Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Review Article
  • Published:

Block copolymers in tomorrow's plastics

Nature Materials volume 4, pages 19–31 (2005)Cite this article

Abstract

In this era of portability and rapid technological advances, polymers are more than ever under pressure to be cheap and offer tailored property profiles. Often, the key lies in designing blends and alloys carefully structured at the appropriate scale (preferably less than a micrometre) from existing polymers. Block copolymers — two or more different polymer chains linked together — have long been thought to offer the solution. Local segregation of the different polymer blocks yields molecular-scale aggregates of nanometre size. Recent progress in synthetic chemistry has unveiled unprecedented opportunities to prepare tailored block copolymers at reasonable cost. Over twenty years of intense academic research and the advent of powerful statistical theories and computational methods should help predict the equilibrium and even non-equilibrium behaviour of copolymers and their blends with other polymers. The gap between block copolymer self-assembly and affordable nanostructured plastics endowed with still-unexplored combinations of properties is getting narrower.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Compatibilized and nanostructured blends.
Figure 2: Block-copolymer self-assembly in homopolymers.
Figure 3: Bicontinuous microemulsions in A/B/AB ternary blends.
Figure 4: Living copolymers and their self-assembly.
Figure 5: Triblock copolymer nanoframeworks.
Figure 6: SBM/SB self-assembly: towards super-tough plastics.
Figure 7: Block-copolymer nanoframeworks: Towards toughened epoxy.
Figure 8: Reactive blending as a route to nanostructured blends.

Similar content being viewed by others

References

  1. Barlow, J. W., Paul, D. R. & Keskkula, H. Polymer blends in Encyclopedia of Polymer Science and Engineering 2nd edn Vol. 12 (eds Mark, H. F, Bikales, N., Overberger, C. G. & Menges, G.) 399–461 (Wiley, New York, 1988).

    Google Scholar 

  2. Milner, S. T. How do copolymer compatibilizers really work. Mater. Res. Soc. Bull. 22, 38–42 (1997).

    Article  CAS  Google Scholar 

  3. Creton, C., Kramer, E. J., Brown, H. R. & Hui, C. Y. Adhesion and fracture of interfaces between immiscible polymers: From the molecular to the continuum scale. Adv. Polym. Sci. 156, 53–136 (2002).

    Article  CAS  Google Scholar 

  4. Koning, C., Van Duin M., Pagnoulle, C. & Jerome, R. Strategies for compatibilization of polymer blends. Prog. Polym. Sci. 23, 707–757 (1998).

    Article  CAS  Google Scholar 

  5. Baker, W., Scott, C. & Hu, G.-H. Reactive Polymer Blending (Carl Hanser, Munich, 2001).

    Book  Google Scholar 

  6. Gelbart, W. M., Ben-Shaul, A. & Roux, D. Micelles, Membranes, Microemulsions and Monolayers (Springer, New York, 1994).

    Book  Google Scholar 

  7. Holden, G., Legge, N. R., Quirk, R. & Schroeder, H. E. Thermoplastic Elastomers (Hanser, Munich, Germany, 1996).

    Google Scholar 

  8. Knoll, K. & Niessner, N. Styrolux and Styroflex – from transparent high impact polystyrene to new thermoplastic elastomers. Macromol. Symp. 132, 231–243 (1998).

    Article  CAS  Google Scholar 

  9. Ryu, C. Y., Ruokolainen, J., Fredrickson, G. H., Kramer, E. J. & Hahn, S. F. Chain architecture effects on deformation and fracture of block copolymers with unentangled matrices. Macromolecules 35, 2157–2166 (2002).

    Article  CAS  Google Scholar 

  10. de Gennes, P. G. & Taupin, C. Microemulsions and the flexibility of oil/water interfaces. J. Phys. Chem. 86, 2294–2304 (1982).

    Article  CAS  Google Scholar 

  11. Roe, R. J. Phase-relations and miscibility in polymer blends containing copolymers. Adv. Polym. Sci. 82, 103–139 (1987).

    Article  CAS  Google Scholar 

  12. Hamley, I. W. The Physics of Block Copolymers Ch. 6 (Oxford Univ. Press, Oxford, England, 1999).

    Google Scholar 

  13. Spontak, R. J. & Patel, N. P. in Developments in Block Copolymer Science and Technology (ed. Hamley, I. W.) 159 (Wiley, New York, 2004).

