Colloid and Polymer Science

, Volume 286, Issue 13, pp 1465–1474 | Cite as

Gradient copolymers



Gradient copolymers represent a relative new class of copolymers containing at least one section of the macromolecule where the chemical composition continuously changes along the polymer chain. Due to their structural relation to block copolymers, microphase-segregated structures can be formed in bulk, in solution, at surfaces, and interfaces exhibiting a blurred, less-defined border region between phases. The article reviews the preparation methods, the main physical peculiarities, and some proposed applications of gradient copolymers.


Gradient copolymer Gradient block copolymer Definition Preparation Properties Application 


  1. 1.
    IUPAC (1974) Pure Appl Chem 40:477–491CrossRefGoogle Scholar
  2. 2.
    Greszta D, Matyjaszewski K (1996) Polym Prepr 37(1):569–570Google Scholar
  3. 3.
    Arehart SV, Greszta D, Matyjaszewski K (1997) Polym Prepr 38(1):705–706Google Scholar
  4. 4.
    Klumperman B (2007) In: Matyjaszewski K, Gnanou Y, Leibler L (eds). Macromolecular Engineering, vol. 2. Wiley, p 813–838Google Scholar
  5. 5.
    Kryszewski M (1998) Polym Adv Technol 9:244–259CrossRefGoogle Scholar
  6. 6.
    Matyjaszewski K, Ziegler MJ, Arehart SV, Greszta D, Pakula T (2000) J Phys Org Chem 13:775–786CrossRefGoogle Scholar
  7. 7.
    Akovali G, Biliyar K, Shen M (1975) Gov Rep Announce Index (U. S.) 75:52–77Google Scholar
  8. 8.
    Shen M, Bever MB (1972) J Mat Sci 7:741–746CrossRefGoogle Scholar
  9. 9.
    Marchuk GI (1982) Methods of numerical mathematics, 2nd edn. Springer, New YorkGoogle Scholar
  10. 10.
    Ray WH, Gall CE (1969) Macromolecules 2:425–428CrossRefGoogle Scholar
  11. 11.
    Odian G (1991) Principles of polymerization, 3rd edn. Wiley, New York, pp 454–457Google Scholar
  12. 12.
    Odian G (1991) Principles of polymerization, 3rd edn. Wiley, New York, p 274Google Scholar
  13. 13.
    Darling TR, Davis TP, Fryd M, Gridnev AA, Haddleton DM, Ittel SD, Matheson RR Jr, Moad G, Rizzardo E (2000) J Polym Sci A Polym Chem 38:1705–1709CrossRefGoogle Scholar
  14. 14.
    Jouenne S, Gonzalez-Leon JA, Ruzette A-V, Lodefier P, Tence-Girault S, Leibler L (2007) Macromolecules 40:2432–2442CrossRefGoogle Scholar
  15. 15.
    Cypryk M, Delczyk B (2006) Polimery 51:499–506Google Scholar
  16. 16.
    Chojnowski J, Cypryk M, Fortuniak W, Kazmierski K, Rozga-Wijas K, Scibiorek M (2003) ACS Symp Ser 854:12–24CrossRefGoogle Scholar
  17. 17.
    Szwarc M (1968) Carbanions, living polymers and electron transfer process. Interscience, New YorkGoogle Scholar
  18. 18.
    Aoshima S, Kanaoka S (2008) Adv Polym Sci 210:169–208CrossRefGoogle Scholar
  19. 19.
    Aoshima S, Sugihara S, Shibayama M, Kanaoka S (2004) Macromol Symp 215:151–163CrossRefGoogle Scholar
