis of starburst poly(ether ketone) dendrons. Macromolecules 26, 6324–6329 (1993).
Ishida, Y., Jikei, M. & Kakimoto, M. Rapid synthesis of aromatic polyamide dendrimers by orthogonal and a double-stage convergent approach. Macromolecules 33, 3202–3211 (2000).
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Morikawa, A., Akagi, M. Hyperbranched poly(ether ether ketone)s: preparation and comparison of properties with the corresponding dendrimers. Polym J 45, 614–621 (2013). https://doi.org/10.1038/pj.2012.188
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DOI: https://doi.org/10.1038/pj.2012.188