    Book  Google Scholar 

  14. Kinning, D. J., Winey, K. & Thomas, E. L. Structural transitions from spherical to nonspherical micelles in blends of poly(styrene-butadiene) diblock copolymer and polystyrene homopolymers. Macromolecules 21, 3502–3506 (1988).

    Article  CAS  Google Scholar 

  15. Roe, R.-J. & Zin, W.-C. Phase equilibria and transition in mixtures of a homopolymer and a block copolymer. 2. Phase diagram. Macromolecules 17, 189–194 (1984).

    Article  CAS  Google Scholar 

  16. Koizumi, S., Hasegawa, H. & Hashimoto, T. Ordered structure of block polymer homopolymer mixtures. 4. Vesicle formation and macrophase separation. Makromol. Chem-Macromol. Symp. 62, 75–91 (1992).

    Article  CAS  Google Scholar 

  17. Koizumi, S., Hasegawa, H. & Hashimoto, T. Ordered structures of block copolymer/homopolymer mixtures. 5. Interplay of macro- and microphase separation. Macromolecules 27, 6532–6540 (1994).

    Article  CAS  Google Scholar 

  18. Bates, F. S. et al. Polymeric bicontinuous microemulsions. Phys. Rev. Lett. 79, 849–852 (1997).

    Article  CAS  Google Scholar 

  19. de Gennes, P.-G. in Solid State Physics (ed. Liebert, L.) (Academic, New York, 1978).

    Google Scholar 

  20. Semenov, A. N. Contribution to the theory of microphase layering in block copolymer melts. ZH EKSP TEOR FIZ 88, 1242–1256 (1985).

    CAS  Google Scholar 

  21. Helfand, E. Theory of inhomogeneous polymers – fundamentals of Gaussian random-walk model. J. Chem. Phys 62, 999–1005 (1975).

    Article  CAS  Google Scholar 

  22. Semenov, A. N. Theory of diblock-copolymer segregation to the interface and free surface of a homopolymer layer. Macromolecules 25, 4967–4977 (1992).

    Article  CAS  Google Scholar 

  23. Shibayama, M., Hashimoto, T. & Kawai, H. Ordered structure in block polymer solutions. 5. Equilibrium and non-equilibrium aspects of microdomain formation. Macromolecules 16, 1434–1443 (1983).

    Article  CAS  Google Scholar 

  24. Lodge, T. P., Bryant, P. & Hanley, K. J. The full phase behaviour of block copolymers in sovlvents of varying selectivity. Macromolecules 35, 4707–4717 (2002).

    Article  CAS  Google Scholar 

  25. Corte, L, Yamauchi, K., Court, F., Cloître, M., Hashimoto, T. & Leibler, L. Annealing and defect trapping in lamellar phases of triblock terpolymers. Macromolecules 36, 7695–7706 (2003).

    Article  CAS  Google Scholar 

  26. Fredrickson, G. H., Ganesan, V. & Drolet, F. Field-theoretic computer simulation methods for polymers and complex fluids. Macromolecules 35, 16–39 (2002).

    Article  CAS  Google Scholar 

  27. Binder, K. & Müller, M. Monte Carlo simulation of block copolymers. Curr. Opin. Colloid. Interface Sci. 5, 315–323 (2000).

    Article  CAS  Google Scholar 

  28. Hadjichristidis, N., Pispas, S. & Floudas, G. Block Copolymers: Synthetic Strategies, Physical Properties, and Applications (Wiley, New Jersey, 2003).

    Google Scholar 

  29. Szwarc, M. Living polymers. Their discovery, characterization and properties. J. Polym. Sci. A 36, 9–15 (1998).

    Google Scholar 

  30. Holden, G. & Milkovich, R. Block polymers of monovinyl aromatic hydrocarbons and conjugated dienes. US Patent, 3,265,765 (1966).

  31. Bates, F. S., Fredrickson, G. H., Hucul, D. & Hahn, S. F. PCHE-Based pentablock copolymers: evolution of a new plastic. AlChE J. 47, 762–765 (2001).

    Article  CAS  Google Scholar 

  32. Riess, G., Schlienger, M. & Marti, S. New morphologies in rubber-modified polymers. J. Macrom. Sci. Phys. 2, 355–374 (1980).

    Article  Google Scholar 

  33. Stadler, R. et al. Morphology and thermodynamics of symmetric poly(A-block-B-block-C) triblock copolymers. Macromolecules 28, 3080–3097 (1995).

    Article  CAS  Google Scholar 

  34. Hong, K., Uhrig, D. & Mays, J. W. Living anionic polymerization. Curr. Opin. Solid State Mater. Sci. 4, 531–538 (1999).

    Article  CAS  Google Scholar 

  35. Jérôme, R., Teyssié, Ph., Vuillemin, B., Zundel, T. & Zune, C. Recent achievements in anionic polymerization of (meth)acrylates. J. Polym. Sci. A 37, 1–10 (1999).

    Article  Google Scholar 

  36. Navarro, C., Marcarian, X. & Vuillemin, B. Ligated anionic polymerization: An innovative elf-atochem technology for the polymerization of (meth)acrylates. Macromol. Symp. 132, 263–272 (1998).

    Article  CAS  Google Scholar 

  37. Matsushita, Y., Choshi, H., Fujimoto, T. & Nagasawa, M. Preparation and morphological properties of a triblock copolymer of the ABC type. Macromolecules 13, 1053–1058 (1980).

    Article  CAS  Google Scholar 

  38. Krappe, U., Stadler, R. & Voigt-Martin, I. Chiral Assembly in amorphous ABC triblock copolymers. Formation of a helical morphology in polystyrene-block-polybutadiene-block-poly(methylmethacrylate) block copolymers. Macromolecules 28, 4558–4561 (1995).

    Article  CAS  Google Scholar 

  39. Abetz, V. & Goldacker, T. Formation of superlattices via blending of block copolymers. Macromol. Rapid. Commun. 21, 16–34 (2000).

    Article  CAS  Google Scholar 

  40. Breiner, U., Krappe, U., Thomas, E. L. & Stadler, R. Structural characterization of the “knitting pattern” in polystyrene-block-poly(ethylene-co-butylene)-block-poly(methyl methacrylate) triblock copolymers. Macromolecules 31, 135–141 (1998).

    Article  CAS  Google Scholar 

  41. Goldacker, T., Abetz, V., Stadler, R., Erukhimovich, I. & Leibler, L. Non-centrosymmetric superlattices in block copolymer blends. Nature 398, 137–139 (1999).

    Article  CAS  Google Scholar 

  42. Miyamoto, M., Sawamoto, M. & Higashimura, T. Living polymerization of isobutyl vinyl ether with hydrogen iodide/iodine initiating system. Macromolecules 17, 265–268 (1984).

    Article  CAS  Google Scholar 

  43. Kwon, Y. & Faust, R. Synthesis of polyisobutylene-based block copolymers with precisely controlled architecture by living cationic polymerization. Adv. Polym. Sci. 167, 107–135 (2004).

    Article  CAS  Google Scholar 

  44. Moad, G., Rizzardo, E. & Solomon, D. H. Selectivity of the reaction of free radicals with styrene. Macromolecules 15, 909–914 (1982).

    Article  CAS  Google Scholar 

  45. Listigovers, N. A., Georges, M. K., Odell, P. G. & Keoshkerian, B. Narrow-polydispersity diblock and triblock copolymers of alkyl acrylates by a “living” stable free radical polymerization. Macromolecules 29, 8992–8993 (1996).

    Article  CAS  Google Scholar 

  46. Grimaldi, S. et al. Acyclic b-phosphonylated nitroxides: a new series of counter-radicals for ≪living≫/controlled free radical polymerization. Macromolecules 33, 1141–1147 (2000).

    Article  CAS  Google Scholar 

  47. Hawker, C. J., Bosman, A. W. & Harth, E. New polymer synthesis by nitroxide mediated living radical polymerizations. Chem. Rev. 101, 3661–3668 (2001).

    Article  CAS  Google Scholar 

  48. Wang, J.-S. & Matyjaszewski, K. Controlled/“living” radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes. J. Am. Chem. Soc. 117, 5614–5615 (1995).

    Article  CAS  Google Scholar 

  49. Kato, M., Kamigaito, M., Sawamoto, M. & Higashimura, T. Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris-(triphenylphosphine)ruthenium (II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization. Macromolecules 28, 1721–1723 (1995).

    Article  CAS  Google Scholar 

  50. Matyjaszewski, K. Macromolecular engineering by controlled/living ionic and radical polymerizations. Macromol. Symp. 174, 51–67 (2001).

    Article  CAS  Google Scholar 

  51. Chiefari, J. et al. Living free-radical polymerization by reversible addition-fragmentation chain transfer: the raft process. Macromolecules 31, 5559–5562 (1998).

    Article  CAS  Google Scholar 

  52. Moad, G., Mayadunne, R. T. A., Rizzardo, E., Skidmore, M. & Thang, S. H. Synthesis of novel architectures by radical polymerization with reversible addition fragmentation chain transfer (RAFT polymerization). Macromol. Symp. 192, 1–12 (2003).

    Article  CAS  Google Scholar 

  53. Nicolas, J., Charleux, B., Guerret, O. & Magnet, S. Novel SG1-based water-soluble alkoxyamine for nitroxide-mediated controlled free-radical polymerization of styrene and n-butyl acrylate in miniemulsion. Macromolecules 37, 4453–4463 (2004).

    Article  CAS  Google Scholar 

  54. Coates, G. W., Hustad, P. D. & Reinartz, S. Catalysts for the living insertion polymerization of alkenes: access to new polyolefin architectures using Ziegler-Natta chemistry. Angew. Chem. Int. Edn 41, 2236–2257 (2002).

    Article  CAS  Google Scholar 

  55. Coates, G. W. Precise control of polyolefin stereochemistry using single-site metal catalysts. Chem. Rev. 100, 1223–1252 (2000).

    Article  CAS  Google Scholar 

  56. Piotti, M. E. Ring opening metathesis polymerization. Curr. Opin. Solid State Mater. Sci. 4, 539–547 (1999).

    Article  CAS  Google Scholar 

  57. Bendejacq, D., Ponsinet, V., Joanicot, M., Loo, Y.-L. & Register, R. A. Well-ordered microdomain structures in polydisperse poly(styrene)-poly(acrylic acid) diblock copolymers from controlled radical polymerization. Macromolecules 35, 6645–6649 (2002).

    Article  CAS  Google Scholar 

  58. Hashimoto, T., Koizumi, S., Hasegawa, H., Izumitani, T. & Hyde, S. T. Observation of “mesh” and “strut” structures in block copolymer/homopolymer mixtures. Macromolecules 25, 1433–1439 (1992).

    Article  CAS  Google Scholar 

  59. Spontak, R. J., Smith, S. D. & Ashraf, A. Linear multiblock copolymer/homopolymer blends of constant composition. 1. Low-molecular-weight homopolymers. Macromolecules 26, 5118–5124 (1993).

    Article  CAS  Google Scholar 

  60. Lohse, D. & Hadjichristidis, N. Microphase separation in block copolymers. Curr. Opin. Colloid Interface Sci. 2, 171–176 (1997).

    Article  CAS  Google Scholar 

  61. Yang, L. Z., Gido, S. P., Mays, J. W., Pispas, S. & Hadjichristidis, N. Phase behaviour of I2S single graft block copolymer/homopolymer blends. Macromolecules 34, 4235–4243 (2001).

    Article  CAS  Google Scholar 

  62. Avgeropoulos, A., Dair, B. J., Thomas, E. L. & Hadjichristidis, N. Swelling behavior of ordered miktoarm star block copolymer-homopolymer blends. Polymer 43, 3257–3266 (2002).

    Article  CAS  Google Scholar 

  63. Lyatskaya, Y., Gersappe, D., Gross, N. A. & Balazs, A. C. Designing compatibilizers to reduce interfacial tension in polymer blends. J. Phys. Chem. 100, 1449–1458 (1996).

    Article  CAS  Google Scholar 

  64. Leibler, L., Orland, H. & Wheeler, J. C. Theory of critical micelle concentration for solutions of block copolymers. J. Chem. Phys. 79, 3550–3557 (1983).

    Article  CAS  Google Scholar 

  65. Whitmore, M. D. & Noolandi, J. Theory of phase equilibria in block copolymer-homopolymer blends. Macromolecules 18, 2486–2497 (1985).

    Article  CAS  Google Scholar 

  66. Mayes, A. M. & Olvera de la Cruz, M. Cylindrical versus spherical micelle formation in block copolymer/homopolymer blends. Macromolecules 21, 2543–2547 (1988).

    Article  CAS  Google Scholar 

  67. Semenov, A. N. Phase equilibria in block copolymer-homopolymer mixtures. Macromolecules 26, 2273–2281 (1993).

    Article  CAS  Google Scholar 

  68. Matsen, M. W. Phase behavior of block copolymer/homopolymer blends. Macromolecules 28, 5765–5773 (1995).

    Article  CAS  Google Scholar 

  69. Janert, P. K. & Schick, M. Phase behavior of binary homopolymer/diblock blends: temperature and chain length dependence. Macromolecules 31, 1109–1113 (1998).

    Article  CAS  Google Scholar 

  70. Sides, S. W. & Fredrickson, G. H. Parallel algorithm for numerical self-consistent field theory simulations of block copolymer structure. Polymer 44, 5859–5866 (2003).

    Article  CAS  Google Scholar 

  71. Leibler, L. & Pincus, P. Ordering transition of copolymer micelles. Macromolecules 17, 2922–2924 (1984).

    Article  CAS  Google Scholar 

  72. Gast, A. P. & Leibler, L. Interactions of sterically stabilized particles suspended in a polymer-solution. Macromolecules 19, 686–691 (1986).

    Article  CAS  Google Scholar 

  73. Hasegawa, R., Aoki, Y. & Doi, M. Optimum graft density for dispersing particles in polymer melts. Macromolecules 29, 6656–6662 (1996).

    Article  CAS  Google Scholar 

  74. de Gennes, P. G. Conformations of polymers attached to an interface. Macromolecules 13, 1069–1075 (1980).

    Article  CAS  Google Scholar 

  75. Leibler, L, Ajdari, A., Mourran, A., Coulon, G. & Chatenay, D. in Ordering in Macromolecular Systems 301 (Springer, Berlin, 1994).

    Book  Google Scholar 

  76. Shull, K. R. Wetting autophobicity of polymer melts. Faraday Discuss. 98, 203–217 (1994).

    Article  CAS  Google Scholar 

  77. Janert, P. K. & Schick, M. First-order unbinding and preunbinding in amphiphilic systems. Phys. Rev. E. 54, R33–R35 (1996).

    Article  CAS  Google Scholar 

  78. Ajdari, A. & Leibler, L. Bending moduli and stability of copolymer bilayers. Macromolecules 24, 6803–6805 (1991).

    Article  CAS  Google Scholar 

  79. Wang, Z.-G. Curvature instability of diblock copolymer bilayers. Macromolecules 25, 3702–3705 (1992).

    Article  CAS  Google Scholar 

  80. Xi, H. & Milner, S. T. Bicontinuous phase in diblock copolymer melts with added homopolymer. Macromolecules 29, 2404–2411 (1996).

    Article  CAS  Google Scholar 

  81. Leibler, L. Theory of phase equilibria in mixtures of copolymers and homopolymers. I Phase diagram. Makromol. Chem. Rapid. Commun. 2, 393–400 (1981).

    Article  CAS  Google Scholar 

  82. Janert, P. K. & Schick, M. Phase behavior of ternary homopolymer/diblock blends: microphase unbinding in the symmetric system. Macromolecules 30, 3916–3920 (1997).

    Article  CAS  Google Scholar 

  83. Jeon, H. S., Lee, J. H., Balsara, N. P. & Newstein, M. C. An experimental study of the thermodynamic properties of multicomponent polyolefin blends with ordered and disordered phases. Macromolecules 31, 3340–3352 (1998).

    Article  CAS  Google Scholar 

  84. Morkved, T. L., Chapman, B. R., Bates, F. S., Lodge, T. P., Stepanek, P. & Almdal, K. Dynamics of ternary polymer blends: disordered, ordered and bicontinuous microemulsion phases. Faraday Discuss. 112, 335–350 (1999).

    Article  CAS  Google Scholar 

  85. Müller, M. & Schick, M. Bulk and interfacial dynamics of a symmetric, ternary homopolymer-copolymer mixture: a Monte-Carlo study. J. Chem. Phys. 105, 8885–8901 (1996).

    Article  Google Scholar 

  86. Fredrickson, G. H. & Bates, F. S. Design of bicontinuous microemulsions. J. Polym. Sci. B 35, 2775–2786 (1997).

    Article  CAS  Google Scholar 

  87. Naughton, J. R. & Matsen, M. W. Non periodic lamellar phase in ternary diblock copolymer/homopolymer blends. Macromolecules 35, 8926–8928 (2002).

    Article  CAS  Google Scholar 

  88. Vilgis, T. A. & Noolandi, J. Theory of homopolymer-block copolymer blends. The search for a universal compatibilizer. Macromolecules 23, 2941–2947 (1990).

    Article  CAS  Google Scholar 

  89. Brown, H. R., Char, K. & Deline, V. R. Enthalpy-driven swelling of a polymer brush. Macromolecules 23, 3383–3385 (1990).

    Article  CAS  Google Scholar 

  90. Borukhov, I. & Leibler, L. Stabilizing grafted colloids in a polymer melt: favourable enthalpic interactions. Phys. Rev. E. 62, R41–R44 (2000).

    Article  CAS  Google Scholar 

  91. Löwenhaupt, B., Steurer, A., Hellmann, G. P. & Gallot, Y. Microphases and macrophases in polymer blends with a diblock copolymer. Macromolecules 27, 908–916 (1994).

    Article  Google Scholar 

  92. Adedeji, A., Hudson, S. D. & Jamieson, A. M. Effect of exothermic interfacial mixing on interfacial activity of a block copolymer. Macromolecules 29, 2449–2456 (1996).

    Article  CAS  Google Scholar 

  93. Prahsarn, C. & Jamieson, A. M. Morphological studies of binary homopolymer/block copolymer blends: effect of molecular weight. Polymer 38, 1273–1283 (1997).

    Article  CAS  Google Scholar 

  94. Lee, J. H. et al. Phase behavior of highly immiscible polymer blends stabilized by a balanced block copolymer surfactant. Macromolecules 36, 6537–6548 (2003).

    Article  CAS  Google Scholar 

  95. Fredrickson, G. H. & Bates, F. S. Stabilizing co-continuous polymer blend morphologies with ABC block copolymers. Eur. Phys. J. B 1, 71–76 (1998).

    Article  CAS  Google Scholar 

  96. Auschra, C. & Stadler, R. Polymer alloys based on poly(2,6-dimethyl-1,4-phenylene ether) and poly(styrene-co-acrylonitrile) using poly(styrene-b-(ethylene-co-butylene)-b-methyl methacrylate) triblock copolymers as compatibilizers. Macromolecules 26, 6364–6377 (1993).

    Article  CAS  Google Scholar 

  97. Court, F., Leibler, L., Mourran, A., Navarro, C. & Royackkers, V. Compositions à base de résines thermoplastiques semi-cristallines à tenue mécanique et thermique améliorées, leur procédé de préparation et leurs utilisations. French patent FR 97.15389 (1997).

  98. Koulic, C. & Jerome, R. Nanostructured PMMA: from lamellar sheets to double-layered vesicles. Macromolecules 37, 888–893 (2004).

    Article  CAS  Google Scholar 

  99. Hillmyer, M. A., Lipic, P. M., Hajduk, D. A., Almdal, K. & Bates, F. S. Self-assembly and polymerization of epoxy resin-amphiphilic block copolymer nanocomposites. J. Am. Chem. Soc. 119, 2749–2750 (1997).

    Article  CAS  Google Scholar 

  100. Dean, J. M., Grubbs, R. B., Saad, W., Cook, R. F. & Bates, F. S. Mechanical properties of block copolymer vesicle and micelle modified epoxies. J. Polym. Sci. B 41, 2444–2456 (2003).

    Article  CAS  Google Scholar 

  101. Girard-Reydet, E., Pascault, J.-P., Bonnet, A., Court, F. & Leibler, L. A new class of epoxy thermosets. Macromol. Symp. 198, 309–322 (2003).

    Article  CAS  Google Scholar 

  102. Rebizant, V., Venet, A.-S., Tournilhac, F., Girard-Reydet, E., Navarro, C., Pascault, J.-P. & Leibler, L. Chemistry and mechanical properties of epoxy-based thermosets reinforced by reactive and nonreactive SBMX block copolymers. Macromolecules 37, 8017–8027 (2004).

    Article  CAS  Google Scholar 

  103. Milner, S. T., Witten, T. A. & Cates, M. E. Effects of polydispersity in the end-grafted polymer brush. Macromolecules 22, 853–861 (1989).

    Article  CAS  Google Scholar 

  104. Dan, N. & Safran, S. A. Self-assembly in mixtures of diblock copolymers. Macromolecules 27, 5766–5772 (1994).

    Article  CAS  Google Scholar 

  105. Thompson, R. B. & Matsen, M. W. Improving polymeric microemulsions with block copolymer polydispersity. Phys. Rev. Lett. 85, 670–673 (2000).

    Article  CAS  Google Scholar 

  106. Edgecombe, S. R., Gardiner, J. M. & Matsen, M. W. Suppressing autophobic dewetting by using a bimodal brush. Macromolecules 35, 6475–6477 (2002).

    Article  CAS  Google Scholar 

  107. Fredrickson, G. H. & Sides, S. W. Theory of polydisperse inhomogeneous polymers. Macromolecules 36, 5415–5423 (2003).

    Article  CAS  Google Scholar 

  108. Pernot, H., Baumert, M., Court, F. & Leibler, L. Design and properties of co-continuous nanostructured polymers by reactive blending. Nature Mater. 1, 54–58 (2002).

    Article  CAS  Google Scholar 

  109. Orr, C. A., Adedeji, A., Hirao, A., Bates, F. S. & Macosko, C. W. Flow-induced reactive self-assembly. Macromolecules 30, 1243–1246 (1997).

    Article  CAS  Google Scholar 

  110. Schenck, H. U. New trends in industrial polymer research. Macromol. Symp. 195, 19–24 (2003).

    Article  CAS  Google Scholar 

  111. Lodge, T. P. Block copolymers: past successes and future challenges. Macromol. Chem. Phys. 204, 265–273 (2003).

    Article  CAS  Google Scholar 

  112. Park, C., Yoon, J. & Thomas, E. L. Enabling nanotechnology with self-assembled block copolymer patterns. Polymer 44, 6725–6760 (2003).

    Article  CAS  Google Scholar 

  113. Ruokolainen, J, Mezzenga, R., Fredrickson G. H., Kramer, E. J., Hustad, P. D. & Coates, G. W. Morphology and thermodynamic behavior of syndiotactic-polypropylene-poly(ethylene-co-propylene) block copolymers prepared by living olefin polymerization. Macromolecules (in the press).

  114. Falus, P., Xiang, H., Borthwick, M. A., Russell, T. P. & Mochrie, S. G. J. Symmetric-to-asymmetric transition in triblock copolymer-homopolymer blends. Phys. Rev. Lett. 93, 145701 (2004).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We are indebted to V. Abetz, F. S. Bates, T. Hashimoto, E. J. Kramer, C. Macosko and E. L. Thomas for allowing us to reproduce some of their results and providing original micrographs. We have greatly benefited from long-standing collaborations with our colleagues: M. Baumert, A. Bonnet, F. Chauvin, F. Court, J.-J. Flat, P. Gerard, O. Guerret, C. Navarro (ARKEMA), P. Lodefier and B. Vuillemin (TOTAL Petrochemicals), V. Abetz (University of Kiel, Germany), G. H. Fredrickson (UCSB), J.-P. Pascault (INSA, Villeurbane), M. Cloître, L. Corte, M. Freluche, S. Girault, I. Iliopoulos, S. Jouenne, M. Millequant, H. Pernot, V. Rebizant and F. Tournilhac (Matière Molle et Chimie, ESPCI). L.L.'s interest in ABC triblock copolymers has been stimulated and greatly influenced by the late R. Stadler. We also acknowledge finanical support over the years from CNRS, ESPCI, ARKEMA and TOTAL Petrochemicals and authorization to publish some results on triblock copolymers.

Author information

Authors and Affiliations

  1. the Laboratoire Matière Molle et Chimie, ESPCI-CNRS (UMR 167), ESPCI, 10 rue Vauquelin, Paris, 75005, France

    Anne-Valérie Ruzette & Ludwik Leibler

Authors
  1. Anne-Valérie Ruzette
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ludwik Leibler
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Anne-Valérie Ruzette.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ruzette, AV., Leibler, L. Block copolymers in tomorrow's plastics. Nature Mater 4, 19–31 (2005). https://doi.org/10.1038/nmat1295

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat1295

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing