Group Transfer Polymerization: A Critical Review of Its Mechanism and Comparison with Other Methods for Controlled Polymerization of Acrylic Monomers

  • Owen W. WebsterEmail author
Part of the Advances in Polymer Science book series (POLYMER, volume 167)


Group transfer polymerization (GTP) was announced 20 years ago by DuPont as a method for synthesis of acrylic block polymers. It operates at high enough temperatures to allow reactor cooling by water-cooled reflux condensers, rather than more costly refrigeration units. GTP uses 1-methoxy-1-(trimethylsiloxy)-2-methylprop-1-ene (MTS) as initiator and a carboxylic acid salt as catalyst. The number of growing polymer chains corresponds to the amount of MTS used. Chain growth stops when the monomer is depleted. Addition of a new monomer at this point starts chain growth again to produce a block polymer. DuPont sells pigmented inks containing GTP block polymer dispersing agents.

Initial mechanism studies pointed to a trimethylsilyl transfer process that now appears to be incorrect. Strong evidence is presented for a dissociative anionic process. Reactivation of silylated chain ends by the alkoxide eliminated during end group cyclization is proposed as the reason GTP works at 80 °C.

A comparison of GTP with other methods for block polymer synthesis is presented.


Group transfer polymerization Polymethacrylates Polyacrylates Living polymerization GTP mechanism Living anionic polymerization of MMA 

List of Abbreviations




Atom transfer polymerization


Butyl methacrylate




Catalytic chain transfer


Degree of polymerization


Group transfer polymerization


Methyl acrylate


Methyl methacrylate




Number average molecular weight


Weight average molecular weight


Molecular weight dispersity, Mw/Mn


Molecular weight






Poly(butyl methacrylate)


Poly(methyl acrylate)


Poly(methyl methacrylate)


Reversible addition fragmentation transfer




Stable free radical polymerization












Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.



The bulk of the DuPont work described herein was conducted by research workers in the Automotive Finishes and Central Research Departments. I wish to especially thank Dotsi Sogah, Wally Hertler, Bill Farnham, T.V. RajanBabu, and Professors Jack Roberts and Barry Trost for many hours of discussion on various aspects of GTP technology.


  1. 1.
    Webster OW, Hertler WR, Sogah DY, Farnham WB, RajanBabu TV (1983) J Am Chem Soc 105:5706Google Scholar
  2. 2.
    Eastmond GC, Webster OW (1991) Group transfer polymerization. In: Ebdon JR (ed) New methods of polymer synthesis. Blackie, London, p 24Google Scholar
  3. 3.
    Webster OW, Anderson BC (1992) Group transfer polymerization. In: Mijs WJ (ed) New methods for polymer synthesis. Plenum, New York, p 1Google Scholar
  4. 4.
    Hertler WR (1996) Group transfer polymerization. In: Kricheldorf HR (ed) Silicon in polymer synthesis. Springer, Berlin Heidelberg New York, p 69Google Scholar
  5. 5.
    Hertler WR (1997) Group transfer polymerization for controlled polymer architecture. In: Hatada K, Kitayama T, Vogl O (eds) Macromolecular design of polymeric materials. Marcel Dekker, New York, p 109Google Scholar
  6. 6.
    Quirk RP, Kim J-S (1995) J Phy Org Chem 8:242Google Scholar
  7. 7.
    Anderson BC, Andrews GD, Arthur P Jr, Jacobson HW, Melby LR, Playtis AJ, Sharkey WH (1984) Macromolecules 14:1599Google Scholar
  8. 8.
    Asami R, Kondo Y, Takaki M (1987) In: Hogen-Esch TE, Smid J (eds) Recent Advances in Anionic Polymers. Proceedings of the International Symposium. Elsevier, New York, p 381Google Scholar
  9. 9.
    Sogah DY, Hertler WR, Webster OW, Cohen GM (1987) Macromolecules 20:1473Google Scholar
  10. 10.
    Simms JA (1991) Rubber Chem Technol 64:139Google Scholar
  11. 11.
    Dicker IB, Cohen GM, Farnham WB, Hertler WR, Laganis ED, Sogah DY (1990) Macromolecules 23:4034Google Scholar
  12. 12.
    Brittain WJ, Dicker IB (1989) Macromolecules 22:1054Google Scholar
  13. 13.
    Reetz MT, Hutte S, Goddard R (1995) J Phys Org Chem 8:231Google Scholar
  14. 14.
    Hertler WR, Sogah DY, Webster OW, Trost BM (1984) Macromolecules 17:1415Google Scholar
  15. 15.
    Zhuang R, Muller AHE (1995) Macromolecules 28:8043Google Scholar
  16. 16.
    Hertler WR, RajanBabu TV, Overnal DW, Reddy GS, Sogah DY (1988) J Am Chem Soc 110:5841Google Scholar
  17. 17.
    Sogah DY, Webster OW (1986) Macromolecules 19:1775Google Scholar
  18. 18.
    Hirabayashi T, Itoh T (1988) Polym J 20:1041Google Scholar
  19. 19.
    Martin DT, Bywater S (1992) Makromol Chem 193:1011Google Scholar
  20. 20.
    Zou YXH, Pan R (1990) Chin Chem Lett 1:265Google Scholar
  21. 21.
    Miller J, Jenkins AD, Tsartolia E, Watson DRM, Stejskal J, Kratochvil P (1988) Polym Bull 20:247Google Scholar
  22. 22.
    Corbin DR, Sormani PME (1992) U.S. Patent 5,162,467 (to DuPont)Google Scholar
  23. 23.
    Berl V, Helmchen G, Preston S (1994) Tetrahedron Lett 35:233Google Scholar
  24. 24.
    Mei M, Muller AHE (1987) Makromol Chem Rapid Commun 8:99Google Scholar
  25. 25.
    Dixon DA, Hertler WR, Chase DB, Farnham WB, Davidson F (1988) Inorg Chem 27:4012Google Scholar
  26. 26.
    Sitz H-D, Bandermann F (1987) Group transfer of methyl methacrylate with basic catalysts In: Fontanille M, Guyot M (eds) Recent advances in mechanistic aspects of polymerization. Reidel, p 41Google Scholar
  27. 27.
    Seebach D (1988) Angew Chem Int Ed Engl 100:1624Google Scholar
  28. 28.
    Hertler WR (1994) Macromol Symp 88:55Google Scholar
  29. 29.
    Schneider LV, Dicker IB (1988) U.S. Patent 4,736,003 (to DuPont)Google Scholar
  30. 30.
    Brittain WJ (1988) J Am Chem Soc 110:7440Google Scholar
  31. 31.
    Vamvakaki M (U Crete), Patrickios CS (U Cyprus), Webster OW unpublished results. MMA, MTS, TMS benzoate (made by reaction of MTS with benzoic acid) and TBA benzoate were combined in THF (25% solution) at molar ratios of 20/1/5/0.02. The polymerization was 65% complete in 2.5 h (GPC), Mn 3300, MWD 1.07. After 24 h, Mn 4900, MWD 1.07. With no TMS benzoate the polymerization was complete in 10 min, Mn 2600, MWD 1.37Google Scholar
  32. 32.
    Uschida S (present location Tokyo Inst Tech), Webster OW unpublished results. MMA, MTS, TMS Ac, and TBA Ac were combined in THF (20% solution) at a molar ratio of 20/1/5/0.02. The polymerization was complete in 30 min (NMR). Mn 1632, MWD 1.17. Without the TMS Ac the THF refluxed and the polymerization was over in less than 1 minGoogle Scholar
  33. 33.
    Farnham WB, Sogah DY (1986) Polym Prepr Am Chem Soc Div Polym Chem 27:167Google Scholar
  34. 34.
    Sogah DY, Farnham WB (1985) In: Sakurai (ed) Organosilicon and biooganosilicon chemistry: stucture, bonding, reactivity and synthetic application. Ellis Horwood, Chichester, chap 20, p 219Google Scholar
  35. 35.
    Raucher S, Schindel BC (1987) Syn Comm 17:637Google Scholar
  36. 36.
    Webster OW, unpublished resultsGoogle Scholar
  37. 37.
    Quirk RP, Ren J (1992) Macromolecules 25:6612Google Scholar
  38. 38.
    Webster OW, Hertler WR, unpublished resultsGoogle Scholar
  39. 39.
    Haddleton DM, Crossman MC, Hunt KH, Topping C, Waterson C, Suddaby KG (1997) Macromolecules 30:3992Google Scholar
  40. 40.
    Jenkins AD, Tsartolla E, Walton DRM, Stejskal J, Kratochvil P (1988) Polym Bull 20:97Google Scholar
  41. 41.
    Muller MA, Stickler M (1986) Makromol Chem Rapid Commun 7:575Google Scholar
  42. 42.
    Fox TG, Schnecko HW (1962) Polymer 3:575Google Scholar
  43. 43.
    Wei Y, Wenk GE (1987) Polym Prepr Am Chem Soc Div Polym Chem 28:252Google Scholar
  44. 44.
    Gabor AH, Ober CK (1996) Chem Mater 8:2272Google Scholar
  45. 45.
    Rannard SP, Bilingham NC, Armes SP, Mykytiuk J (1993) Eur Polym J 29:407Google Scholar
  46. 46.
    Patrickios CS, Hertler WR, Abbott NL, Hatton TA (1994) Macromolecules 27:930Google Scholar
  47. 47.
    Mai PM, Muller AHE (1987) Makromol Chem Rapid Commun 8:247Google Scholar
  48. 48.
    Muller AHE (1990) Makromol Chem Makromol Shymp 32:87Google Scholar
  49. 49.
    Schubert W, Sitz H-D, Bandermann F (1989) Makromol Chem 190:2193Google Scholar
  50. 50.
    Shubert W, Bandermann F (1989) Makromol Chem 190:2721Google Scholar
  51. 51.
    Sitz HD, Speilkamp HD, Bandermann F (1988) Makromol Chem 189:429Google Scholar
  52. 52.
    Spinelli HJ (1996) Prog Org Coat 27:255Google Scholar
  53. 53.
    Szwarc M (1956) Nature 178:1168Google Scholar
  54. 54.
    Miyamoto M, Sawamoto M, Higasimura T (1984) Macromolecules 17:265, 2228Google Scholar
  55. 55.
    Faust R, Kennedy J (1986) Polym Bull 17:7Google Scholar
  56. 56.
    Adachi T, Sugimoto H, Aida T, Inoue S (1993) Macromolecules 26:1238Google Scholar
  57. 57.
    Aida T, Sugimoto H, Kuroli M, Inoue S (1995) J Phys Org Chem 8:249Google Scholar
  58. 58.
    Inoue S (2000) J Polym Sci Part A Polym Chem 38:2861Google Scholar
  59. 59.
    Yasuda H, Yamamoto H, Takemoto Y, Yamashita M, Yokoto K, Miyaki S, Nakamure A (1993) Makromol Chem Macromol Symp 67:187Google Scholar
  60. 60.
    Yasuda H (2001) J Polym Sci Part A Polym Chem 39:1955Google Scholar
  61. 61.
    Boffa LS, Novak BM (1994) Macromolecules 27:6993Google Scholar
  62. 62.
    Collins S, Ward DG, Suddaby KF (1994) Macromolecules 27:7222Google Scholar
  63. 63.
    Wang J-S, Jerome R, Teyssie P (1995) J Phys Org Chem 8:208Google Scholar
  64. 64.
    Ballard DGH, Bowles RJ, Haddleton DM, Richards SN, Sellens R, Twose DL (1992) Macromolecules 25:5907Google Scholar
  65. 65.
    Reetz MT, Knauf T, Minet U, Bingel C (1988) Angew Chem Int Ed Engl 27:1373Google Scholar
  66. 66.
    Sivaram S, Dhal PK, Kashikal SP, Khisti RS, Shinde BM, Baskaran D (1991) Polym Bull 25:77Google Scholar
  67. 67.
    Webster OW (1994) J Macromol Sci Pure Appl Chem A31:927Google Scholar
  68. 68.
    Haggard RA, Lewis SN (1984) Prog Org Coatings 12:1Google Scholar
  69. 69.
    Pietzonka T, Seebach D (1993) Angew Chem Int Ed Engl 32:716Google Scholar
  70. 70.
    Baskaran D, Muller AHE (2000) Macromol Rapid Commun 21:390Google Scholar
  71. 71.
    Konigsmann H, Jungling S, Muller HE (2000) Macromol Rapid Comm 21:758Google Scholar
  72. 72.
    Zagata AP, Hogen-Esch TE (1996) Macromolecules 29:3038Google Scholar
  73. 73.
    Baskaran D, Muller AHE (1997) Macromolecules 30:1869Google Scholar
  74. 74.
    Otsu T, Yoshida M, Tazaki T (1982) Makromol Chem Rapid Commun 3:127, 3:133Google Scholar
  75. 75.
    Bledzki A, Braun D (1981) Makromol Chem 182:1047Google Scholar
  76. 76.
    Otsu T (2000) J Polym Sci Part A Polym Chem 38:2121Google Scholar
  77. 77.
    Solomon DH, Rizzardo E, Cacioli P (1985) U.S. Patent 4,581,429Google Scholar
  78. 78.
    Rizzardo E (1987) Chem Aust 54:32Google Scholar
  79. 79.
    Georges MK, Vergin RPN, KazmaierPM, Hamer GK (1993) Macromolecules 26:2987Google Scholar
  80. 80.
    Benoit D, Chaplinski V, Braslau R, Hawker CJ (1999) J Am Chem Soc 121:3904Google Scholar
  81. 81.
    Benoit D, Grimaldi S, Robin S, Finet J-P, Tordo P, Gnanou Y (2000) J Am Chem Soc 122:5929Google Scholar
  82. 82.
    Hawker CJ, Bosman AW, Harth E (2001) Chem Rev 101:3661Google Scholar
  83. 83.
    Wang J-S, Matyjaszewski K (1995) J Am Chem Soc 117:5614Google Scholar
  84. 84.
    Kato M, Kamigaito M, Sawamoto M, Higashimura T (1995) Macromolecules 28:1721Google Scholar
  85. 85.
    Percec V, Barbiou B (1995) Macromolecules 28:7970Google Scholar
  86. 86.
    Percec V, Barbiou B, Kim H-J (1998) J Am Chem Soc 120:305Google Scholar
  87. 87.
    Matyjaszewski K, Xia J (2001) Chem Rev 101:2921Google Scholar
  88. 88.
    Kamigaito M, Ando T, Sawamoto M (2002) Chem Rev 101:3689Google Scholar
  89. 89.
    Chiefari J, Chong YKB, Ercole F, Krstina J, Jeffery J, Letp T, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH (1998) Macromolecules 31:5559Google Scholar
  90. 90.
    Mayadunne RTA, Rizzardo E, Chiefari J, Chong YK, Moad G, Thang SH (1999) Macromolecules 32:6977Google Scholar
  91. 91.
    Davis TP (2002) Private communicationGoogle Scholar
  92. 92.
    Wieland PC, Raether B, Nuyken O (2001) Macromol Rapid Commun 22:700Google Scholar
  93. 93.
    Gridnev A, Ittel SD (2001) Chem Rev 101:3611Google Scholar
  94. 94.
    Gridnev A (2000) J Polym Chem Part A Polym Chem 38:1753Google Scholar
  95. 95.
    Wayland BB, Pasmik G, Mukerjee SL, Fryd M (1994) J Am Chem Soc 116:7943Google Scholar

Copyright information

© Springer-Verlag 2003

Authors and Affiliations

  1. 1.Chadds FordUSA

Personalised recommendations