  20. 20.
    Kemp LK, Storey RF (2006) Polym Prepr 47(1):149–150Google Scholar
  21. 21.
    Chojnowski J, Cypryk M, Fortuniak W, Kazmierski K, Rozga-Wijas K, Scibiorek M (2003) ACS Symp Ser 854:12–25Google Scholar
  22. 22.
    Dettmer CM, Gray MK, Torkelson JM, Nguyen SBT (2004) Macromolecules 37:5504–5512CrossRefGoogle Scholar
  23. 23.
    Bello A, Delgado JA (2000) Rev Plast Modern 79:55–63Google Scholar
  24. 24.
    Mignard E, Leblanc T, Bertin D, Guerret O, Reed WF (2004) Macromolecules 37:966–975CrossRefGoogle Scholar
  25. 25.
    Kim J, Torkelson JM (2007) Polym Prepr 48(1):944–945Google Scholar
  26. 26.
    Kim J, Mok MM, Sandoval RW, Woo DJ, Torkelson JM (2006) Macromolecules 39:6152–6160CrossRefGoogle Scholar
  27. 27.
    Kim J, Zhou H, Nguyen ST, Torkelson JM (2006) Polymer 47:5799–5809CrossRefGoogle Scholar
  28. 28.
    Karaky K, Billon L, Pouchan C, Desbrières J (2007) Macromolecules 40:458–464CrossRefGoogle Scholar
  29. 29.
    Cuervo-Rodrigues R, Bordege V, Fernandez-Monreal MC, Fernandez-Garcia M, Madruga EL (2004) J Polym Sci A 42:4168–4176CrossRefGoogle Scholar
  30. 30.
    Karaky K, Père E, Pouchan C, Garay H, Khoukh A, Francois J, Desbrierees J, Billon L (2006) New J Chem 30:698–705CrossRefGoogle Scholar
  31. 31.
    Karaky K, Clisson G, Reiter G, Billon L (2008) Macromol Chem Phys 209:715–722CrossRefGoogle Scholar
  32. 32.
    Gray MK, Zhou H, Nguyen SBT, Torkelson JM (2004) Macromolecules 37:5586–5595CrossRefGoogle Scholar
  33. 33.
    Moad G, Rizzardo E, Thang SH (2008) Polymer 49:1079–1131Google Scholar
  34. 34.
    Rizzardo E, Chiefari J, Chong BYK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Thang SH (1999) Macromol Symp 143:291–307Google Scholar
  35. 35.
    Goebelt B (2007) EU Patent, EP 1803753 A2 (to: BYK-Chemie GmbH, Germany), 07.04. (CA 147:144928).Google Scholar
  36. 36.
    Lutz J-F, Pakula T, Matyjaszewski K (2003) ACS Symp Ser 854:268–282CrossRefGoogle Scholar
  37. 37.
    Matyjaszewski K, Xia J (2001) Chem Rev 101:2921–2990CrossRefGoogle Scholar
  38. 38.
    Matyjaszewski K, Ziegler MJ, Arehart SV, Greszta D, Pakula T (2000) J Phys Org Chem 13:775–786CrossRefGoogle Scholar
  39. 39.
    Fu Y, Cunningham MF, Hutchinson RA (2007) Macromol Symp 259:151–163CrossRefGoogle Scholar
  40. 40.
    Kim J, Torkelson JM (2007) Polym Prepr 48(1):221–222Google Scholar
  41. 41.
    Qin S, Saget J, Pyun J, Jia S, Kowalewski T, Matyjaszewski K (2003) Macromolecules 36:8969–8977CrossRefGoogle Scholar
  42. 42.
    Lee SB, Russell AJ, Matyjaszewski K (2003) Biomacromolecules 4:1386–1393CrossRefGoogle Scholar
  43. 43.
    Qin S, Pyun J, Saget J, Jia S, Kowalewski T, Matyjaszewski K (2002) Polym Prepr 43(2):235–236Google Scholar
  44. 44.
    Börner HG, Duran D, Matyjaszewski K, da Silva M, Sheiko SS (2002) Macromolecules 35:3387–3394CrossRefGoogle Scholar
  45. 45.
    Shinoda H, Miller PJ, Matyaszewski K (2001) Macromolecules 34:3186–3194CrossRefGoogle Scholar
  46. 46.
    Greszta D, Matyjaszewski K (1997) Polym Prepr 38(1):707–708Google Scholar
  47. 47.
    Skeist I (1946) J Amer Chem Soc 68:1781–1784CrossRefGoogle Scholar
  48. 48.
    Gu B, Sen A (2002) Macromolecules 35:8913–8916CrossRefGoogle Scholar
  49. 49.
    Fujisawa T, Penlidis A (2008) J Macromol Sci 45:115–132CrossRefGoogle Scholar
  50. 50.
    Beginn U (2006) Polymer 47:6880–6894CrossRefGoogle Scholar
  51. 51.
    Kotani Y, Kamigaito M, Sawamoto M (1998) Macromolecules 31:5582–5587CrossRefGoogle Scholar
  52. 52.
    Greszta D, Matyjaszewski K, Pakula T (1997) Polym Prepr 38(1):709–710Google Scholar
  53. 53.
    Dube MA, Soares JBP, Penlidis A, Hamielec AE (1997) Ind Eng Chem Res 36:966–1015CrossRefGoogle Scholar
  54. 54.
    Hamielec AE, MacGregor JF, Penlidis A (1987) Makromol Chem Macromol Symp 10/11:521–570Google Scholar
  55. 55.
    Wang R, Luo Y, Li BG, Sun X, Zhu S (2006) Macromol Theory Simul 15:356–368CrossRefGoogle Scholar
  56. 56.
    Wang R, Luo Y, Li BG, Zhu S (2007) AIChE 53:174–186CrossRefGoogle Scholar
  57. 57.
    Sun X, Luo Y, Wang R, Li BG, Zhu S (2007) Macromolecules 40:849–859CrossRefGoogle Scholar
  58. 58.
    Schmitz C, Beginn U, Möller M (2008) Polymer submitted.Google Scholar
  59. 59.
    Pakula T (1996) Macromol Theory Simul 5(5):987–1006CrossRefGoogle Scholar
  60. 60.
    Aksimentiev A, Hoyst R (1999a) Prog Polym Sci 24:1045–1093CrossRefGoogle Scholar
  61. 61.
    Aksimentiev A, Hoyst R (1999b) J Chem Phys 111:2329–2339CrossRefGoogle Scholar
  62. 62.
    Jiang R, Jin Q, Li B, Ding D, Wickham RA, Shi A-C (2008) Macromolecules 41:5457–5465CrossRefGoogle Scholar
  63. 63.
    Shull KR (2002) Macromolecules 35:8631–8639CrossRefGoogle Scholar
  64. 64.
    Lefebvre MD, Olvera de la Cruz M, Shull KR (2004) Macromolecules 37:1118–1123CrossRefGoogle Scholar
  65. 65.
    Matyjaszewski K, Ziegler MJ, Arehart SV, Greszta D, Pakula T (2000) J Phys Org Chem 13:775–778CrossRefGoogle Scholar
  66. 66.
    Karaky K, Pere E, Pouchan C, Desbrieres J, Derail C, Billon L (2006) Soft Mat 2:770–778CrossRefGoogle Scholar
  67. 67.
    Shinoda H, Matyjaszewski K, Okrasa L, Mierzwa M, Pakula T (2003) Macromolecules 36:4772–4778CrossRefGoogle Scholar
  68. 68.
    Lee H-il, Matyjaszewski K, Yu S, Sheiko SS (2005) Macromolecules 38:8264–8271CrossRefGoogle Scholar
  69. 69.
    Mok MM, Pujari S, Burghardt WR, Dettmer CM, Nguyen SBT, Ellison CJ, Torkelson JM (2008) Macromolecules 41:5818–5829CrossRefGoogle Scholar
  70. 70.
    Pickett GT (2003) J Chem Phys 118:3898–3903CrossRefGoogle Scholar
  71. 71.
    Lefebvre MD, Dettmer CM, McSwain RL, Xu C, Davila JR, Composto RJ, Nguyen SBT, Shull KR (2005) Macromolecules 38:10494–10502CrossRefGoogle Scholar
  72. 72.
    Gohy J-F (2005) Advances in Polymer Science 190(Block Copolymers II):65–136Google Scholar
  73. 73.
    Hamley IW (2005) Block copolymers in solution—fundamentals and application, chap. 2. Wiley, ChichesterGoogle Scholar
  74. 74.
    Wong CLH, Kim J, Roth CB, Torkelson JM (2007) Macromolecules 40:5631–5633CrossRefGoogle Scholar
  75. 75.
    Okabe S, Fuse C, Sugihara S, Aoshima S, Shibayama M (2006) Physica B: Cond Matter 385–386:756–758CrossRefGoogle Scholar
  76. 76.
    Okabe S, Seno K, Kanaoka S, Aoshima S, Shibayama M (2006) Macromolecules 39(4):1592–1597CrossRefGoogle Scholar
  77. 77.
    Bonne TB, Lüdtke K, Jordan R, Papadakis CM (2007) Macromol Chem Phys 208:1402–1408CrossRefGoogle Scholar
  78. 78.
    Bonne TB, Lüdtke K, Jordan R, Papadakis CM (2007) Coll Polym Sci 5:491–497Google Scholar
  79. 79.
    Hoogenboom R, Thijs HML, Wouters D, Hoeppener S, Schubert US (2008) Macromolecules 41:1581–1583CrossRefGoogle Scholar
  80. 80.
    Hoogenboom R, Thijs HML, Fijten MWM, Van Lankvelt BM, Schubert US (2007) J Polym Sci, Part A: Polym Chem 45:416–422CrossRefGoogle Scholar
  81. 81.
    Stuart CMH (2008) Coll Polym Sci 286:855–864CrossRefGoogle Scholar
  82. 82.
    Wang T, Liu F, Luo N, Ying S, Liu Q (2001) Hech Xiang Gon 24:328–330Google Scholar
  83. 83.
    Kim J, Gray MKJ, Zhi H, Nguyen SBT, Torkelson JM (2005) Macromolecules 38:1037–1040CrossRefGoogle Scholar
  84. 84.
    Tao Y, Kim J, Torkelson JM (2006) Polymer 47:6773–6781CrossRefGoogle Scholar
  85. 85.
    Kim J, Zhou H, Nguyen SBT, Torkelson JM (2006) Polymer 47:5799–5809CrossRefGoogle Scholar
  86. 86.
    Hashimoto T, Tsukahara Y, Tachi K, Kawai H (1983) Macromolecules 16:648–657CrossRefGoogle Scholar
  87. 87.
    Mok M, Kim J, Torkelson JM (2008) J Polym Sci B Polym Phys 46:48–58CrossRefGoogle Scholar
  88. 88.
    Askadskii AA, Luchkina LV, Nikiforova GG, Kovriga OV (2007) Plasti Mass 30–33Google Scholar
  89. 89.
    Kemp LK, Storey RF (2006) Abstracts 231st ACS Nation. Meet., March 26–30, 2006Google Scholar
  90. 90.
    Kano Y (2002) Hikaku Kagaku (Science) 48:109–121Google Scholar
  91. 91.
    Genzer J, Bhat R, Tomlinson M (2004) Proc Ann Meet Adhes Soc 27:47–48Google Scholar
  92. 92.
    Goebelt B (2004) FATIPEC Congress 27th(1):303–312Google Scholar
  93. 93.
    Hu Z, Tao M, Zhang Z (2007) Coll Surf A 302:307–311CrossRefGoogle Scholar
  94. 94.
    Goebelt B, Omeis J, Johann S, Koehler S (2008) PCT Int Appl WO. 2008043529 A2 20080417 (to: Byk-Chemie GmbH, Germany)Google Scholar

Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  1. 1.Organic Materials Chemistry, Institute for ChemistryUniversity of OsnabrueckOsnabrueckGermany

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