Skip to main content
SpringerLink
Log in

Radical Polymerization in Direct Mini-Emulsion Systems

  • Chapter
  • First Online:
New Polymerization Techniques and Synthetic Methodologies

Part of the book series: Advances in Polymer Science ((POLYMER,volume 155))

Abstract

Polymerization in direct mini-emulsions is a relatively new polymerization technique which allows the preparation of submicron latex particles within the range 100<particle diameter<500 nm. This process involves the generation of a large population of submicron monomer droplets in water (termed the mini-emulsion) by intensive shear force with the aid of an adequate emulsifier and coemulsifier (or hydrophobe). These stable, homogenized monomer droplets have an extremely large surface area and, therefore, can compete effectively with the monomer-swollen micelles, if present, for the oligomeric radicals generated in water. Monomer droplets may thus become the predominant loci for particle nucleation and polymerization. This article presents a review of the current literature in the field of radical polymerization of conventional monomers and surface-active monomers in direct mini-emulsion systems. Besides a short introduction into some kinetic aspects of radical polymerization in direct emulsion, mini-emulsion and micro-emulsion systems, we mainly focus on the particle nucleation mechanisms and the common and different features between the classical emulsion and finer mini-emulsion polymerization systems. The effects of the type and concentration of initiator, emulsifier, coemulsifier (hydrophobe) and monomer are evaluated. The influence of the complex formation, the close-packed structure, etc. within the mini-emulsion droplet surface layer on the colloidal stability, the nature of the surface film, and the radical entry process are summarized and discussed. These results show that the nature of the coemulsifier (hydrophobe), the weight ratio of emulsifier to coemulsifier, the mechanisms of sonification, the stability of monomer droplets, and the presence or absence of free micelles play a decisive role in the polymerization process.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 169.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 219.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Guo JS, Sudol ED, Vanderhoff JW, El-Aasser MS (1992) J Polym Sci Polym Chem Ed 30:691

    Article  CAS  Google Scholar 

  2. Ostwald W (1901) Phys Chem 37:385

    Google Scholar 

  3. Kabalnov AS, Shchukin ED (1992) Adv Colloid Interface Sci 38:69

    Article  CAS  Google Scholar 

  4. Vollmer J, Vollmer D, Strey R (1997) J Chem Phys 107:3627

    Article  CAS  Google Scholar 

  5. Puig JE, Perez-Luna VH, Perez-Gonzalez M, Macias ER, Rodrigueez BE, Kaler EW, (1993) Colloid Polymer Sci 271:114

    Article  CAS  Google Scholar 

  6. Lezer NJ, Terrisse I, Bruneau F, Tokgoz S, Ferriera L, Seiller D, Grossiord JL (1997) J Control Release 45:1

    Article  Google Scholar 

  7. Tadros ThF (1984) in Structure/Performance Relationships in Surfactants, Rosen MJ (ed), ACS Symp Ser, No. 253, American Chemical Society, Washington, D.C., p. 154

    Google Scholar 

  8. Durbin DP, El-Aasser MS, Sudol ED, Vanderhoff JW (1979) J Appl Polym Sci 24:703

    Article  CAS  Google Scholar 

  9. Chamberlain BJ, Napper DH, Gilbert RG (1982) J Chem Soc Faraday Trans 178:591

    Google Scholar 

  10. Barnette DT, Schork FJ (1987) Chem Eng Prog 83:625

    Google Scholar 

  11. Mouron D, Reimers JL, Schork FJ (1996) J Polym Sci Polym Chem Ed 34:1073

    Article  Google Scholar 

  12. Wang S, Poehlein GW, Schork FJ (1997) J Polym Sci Polym Chem Ed 35:595

    Article  CAS  Google Scholar 

  13. Chern CS, Chen TJ (1997) Colloid Polym Sci 275:546; ibid 275:1067

    Article  CAS  Google Scholar 

  14. Chern CS, Chen TJ (1998) Colloids Surfaces A 138:65

    Article  CAS  Google Scholar 

  15. Chern CS, Liou YC, Chen TJ (1998) Macromol Chem Phys 199:1315

    Article  CAS  Google Scholar 

  16. Chern CS, Liou YC (1998) Macromol Chem Phys 199:2051

    Article  CAS  Google Scholar 

  17. Chern CS, Liou YC (1999) Polymer 40:3763

    Article  CAS  Google Scholar 

  18. Reimers JL, Skelland AHP, Schork FJ (1995) Polym React Eng 3:235

    CAS  Google Scholar 

  19. Reimers JL, Schork FJ (1996) J Appl Polym Sci 59:1833; ibid 60:251

    Article  CAS  Google Scholar 

  20. Alduncin JA, Forcada J, Asua JM (1994) Macromolecules 27:2256

    Article  CAS  Google Scholar 

  21. Alduncin JA, Asua JM (1994) Polymer 35:3758

    Article  CAS  Google Scholar 

  22. Reimers JL, Schork FJ (1997) Ind Eng Chem Res 36:1085

    Article  CAS  Google Scholar 

  23. Chern CS, Chen TJ, Liou YC (1998) Polymer 39:3767

    Article  CAS  Google Scholar 

  24. Gardon JL (1968) J Polym Sci Part A-1 6:623; ibid 6:643

    Article  CAS  Google Scholar 

  25. Harkins WD (1947) J Am Chem Soc 69:1428

    Article  CAS  Google Scholar 

  26. Smith WV, Ewart RH (1948) J Am Chem Soc 70:3695

    Article  CAS  Google Scholar 

  27. Smith WV, Ewart RH (1948) J Chem Phys 16:529

    Article  Google Scholar 

  28. B. Jacobi (1952) Angew Chem 64:539

    Article  Google Scholar 

  29. Priest WJ (1952) J Phys Chem 56:1077

    Article  CAS  Google Scholar 

  30. Fitch RM, Tsai CH (1970) J Polym Sci Polym Lett Ed 8:703

    CAS  Google Scholar 

  31. Fitch RM, Tsai CH (1980) in: Fitch RM (ed), Polymer Colloids, Plenum, New York, p. 73

    Google Scholar 

  32. Hansen FK, Ugelstad J (1982) in: Piirma I (ed), Emulsion Polymerization, Academic Press, New York, p. 51

    Google Scholar 

  33. Billmayer FW (1991) Textbook of Polymer Science, 2nd ed Wiley, New York

    Google Scholar 

  34. Morgan JD, Kaler EW (1998) Macromolecules 31:3197

    Article  CAS  Google Scholar 

  35. Gilbert RG (1995) Emulsion Polymerization. A Mechanistic Approach, Academic Press: London

    Google Scholar 

  36. Barton J, Capek I (1994) Radical Polymerization in Disperse Systems, E. Horwood, Chichester and Veda, Bratislava

    Google Scholar 

  37. Delgado J, El-Aasser MS Silebi CA, Vanderhoff J.W (1990) J Polym Sci Part A Polym Chem 28:777

    Article  CAS  Google Scholar 

  38. Capek I, Barton J (1985) Makromol Chem 186:1297

    Article  CAS  Google Scholar 

  39. Chang HC, Lin YY, Chern CS, Lin SY (1998) Langmuir 14:6632

    Article  CAS  Google Scholar 

  40. Deryagnin BV, Lansau LD (1941) Acta Physicochim USSR 14:633

    Google Scholar 

  41. Verwey EJW, Overbeek JThG (1943) Theory of the Stability of Lyophobic Colloids, New York, Elsevier

    Google Scholar 

  42. Sato T, Ruch R (1980) Stabilization of Colloidal Dispersions by Polymer Adsorption, New York, Marcel Dekker

    Google Scholar 

  43. Napper DH (1983) Polymeric Stabilization of Colloidal Dispersions. London, Academic Press

    Google Scholar 

  44. Jansson L (1983) Master Thesis, Georgia Institute of Technology, Atlanta

    Google Scholar 

  45. Grimm WL, Min TI, El-Aasser MS, Vanderhoff JW (1983) J Colloid Interface Sci 94:531

    Article  CAS  Google Scholar 

  46. El-Aasser MS, Misra SC, Vanderhoff JW, Manson JA (1977) J Coatings Tech 49:71

    CAS  Google Scholar 

  47. El-Aasser MS, Poehlein GW, Vanderhoff JW, (1977) Coatings and Plastics Preprints 37:2

    Google Scholar 

  48. Morton MJ (1954) J Colloid Interface Sci 9:300

    CAS  Google Scholar 

  49. Ugelstad J, Berge A, Ellingsen T, Schmid R, Nilsen TN, Mork PC, Stenstad P, Hornes E, Olsvik O (1992) Prog Polym Sci 17:87

    Article  CAS  Google Scholar 

  50. Lifshitz IM, Slesov VV (1961) J Phys Chem Solids 19:35

    Article  Google Scholar 

  51. Wagner C (1961) Ber Bunsenges Phys Chem 65:581

    CAS  Google Scholar 

  52. Kabalnov AS, Makarov KN, Pertzov AV, Shchukin ED (1989) J Colloid Interface Sci 138:98

    Article  Google Scholar 

  53. Ugelstad J, Mork PC, Hansen FK, Kaggerud KH, Ellingsen T (1981) Pure and Appl Chem 53:323

    Article  CAS  Google Scholar 

  54. Saethre B (1994) Mechanism and Kinetics in Minisuspension Polymerization of Vinyl Chloride, PhD. Dissertation, NTH, Prondheim

    Google Scholar 

  55. Lack CD, El-Aasser MS, Vanderhoff JW, Fowker FM (1985) Macro-and Microemulsions, Theory and Applications, Shah DO (ed), ACS Symp Ser No. 272, American Chemical Society, Washington, DC

    Google Scholar 

  56. Choi YT, El-Aasser MS, Sudol ED, Vanderhoff JW (1985) J Polym Sci Polym Chem Ed 23:2973

    Article  CAS  Google Scholar 

  57. Ugelstad J, El-Aasser M, Vanderhoff JW (1973) J Polym Sci Polym Lett Ed 11:503

    Article  CAS  Google Scholar 

  58. El-Aasser MS, Lack CD, Vanderhoff JW, Fowkes FW (1988) Colloids Surfaces 29:103

    Article  CAS  Google Scholar 

  59. Tang PL, Sudol ED, Silabi CA, El-Aasser MS (1991) J Appl Polym Sci 43:1059

    Article  CAS  Google Scholar 

  60. Higuchi WI, Misra J (1962) J Pharm Sci 51:459

    Article  CAS  Google Scholar 

  61. El-Aasser MS, Lack CD, Choi YT, Min TI, Vanderhoff JW, Fowkes FM, (1984) Colloids Surfaces 12:79

    Article  CAS  Google Scholar 

  62. Pithayanukul P, Pipel N (1982) J Colloid Interface Sci 89:494

    Article  CAS  Google Scholar 

  63. Fowkes FM (1963) J Phys Chem 67:1982

    Article  CAS  Google Scholar 

  64. Choi YT (1986) Formation and Stabilization of Miniemulsions and Latexes, Ph.D. Dissertation, Lehigh University, Bethlehem

    Google Scholar 

  65. MacRitchie F (1967) Nature (London) 170:1159

    Article  Google Scholar 

  66. Vold RD, Mittal KL (1972) J Colloid Interface Sci 38:451

    Article  CAS  Google Scholar 

  67. Lack CD, El-Aasser MS, Silebi CA, Vanderhoff JW, Fowkes FM (1987) Langmuir 3:1155

    Article  CAS  Google Scholar 

  68. Goetz RJ, El-Aasser MS (1990) Langmuir 6:132

    Article  CAS  Google Scholar 

  69. Goetz RJ, Khan A, El-Aasser MS (1990) J Colloid Interface Sci 137:795

    Article  Google Scholar 

  70. Azad ARM, Ugelstad J, Fitch RM, Hansen FK (1976) Emulsion Polymerization, Piirma I, Gardon J (eds), ACS Symp Ser No. 24, American Chemical Society, Washington DC, p. l

    Google Scholar 

  71. Zhou JS, Kamioner M, Dupeyrat M (1987) Microemulsion Systems, Rosano I, Henri (eds), Marcel Dekker, p. 335

    Google Scholar 

  72. Delgado J (1986) Miniemulsion Copolymerization of Vinyl Acetate and n-Butyl Acrylate, Ph.D. Dissertation, Lehigh University, Bethlehem

    Google Scholar 

  73. Delgado J, El-Aasser MS, Vanderhoff JW (1980) J Polym Sci Polym Chem 24:861

    Article  Google Scholar 

  74. Rodripuez VS (1988), Interparticle Monomer Transport in Miniemulsion Copolymerization, Ph.D. Dissertation, Lehigh University, Bethlehem

    Google Scholar 

  75. Elsynski HA (1987) Batch and Semicontinuous Copolymerization of Vinyl Acetate and Methyl Acry]ate, M.S. Research Report, Lehigh University, Bethlehem

    Google Scholar 

  76. Miller CM, Sudol ED, Silebi CA, El-Aasser MS (1995) Macromolecules 28:2754

    Article  CAS  Google Scholar 

  77. Ugelstad J (1980) Adv Colloid Interface Sci 13:101

    Article  CAS  Google Scholar 

  78. Vijayendran BR (1979) J Appl Polym Sci 23:733

    Article  CAS  Google Scholar 

  79. Wang S, Shork FJ (1994) J Appl Polym Sci 54:2164

    Google Scholar 

  80. Wang S, Schork FJ, Poehlein GW, Gooch JW (1996) J Appl Polym Sci 60:2069

    Article  CAS  Google Scholar 

  81. Blythe PJ, Klein A, Sudol ED, El-Aasser MS (1999) Macromolecules 32:6952

    Article  CAS  Google Scholar 

  82. Miller CM, Blythe PJ, Sudol ED, Silebi CA, El-Aasser MS (1994) J Polym Sci Part A Polym Chem 32:2365

    Article  CAS  Google Scholar 

  83. Pelssers EGM, Cohen Stuart MA, Fleer GJ (1990) J Chem Soc Faraday Trans 86:1355

    Article  CAS  Google Scholar 

  84. De Witt JA, van de Ven TGM (1992) Adv Colloid Interface Sci 42:41

    Article  Google Scholar 

  85. Chern CS, Liou YC, Tsai WY (1996) J Macromol Sci Pure Appl Chem A33:1063

    CAS  Google Scholar 

  86. Capek I (1989) Makromol Chem 190:789

    Article  CAS  Google Scholar 

  87. Capek I, Barton J (1985) Makromol Chem 186:1297

    Article  CAS  Google Scholar 

  88. Capek I, Potisk P (1992) Polymer J 24:1037

    Google Scholar 

  89. Matsumoto A, Kodama K, Aota H, Capek I (1999) Eur Polymer J 35:1509

    Article  CAS  Google Scholar 

  90. Miller CM, Sudol ED, Silebi CA, El-Aasser MS (1995) J Polym Sci Part A Polym Chem Ed 33:1391

    Article  CAS  Google Scholar 

  91. Napper DH, Gilbert RG (1987) Makromol Chem Macromol Symp 10/11:503

    Google Scholar 

  92. Blythe PJ, Morrison BR, Mathauer KA, Sudol ED, El-Aasser MS (1999) Macromolecules 32:6944

    Article  CAS  Google Scholar 

  93. Miller CM, Sudol ED, Silebi CA, El-Aasser MS (1995) Macromolecules 28:2765

    Article  CAS  Google Scholar 

  94. Person LT, Louis PEJ, Gilbert RG, Napper DH (1991) J Polym Sci Polym Chem Ed 29:515

    Article  Google Scholar 

  95. Russell G, Napper DH, Gilbert RG (1988) Macromolecules 21:2141

    Article  CAS  Google Scholar 

  96. Ito K (1973) J Polym Sci Polym Chem Ed 13:401

    Article  Google Scholar 

  97. Capek I, Riza M, Akashi M (1992) Polym J 24:959

    Article  CAS  Google Scholar 

  98. Delgado J, El-Aasser MS, Silebi CA, Vanderhoff JW, Guillot J (1988) J Polym Sci Polym Phys Ed 26:1495

    Article  CAS  Google Scholar 

  99. Delgado J, El-Aasser MS, Silebi CA, Vanderhoff JW (1989) J Polym Sci Polym Chem Ed 27:193

    Article  CAS  Google Scholar 

  100. Nomura M, Harada M, Eguchi W, Nagata S (1976) in: Emulsion Polymerization, Piirma I, Gardon JL (eds), ACS Symp Seri, No. 24, American Chemical Society, Washington DC, p. 102

    Google Scholar 

  101. Friis N, Nyhagen L, (1973) J Appl Polym Sci 17:2311

    Article  CAS  Google Scholar 

  102. Landfester K, Bechthold N, Tiarks F, Antonietti M (1999) Macromolecules 32:2679

    Article  CAS  Google Scholar 

  103. Landfester K, Bechthold N, Forster S, Antonietti M (1999) Macromol Rapid Commun 20:81

    Article  CAS  Google Scholar 

  104. Edelhauser H, Braitenbach JW (1959) J Polym Sci 35:423

    Article  CAS  Google Scholar 

  105. Wang CC, Yu NS, Chen CY, Kuo JF (1996) Polymer 37:2509

    Article  CAS  Google Scholar 

  106. Ugelstad J, Mork PC, Kaggerud KH, Ellingsen T, Berge A (1980) Adv Colloids Interface Sci 13:101

    Article  CAS  Google Scholar 

  107. Shah DO (1971) J Colloid Interface Sci 37:744

    Article  CAS  Google Scholar 

  108. Fontenot K, Schork FJ (1993) J Appl Polym Sci 49:633

    Article  CAS  Google Scholar 

  109. Miller CM, Sudol ED, Silebi CA, El-Aasser MS (1995) Macromolecules 28:2772

    Article  CAS  Google Scholar 

  110. Wu SQ, Schork FJ, Gooch JW (1999) J Polym Sci Polym Chem 37:4159

    Article  CAS  Google Scholar 

  111. Reimers J, Schork FJ (1996) Polym React Eng 4:135

    CAS  Google Scholar 

  112. Capek I, Barton J, Tuan LQ, Svoboda V, Novotny V (1987) Makromol Chem 188:1723

    Article  CAS  Google Scholar 

  113. Chern CS, Lin SY, Chang SC, Lin JY, Lin YF (1998) Polymer 39:2281

    Article  CAS  Google Scholar 

  114. Chern CS, Lin SY, Chen LJ, Wu SC (1997) Polymer 38:1977

    Article  CAS  Google Scholar 

  115. Chen LJ, Lin SY, Chern CS, Wu SC (1997) Colloids Surfaces A 122:161

    Article  CAS  Google Scholar 

  116. Chern CS, Liou YC (1999) J Polym Sci Part A Polym Chem 37:2537

    Google Scholar 

  117. Capek I (1999) Adv Colloid Interface Sci 80:85

    Article  CAS  Google Scholar 

  118. Matsumoto A, Murakami N, Aota H, Ikeda J, Capek I (1999) Polymer 40:5687

    Article  CAS  Google Scholar 

  119. Matsumoto A, Kodama K, Aota H, Capek I (1999) Eur Polym J 35:1509

    Article  CAS  Google Scholar 

  120. Alducin JA, Forcada J, Barandiaran, Asua J. M (1991) J Polym Sci Polym Chem Ed 29:1265

    Article  Google Scholar 

  121. Capek I (2000) Polym J 32:670

    Article  CAS  Google Scholar 

  122. Capek I (1999) Eur Polym Sci 36:255

    Article  Google Scholar 

  123. Chern CS, Lin SY, Hsu TJ (1999) Polymer J 31:516

    Article  CAS  Google Scholar 

  124. Capek I, Lin SY, Hsu TJ, Chern CS (2000) J Polym Sci Polym Chem Ed, 38:1477

    Article  CAS  Google Scholar 

  125. Capek I, Chudej J (1999) Polym Bul 43:417

    Article  CAS  Google Scholar 

  126. Chudej J, Capek I (2000) Polymer, in press

    Google Scholar 

  127. Garti N, Aserin A (1996) Adv Colloid Interface Sci 65:37

    Article  CAS  Google Scholar 

  128. Coen E, Lyons RA, Gilbert RG (1996) Macromolecules 29:5128

    Article  CAS  Google Scholar 

  129. Kusters JMH, Napper DH, Gilbert RG, German AL (1992) Macromolecules 25:7043

    Article  CAS  Google Scholar 

  130. Harada M, Nomura M, Eguchi W, Nagata S (1991) J Chem Eng Jpn 4:54

    Article  Google Scholar 

  131. Lansalot M, Farcet C, Charleux B, Vairon JP, Pirri R (1999) Macromolecules 32:7354

    Article  CAS  Google Scholar 

  132. Landfester K, Willert M, Antonietti M (1999) Macromolecules 33:2370

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 842 36, Bratislava, Slovak Republic

    Ignác Capek

  2. Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, 106, Taiwan

    Chorng-Shyan Chern

Authors
  1. Ignác Capek
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chorng-Shyan Chern
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

Copyright information

© 2001 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Capek, I., Chern, CS. (2001). Radical Polymerization in Direct Mini-Emulsion Systems. In: New Polymerization Techniques and Synthetic Methodologies. Advances in Polymer Science, vol 155. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-44473-4_2

Download citation

  • DOI: https://doi.org/10.1007/3-540-44473-4_2

  • Received:

  • Published:

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-41435-3

  • Online ISBN: 978-3-540-44473-2

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation