[en] A new type of macromolecular architecture, denoted as dendrimer-like star block copolymers, is reported. These block copolymers are described by a radial geometry where the different generations or layers are comprised of high molecular weight polymer emanating from a central core. A hexahydroxyl functional core was used as an initiator for the “living” ring opening polymerization (ROP) of ε-caprolactone producing a hydroxyl terminated six arm star polymer with controlled molecular weight and narrow polydispersities (PD < 1.1). Capping these chain ends with dendrons containing activated bromide moieties produced “macro-initiators” for atom transfer radical polymerization (ATRP). Methyl methacrylate was polymerized from these “macro-initiators” in the presence of an organometallic promoter to produce the requisite dendrimer-like star polymers. High molecular weight was obtained with low polydispersities (<1.2). Alternatively, amphiphilic character could be introduced by designing the different layers or generations to be either hydrophobic or hydrophilic. For example, methyl methacrylate (MMA) with either hydroxyethyl methacrylate (HEMA) or methacrylate functional ethylene oxide macromonomers (EO) were polymerized from these “macro-initiators” to provide a hydrophilic outer layer. The use of macromolecular building blocks allows rapid attainment of high polymer in a limited number of steps with purification between transformation requiring only polymer precipitation.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Hedrick, James L.; IBM Research Division, San José, California, USA
Trollsas, Mikael; IBM Research Division, San José, California, USA
Hawker, Craig Jon; IBM Research Division, San José, California, USA
Atthoff, Björn; IBM Research Division, San José, California, USA
Claesson, Hans; IBM Research Division, San José, California, USA
Heise, Andreas; IBM Research Division, San José, California, USA
Miller, Robert D.; IBM Research Division, San José, California, USA
Mecerreyes, David; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Depmartment of Chemistry > Center for Education and Research on Macromolecules (CERM)
Dubois, Philippe ; University of Mons-Hainaut (UMH) > Laboratory of Polymer and Composite Materials
Language :
English
Title :
Dendrimer-like star block and amphiphilic copolymers by combination of ring opening and atom transfer radical polymerization
Publication date :
15 December 1998
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
(a) Reiss, G.; Hurtrez, G.; Bahadur, P. Block Copolymers. In Encyclopedia of Polymer Science and Engineering; Korschwitz, J. I., Ed.; Wiley-Interscience: New York, 1985.
(b) Thomas, E. L.; Anderson, D. M.; Henkee, C. S.; Hoffman, D. Nature 1988, 334, 598.
(c) Bates, F. S.; Fredrickson, G. H. Annu. Rev. Phys. Chem. 1990, 41, 525.
(c) Gast, A. P. Scientific Methods for the Study of Polymer Colloids and Their Applications; Kluwer: Dordrecht, The Netherlands 1990; Chapter on Block Copolymers at Interfaces, pp 311-328.
(d) Halperin, A.; Tirrell, M.; Lodge, T. P. Adv. Polym. Sci. 1992, 100, 31.
(a) Davies, M. E.; Saldarriaga, C.; Montes, C.; Garces, J.; Crowder, C. Nature 1988, 331, 698.
(b) McCusker, L. B.; Bacrlocher, C.; Jahn, E.; Bülow, M. Zeolites 1991, 11, 308.
(c) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S. Nature 1992, 359, 710.
(d) Göltner, C. G.; Antonietti, M. Adv. Mater. 1997, 9, 431.
(e) Monnier, A.; Schüth, F.; Huo, Q.; Kumar, D.; Margolese, D.; Maxwell, R. S.; Stucky, G. D.; Krishnamurty, M.; Petroff, P.; Firouzi, A.; Janicke, M.; Chmelka, B. F. Science 1993, 261, 1299.
(f) Huo, Q.; Margolese, D. I.; Ciesla, U.; Demuth, D. G.; Feng, P.; Gier, T. E.; Sieger, P.; Firouzi, A.; Chmelka, B. F.; Schüth, F.; Stucky, G. D. Chem. Mater. 1994, 6, 1176.
(g) Beck, J. S.; et al. J. Am. Chem. Soc. 1992, 114, 10834.
(a) Zhao, D.; Feng, J.; Huo, Q.; Melosh, N.; Fredrickson, G. H.; Chmelka, B. F.; Stucky, G. D. Science 1998, 279, 548.
(b) Templin, M.; Franck, A.; Chesne, A. D.; Leist, H.; Zgang, Y.; Ulrich, R.; Schädler, U.; Wiesner, U. Science 1997, 278, 1795.
(c) Zhao, D.; Huo, Q.; Feng, J.; Chmelka, B. F.; Stucky, G. D. J. Am. Chem. Soc. 1998, 120, 6024.
(a) Tomala, D. A.; Berry, U.; Hall, M.; Hedstrand, D. M. Macromolecules 1987,20, 1167.
(b) Neukome, G. R.; Yao, Z.-Q.; Baker, G. R.; Gupta, V. K.; Russo, P. S.; Sanders, M. J. J. Am. Chem. Soc. 1986, 108, 849.
(c) Kim, Y. H.; Webster, O. W. J. Am. Chem. Soc. 1990, 112, 4592.
(d) Pesak, D. J.; Moore, J. S.; Wheat, T. E. Macromolecules 1997, 30, 6467.
(e) Chapman, T. M.; Hillyer, G. L.; Mahan, E. J.; Shaffer, K. A. J. Am. Chem. Soc. 1994, 116, 11195.
(f) Gitsov, L.; Fréchet, J. M. J. J. Am. Chem. Soc. 1996, 118, 3785.
(g) Gitsov, I.; Fréchet, J. M. J. Macromolecules 1993, 26, 6536.
(h) Gitsov, I.; Wooley, K. L.; Fréchet, J. M. J. Angew. Chem., Int. Ed. Engl. 1992, 31, 1200.
(i) Hawker, C. J.; Wooley, K. L.; Fréchet, J. M. J. J. Chem. Soc., Perkin Trans. 1993, 1, 1287.
(j) Jansen, J. F. G. A.; Meijer, E. W. J. Am. Chem. Soc. 1995, 117, 4417.
(k) Ihre, H.; Huit, A.; Fréchet, J. M. J.; Gitsov, I. Macromolecules 1998, 31, 4061.
(a) Latrou, H.; Hadjichristidis, N. Macromolecules 1992, 25, 4649.
(b) Latrou, H.; Hadjichristidis, N. Macromolecules 1993, 26, 2479.
(c) Mayw, J. W. Polym. Bull. 1990, 23, 247.
(d) Schulz, G. O.; Milkovich, R. J. Appl. Polym. Sci. 1982, 27, 4773.
(a) Vasilenko, N. G.; Rebrov, E. A.; Muzafarov, A. M.; Dbwein, B.; Striegel, B.; Möller, M. Macromol. Chem. Phys. 1998, 199, 889.
(b) Kim, Y. H.; Webster, O. W. Macromolecules 1992, 25, 5561
Olvera de la Cruz, M.; Sanchez, I. C. Macromolecules 1986, 19, 2501.
Hadjichristidis, N.; Latrou, H.; Bahal, S. K.; Chludzinski, J. J.; Disko, M. M.; Garner, R. T.; Garner, K. S.; Liang, D. J. Macromolecules 1993, 26, 5812.
(a) Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K. Trends Polym. Sci. 1994, 2, 66.
(b) Sawamoto, M.; Kamigaito, M. Trends Polym. Sci. 1996, 4, 183.
(c) Hawker, C. J. Acc. Chem. Res. 1997, 30, 373.
(a) Moad, G.; Rizzardo, E. Macromolecules 1995, 28, 8722.
(b) Yoshida, E.; Fujii, T. J. Polym. Sci., Polym. Chem. 1997, 35, 2371.
(c) Goto, A.; Fukuda, T. Macromolecules 1997, 30, 4272.
(d) Ide, N.; Fukuda, T. Macromolecules 1997, 30, 4268.
(e) Yoshida, E.; Tanimoto, S. Macromolecules 1997, 30, 4018.
(f) Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K. Macromolecules 1993, 26, 2987.
(g) Baldovi, M. V.; Mohtat, N.; Scaiano, J. C. Macromolecules 1996, 29, 5497.
(h) Hammouch, S. O.; Catala, J. M. Macromol. Rapid Commun. 1996, 17, 149.
(i) Kazmaier, P. M.; Moffat, K. A.; Georges, M. K.; Veregin, R. P. N.; Hamer, G. K. Macromolecules 1995, 28, 1841.
(j) Li, I.; Howell, B. A.; Matyjaszewski, K.; Shigemoto, T.; Smith, P. B.; Priddy, D. B. Macromolecules 1995, 28, 1841.
(k) Howell, B. A.; Priddy, D. B.; Li, I. Q.; Smith, P. B.; Kastl, P. E. Polym. Bull. 1996, 37, 451.
(l) Hawker, C. J.; Mecerreyes, D.; Hedrick, J. L.; Dubois, Ph.; Jérôme, R. Macromol. Chem. Phys. 1997, 298, 155.
(a) Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T. Macromolecules 1995, 28, 1721.
(b) Nishikawa, T.; Ando, T.; Kamigaito, M.; Sawamoto, M. Macromolecules 1997, 30, 2244.
(c) Grimaud, T.; Matyjaszewski, K. Macromolecules 1997, 30, 2216.
(d) Patten, T. E.; Xia, J.; Abernathy, T.; Matyjaszewski, K. Science 1996, 272, 866.
(e) Percec, V.; Barboiu, B. Macromolecules 1995, 28, 7970.
(f) Haddleton, D. M.; Jasieczek, C. B.; Hannon, M. J.; Shooter, A. J. Macromolecules 1997, 30, 2190.
(h) Uegaki, H.; Kotani, Y.; Kamigaito, M.; Sawamoto, M. Macromolecules 1997, 30, 2249.
(i) Percéc, V.; Barboiu, B.; Neumann, A.; Ronda, J. C.; Zhao, M. Macromolecules 1996, 29, 3665.
(j) Haddleton, D. M.; Clark, A. J.; Crossman, M. C.; Duncalf, D. J.; Heming, A. M.; Morsley, S. R.; Shooter, A. J. J. Chem. Soc., Chem. Commun. 1997, 1173.
(k) Wang, J. S.; Matyjaszewski, K. Macromolecules 1995, 28, 7901.
(l) Matyjaszewski, K.; Patten, T. E.; Xia, J. J. Am. Chem. Soc. 1997, 119, 674.
(m) Matyjaszewski, K. Ed., ACS Symp. Series 1998, 685.
(n) Matyjaszewski, K.; Gaynor, S. G. ACS Symp. Series 1998, 685, 396.
(o) Matyjaszewski, K. ACS Symp. Series 1998, 685, 258.
(a) Puts, R. D.; Sogah, D. Y. Macromolecules 1996, 29, 3323.
(b) Hawker, C. J.; Barclay, G. G.; Orellana, A.; Dao, J.; Devonport, W. Macromolecules 1996, 29, 5245.
(c) Wang, J. S.; Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117, 5614.
(a) Li, I. Q.; Howell, B. A.; Koster, R. A.; Priddy, D. B. Macromolecules 1996, 29, 8554.
(b) Keoshkerian, B.; Georges, M. K.; Boils-Boissier, D. Macromolecules 1995, 28, 6381.
(c) Hawker, C. J. J. Am. Chem. Soc. 1994, 116, 11314.
