Colloid and Polymer Science

, Volume 291, Issue 5, pp 1171–1180 | Cite as

Thiol-terminated hydroxy-functional polymer as a transtab toward polymer latex particles

  • Syuji FujiiEmail author
  • Shinji Yamashita
  • Yuichi Kakigi
  • Kodai Aono
  • Sho Hamasaki
  • Shin-ichi Yusa
  • Yoshinobu Nakamura
Original Contribution


Hydroxy-functional macrodisulfides have been synthesized by atom transfer radical polymerization of 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate in 2-propanol. Mean degrees of polymerization of the polymer chains beside the disulfide were fixed at 30, 60, and 90; since ATRP has reasonably good living character, the molecular weight distribution is relatively narrow. Furthermore, the macrodisulfides were reduced to synthesize corresponding thiol-terminated polymers with relatively narrow molecular weight distributions. 1H nuclear magnetic resonance and gel permeation chromatography were used to characterize the macrodisulfides and thiol-terminated polymers in terms of their chemical structure, molecular weight, and polydispersity, respectively. Dispersion polymerizations of styrene using the thiol-terminated hydroxy-functional polymers as a transtab (chain transfer agent + colloidal stabilizer) in ethanol resulted in colloidally stable submicrometer-sized polystyrene latex particles. Scanning electron microscopy, Fourier transform infrared spectroscopy, and elemental microanalysis were used to characterize the particles in terms of their morphologies, particle sizes and their distributions, and chemical compositions.


Hydroxy-functional polymers Macrodisulfides Thiol group Latex particles Dispersion polymerization 



This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Molecular Soft-Interface Science” from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

Supplementary material

396_2012_2845_MOESM1_ESM.doc (198 kb)
ESM 1 (DOC 198 kb)


  1. 1.
    Wichterle O, Lim D (1960) Nature 185:118CrossRefGoogle Scholar
  2. 2.
    Barrett GD, Constable IJ, Steward AD (1986) J Cataract Refract Surg 12:623Google Scholar
  3. 3.
    Menace R, Skorpik C, Juchem M, Scheidel W, Schranz RI (1989) J Cataract Refract Surg 15:264Google Scholar
  4. 4.
    Bennet HS, Wyricks AD, Lee SW, McNeil H (1976) J Stain Technol 51:71Google Scholar
  5. 5.
    Canal T, Peppas NA (1989) J Biomed Mater Res 23:1183CrossRefGoogle Scholar
  6. 6.
    Miyajima M, Okano T, Kim TSW, Higushi WI (1987) J Control Release 5:179CrossRefGoogle Scholar
  7. 7.
    Lewis AL, Cumming ZL, Stratford PW (2001) Biomaterials 22:99CrossRefGoogle Scholar
  8. 8.
    Carlemalm E (1984) Chemische Werke Lowi G.m.b.H, US patent 4424329Google Scholar
  9. 9.
    Weiss KD (1997) Prog Polym Sci 22:203CrossRefGoogle Scholar
  10. 10.
    Guojun L, Carl KS, Nanxing H, Jian T (1996) Macromolecules 29:220CrossRefGoogle Scholar
  11. 11.
    Beers KL, Boo S, Gaynor SG, Matyjaszewski K (1999) Macromolecules 32:5772CrossRefGoogle Scholar
  12. 12.
    Weaver JVM, Bannister I, Robinson KL, Bories-Azeau X, Armes SP, Smallridge M, McKenna P (2004) Macromolecules 37:2395CrossRefGoogle Scholar
  13. 13.
    Guice KB, Marrou SR, Gondi RS, Sumerlin BS, Loo YL (2008) Macromolecules 41:4390CrossRefGoogle Scholar
  14. 14.
    Fujii S, Suzaki M, Kakigi Y, Aono K, Yusa S, Nakamura Y (2011) J Polym Sci A Polym Chem 49:1633CrossRefGoogle Scholar
  15. 15.
    Horák D, Karpíšek M, Turková J, Beneš M (1999) Biotechnol Prog 15:208CrossRefGoogle Scholar
  16. 16.
    Chen X, Armes SP (2003) Adv Mater 15:1558CrossRefGoogle Scholar
  17. 17.
    Ali AMI, Pareek P, Sewell L, Schmid A, Fujii S, Armes SP, Shirley IM (2007) Soft Matter 3:1003CrossRefGoogle Scholar
  18. 18.
    Li Y, Armes SP (2005) Macromolecules 38:8155CrossRefGoogle Scholar
  19. 19.
    Daniel MC, Astruc D (2004) Chem Rev 104:293CrossRefGoogle Scholar
  20. 20.
    Sardar R, Funston AM, Mulvaney P, Murray RW (2009) Langmuir 25:13840CrossRefGoogle Scholar
  21. 21.
    Lundblad RL (1995) Techniques in protein modification. CRC, Boca RatonGoogle Scholar
  22. 22.
    Hermanson GT (1996) Bioconjugate techniques. Academic, New YorkGoogle Scholar
  23. 23.
    Jocelyn PC (1987) Methods Enzymol 143:246CrossRefGoogle Scholar
  24. 24.
    Gilbert HF (1997) Bioelectrochem Princ Pract 5:256Google Scholar
  25. 25.
    Tsarevsky NV, Matyjaszewski K (2002) Macromolecules 35:9009CrossRefGoogle Scholar
  26. 26.
    Aliyar HA, Hamilton PD, Ravi N (2005) Biomacromolecules 6:204CrossRefGoogle Scholar
  27. 27.
    Tsarevsky NV, Matyjaszewski K (2005) Macromolecules 38:3087CrossRefGoogle Scholar
  28. 28.
    Plunkett KN, Berkowski KL, Moore JS (2005) Biomacromolecules 6:632CrossRefGoogle Scholar
  29. 29.
    Yoshizumi A, Kanayama N, Maehara Y, Ide M, Kitano H (1999) Langmuir 15:482CrossRefGoogle Scholar
  30. 30.
    Debora B, Karina LH, Benjamin AF, Heather DM (2004) J Am Chem Soc 126:15372CrossRefGoogle Scholar
  31. 31.
    Warren NJ, Muise C, Stephens A, Armes SP, Lewis AL (2012) Langmuir 28:2928CrossRefGoogle Scholar
  32. 32.
    Shu XZ, Liu Y, Palumbo F, Prestwich GD (2003) Biomaterials 24:3825CrossRefGoogle Scholar
  33. 33.
    Hisano N, Morikawa N, Iwata H, Ikada Y (1998) J Biomed Mater Res 40:115CrossRefGoogle Scholar
  34. 34.
    Matsusaki M, Yoshida H, Akashi M (2007) Biomaterials 28:2729CrossRefGoogle Scholar
  35. 35.
    Stevens MP (Edn) (1999) Polymer chemistry 3rd Edition: an introduction. Oxford University PressGoogle Scholar
  36. 36.
    Fujii S, Minami H, Okubo M (2004) Colloid Polym Sci 282:569CrossRefGoogle Scholar
  37. 37.
    Fujii S, Kakigi Y, Suzaki M, Yusa S, Muraoka M, Nakamura Y (2009) J Polym Sci A Polym Chem 47:3431CrossRefGoogle Scholar
  38. 38.
    Lovell PA, El-Aasser MS (1997) Emulsion polymerization and emulsion polymers. Wiley, ChichesterGoogle Scholar
  39. 39.
    Kawaguchi S, Ito K (2005) Adv Polym Sci 175:299CrossRefGoogle Scholar
  40. 40.
    Nakamura K, Fujimoto K, Kawaguchi H (1999) Colloids Surf A Physiochem Eng Asp 153:195CrossRefGoogle Scholar
  41. 41.
    Okubo M, Fujii S, Maenaka H, Minami H (2002) Colloid Polym Sci 280:183CrossRefGoogle Scholar
  42. 42.
    Kitano H, Kawabata J (1996) Macromol Chem Phys 197:1721CrossRefGoogle Scholar
  43. 43.
    Kitano H, Kawabata J, Muramoto T (1996) Macromol Chem Phys 197:3657CrossRefGoogle Scholar
  44. 44.
    Tauer K (1995) Polym Adv Technol 6:435CrossRefGoogle Scholar
  45. 45.
    Fujii S, Aono K, Suzaki M, Hamasaki S, Yusa S, Nakamura Y (2012) Macromolecules 45:2863CrossRefGoogle Scholar
  46. 46.
    Almog Y, Reich S, Levy MB (1982) Polym J 14:131CrossRefGoogle Scholar
  47. 47.
    Tseng CM, Lu YY, El-Aasser MS, Vanderhoff JW (1986) J Polym Sci Polym Chem Ed 24:2995CrossRefGoogle Scholar
  48. 48.
    Lok KP, Ober CK (1985) Can J Chem 63:209CrossRefGoogle Scholar
  49. 49.
    Ober CK, Lok KP, Hair ML (1985) J Polym Sci Lett Ed 23:103CrossRefGoogle Scholar
  50. 50.
    Lok KP, Ober CK (1987) Macromolecules 20:268CrossRefGoogle Scholar
  51. 51.
    Winnik MA, Lukas R, Chen WF, Furlong P, Croucher MD (1987) Macromol Chem Macromol Symp 10/11:483CrossRefGoogle Scholar
  52. 52.
    Paine AJ (1990) J Colloid Interface Sci 138:157CrossRefGoogle Scholar
  53. 53.
    Paine AJ (1990) Macromolecules 23:3104CrossRefGoogle Scholar
  54. 54.
    Paine AJ (1990) J Polym Sci Polym Chem Ed 18:2485Google Scholar
  55. 55.
    Napper DH (1997) J Colloid Interface Sci 58:390CrossRefGoogle Scholar
  56. 56.
    Pelton RH, Osterroth A, Brook MA (1990) J Colloid Interface Sci 137:120CrossRefGoogle Scholar
  57. 57.
    Pelton RH, Osterroth A, Brook MA (1991) J Colloid Interface Sci 147:523CrossRefGoogle Scholar
  58. 58.
    Dawkins JV, Taylor G (1979) Polymer 20:599CrossRefGoogle Scholar
  59. 59.
    Jialanella GL, Firer EM, Piirma I (1992) J Polym Sci A Polym Chem 30:1925CrossRefGoogle Scholar
  60. 60.
    Windsor C, Marazek Z, Winnie MA, Croucher MD, Riess G (1994) Eur Polym J 31:121Google Scholar
  61. 61.
    Canelas DA, Betts DE, DeSimone JM (1996) Macromolecules 29:2818CrossRefGoogle Scholar
  62. 62.
    Baines FL, Dionisio S, Billingham NC, Armes SP (1996) Macromolecules 29:3096CrossRefGoogle Scholar
  63. 63.
    Lepilleur C, Beckman EJ (1997) Macromolecules 30:745CrossRefGoogle Scholar
  64. 64.
    Giles MR, Griffiths RMT, Aguiar-Ricardo A, Silva MMCG, Howdle SM (2001) Macromolecules 34:20CrossRefGoogle Scholar
  65. 65.
    Shaffer KA, Jones TA, Canelas DA, DeSimone JM (1996) Macromolecules 29:2704CrossRefGoogle Scholar
  66. 66.
    Lacroix-Desmazes P, Guyot A (1996) Macromolecules 29:4508CrossRefGoogle Scholar
  67. 67.
    Kawaguchi S, Winnik MA, Ito K (1996) Macromolecules 29:4465CrossRefGoogle Scholar
  68. 68.
    Chen M-Q, Kishida A, Akashi M (1996) J Polym Sci Polym Chem 34:2213CrossRefGoogle Scholar
  69. 69.
    Dupin D, Fujii S, Armes SP, Reeve P, Baxter SM (2006) Langmuir 22:3381CrossRefGoogle Scholar
  70. 70.
    Brandrup EH, Immergut HA, Grulke EA (1999) Polymer handbook, 4th edn. Wiley, New YorkGoogle Scholar
  71. 71.
    Fedors RF (1974) Polym Eng Sci 14:147CrossRefGoogle Scholar
  72. 72.
    Bjorklund RB, Liedberg BJ (1986) J Chem Soc Chem Commun 1293Google Scholar
  73. 73.
    Kawaguchi M, Sakata Y, Anada S, Kato T, Takahashi A (1994) Langmuir 10:538CrossRefGoogle Scholar
  74. 74.
    Lascelles SF, Armes SP (1997) J Mater Chem 7(8):1339CrossRefGoogle Scholar
  75. 75.
    Pathak S, Greci MT, Kwong RC, Mercado K, Prakash GKS, Olah GA, Thompson ME (2000) Chem Mater 12:1985CrossRefGoogle Scholar
  76. 76.
    Fujii S, Ryan AJ, Armes SP (2006) J Am Chem Soc 128:7882CrossRefGoogle Scholar
  77. 77.
    Fujii S, Iddon PD, Ryan AJ, Armes SP (2006) Langmuir 22:7512CrossRefGoogle Scholar
  78. 78.
    Kettlewell SL, Schmid A, Fujii S, Dupin D, Armes SP (2007) Langmuir 23:11381CrossRefGoogle Scholar
  79. 79.
    Fujii S, Mochizuki M, Aono K, Hamasaki S, Murakami R, Nakamura Y (2011) Langmuir 27:12902CrossRefGoogle Scholar
  80. 80.
    Binks BP, Horozov TS (2006) (Edn.) Colloidal particles at liquid interfaces, Cambridge University PressGoogle Scholar
  81. 81.
    Fujii S, Read ES, Armes SP, Binks BP (2005) Adv Mater 17:1014CrossRefGoogle Scholar
  82. 82.
    Fujii S, Cai Y, Weaver JVM, Armes SP (2005) J Am Chem Soc 127:7304CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  • Syuji Fujii
    • 1
    Email author
  • Shinji Yamashita
    • 1
  • Yuichi Kakigi
    • 1
  • Kodai Aono
    • 1
  • Sho Hamasaki
    • 1
  • Shin-ichi Yusa
    • 2
  • Yoshinobu Nakamura
    • 1
    • 3
  1. 1.Department of Applied Chemistry, Faculty of EngineeringOsaka Institute of TechnologyOsakaJapan
  2. 2.Graduate School of EngineeringUniversity of HyogoHimejiJapan
  3. 3.Nanomaterials Microdevices Research CenterOsaka Institute of TechnologyOsakaJapan

Personalised recommendations