Effect of Monomers in Vinyl Urethane Macromonomers on Dispersion Polymerization of Polystyrene

  • Received : 2016.06.03
  • Accepted : 2016.06.08
  • Published : 2016.06.30


The four different vinyl monomers in the reaction of isocyanate-terminated polyurethane prepolymer were used for the preparation of macromonomers and successfully employed in the dispersion polymerization of styrene. The chemical structures of vinyl monomer in macromonomers influenced on the polystyrene particle characteristics, such as the conversion, weight average molecular weights ($M_w$), polydispersity index (PDI), weight average diameter ($D_w$), and uniformity. The conversion of polystyrene increased with amounts of methyl group in vinyl monomer. Also the uniformity of polystyrene particles increased with amounts of methyl group in vinyl monomer.


vinyl monomer;urethane macromonomer;dispersion polymerization;polystyrene


  1. S. Lam, A. C. Hellgren, M. Sjoberg, K. Holmberg, H. A. S. Schoonbrood, M. J. Unzue, J. M. Asua, K. Tauer, and D. C. Sherrington, "Surfactants in heterophase polymerization: A study of film formation using force microscopy", J. Appl. Polym. Sci., 66, 187 (1997).<187::AID-APP22>3.0.CO;2-Y
  2. A. D. Chesne, B. Gerharz, and G. Liester, "The Segregation of Surfactant upon Film Formation of Latex Dispersions: an Investigation by Energy Filtering Transmission Electron Microscopy", Polym. Int., 43, 187 (1997).<187::AID-PI752>3.0.CO;2-H
  3. J. L. Cawse, "Dispersion Polymerization in Organic Media", Wiley, New York (1975).
  4. R. B. Greenwald, "PEG drugs: an overview", J. Controlled Release, 74, 159 (2001).
  5. D. Bhadra, S. Bhadra, P. Jain, and N. K. Jain, "Pegnology: a review of PEG-ylated systems", Pharmazie, 57, 5 (2002).
  6. H. Shinoda, P. J. Miller, and K. Matyjaszewski, "Improving the Structural Control of Graft Copolymers by Combining ATRP with the Macromonomer Method", Macromolecules, 34, 3186 (2001).
  7. C. Batis, G. Karanikolopoulos, M. Pitsikalis, and N. Hadjichristidis, "Metallocene-Catalyzed Copolymerization of MMA with Anionically Synthesized Methacryloyl Macromonomers", Macromolecules, 33, 8925 (2000).
  8. V. C. Gibson and T. Okada, "Synthesis of End-Functionalized Polynorbornenes and Polynorbornanes via Metathesis: Novel Macromonomers for Polycondensation Reactions", Macromolecules, 33, 655 (2000).
  9. M. Iijima, Y. Nagasaki, T. Okada, M. Kato, and K. Kataoka, "Core-Polymerized Reactive Micelles from Heterotelechelic Amphiphilic Block Copolymers", Macromolecules, 32, 1140 (1999).
  10. R. Milkovich and Y. T. Chiang, "Acrylate and Methacrylate Terminated Polystyrene Macromolecular Monomers Having a Substantially Uniform Molecular weight Distribution", U.S. Patents 3,842,059 (1974).
  11. O. Henschke, A. Neubauer, and M. Arnold, "Metallocene-Catalyzed Copolymerization of Propene with Polystyrene Macromonomers" Macromolecules, 30, 8097 (1997).
  12. G. Odian, "Principles of Polymerization", Wiley, New York (1991).
  13. M. Trollsas and J. L. Hedrick, "Hyperbranched Poly(${\varepsilon}$-caprolactone) Derived from Intrinsically Branched $AB_2$ Macromonomers", Macromolecules, 31, 4390 (1998).
  14. P. Lacroix-Desmazes and A. Guyot, "Reactive Surfactants in Heterophase Polymerization. 2. Maleate Based Poly(ethylene oxide) Macromonomers as Steric Stabilizer Precursors in the Dispersion Polymerization of Styrene in Ethanol-Water Media", Macromolecules, 29, 4508 (1996).
  15. A. Deffieux and M. Schappacher, "Synthesis and Characterization of Star and Comb Polystyrenes Using Isometric Poly(chloroethyl vinyl ether) Oligomers as Reactive Backbone", Macromolecules, 32, 1797 (1999).
  16. S. Gibanel, V. Heroguez, and J. Forcada, "Surfactant characteristics of polystyrene/poly(ethylene oxide) macromonomers in aqueous solution and on polystyrene latex particles: Twostep emulsion polymerizations", J. Polym. Sci. Part A: Polym. Chem., 39, 2767 (2001).
  17. A. D. Chesne, B. Gerharz, and G. Lieser, "The Segregation of Surfactant upon Film Formation of Latex Dispersions: an Investigation by Energy Filtering Transmission Electron Microscopy", Polym. Int., 43, 187 (1997).<187::AID-PI752>3.0.CO;2-H
  18. K. Li and H. D. Stover Harald, "Highly crosslinked micronrange polymer microspheres by dispersion polymerization of divinylbenzene", J. Polym. Sci. Part A: Polym. Chem., 31, 2473 (1993).
  19. M. Hattory, E. D. Sudol, and M. S. El-Aasser, "Highly cross-linked polymer particles by dispersion polymerization", J. Polym. Sci. Part A: Polym. Chem., 50, 2027 (1993).
  20. K. E. J. Barrette, "Dispersion polymerization in organic media", Wiley, New York (1975).
  21. K. Ito, "Polymeric design by macromonomer technique Review", Prog. Polym. Sci., 23, 581 (1998).
  22. I. Capek, M. Riza, and M. Akashi, "Dispersion copolymerization of poly(oxyethylene) macromonomers and styrene", J. Polym. Sci. Part A: Polym. Chem., 35, 3131 (1997).<3131::AID-POLA6>3.0.CO;2-Z
  23. I. Capek, S. H. Nguyen, and D. Berek, "Polystyrene-graftpoly(ethylene oxide) copolymers prepared by macromonomer technique in dispersion. 2. Mechanism of dispersion copolymerization", Polymer, 41, 7011 (2000).
  24. E. Bourgeat-Lami and A. Guyot, "Thiol-ended polyethylene oxide as reactive stabilizer for dispersion polymerization of styrene", Colloid Polym. Sci., 275, 716 (1997).
  25. R. Shen, C. Akiyama, T. Senyo, and K. Ito, "Emulsion and dispersion polymerization of styrene in the presence of PEO macromonomers with p-vinylphenylalkyl end groups", C. R. Chimie., 6, 1329 (2003).
  26. H. M. Ghazaly, E. S. Daniels, V. L. Dimonie, M. S. El-Aasser, and A. Klein, "Miniemulsion copolymerization of n-butyl methacrylate with crosslinking monomers", J. Appl. Polym. Sci., 81, 1721 (2001).
  27. S. M. Klein, V. N. Manoharan, D. J. Pine, and F. F. Lange, "Preparation of monodisperse PMMA microspheres in nonpolar solvents by dispersion polymerization with a macromonomeric stabilizer", Colloid Polym. Sci., 282, 7 (2003).
  28. Q. Dai, D. Wu, Z. Zhang, and Q. Ye, "Preparation of monodisperse poly(methyl methacrylate) particles by radiation-induced dispersion polymerization using vinyl terminus polysiloxane macromonomer as a polymerizable stabilizer", Polymer, 44, 73 (2003).
  29. H. Jung, K. Lee, S. E. Shim, S. Yang, J. M. Lee, H. Lee, and S. Choe, "Novel macromonomer as a reactive stabilizer in the dispersion polymerization of methylmethacrylate", Macromol. Res., 12, 512 (2004).
  30. S. E. Shim, H. Jung, K. Lee, J. M. Lee, and S. Choe, "Dispersion polymerization of methyl methacrylate with a novel bifunctional polyurethane macromonomer as a reactive stabilizer", J. Colloid Interf. Sci., 279, 464 (2004).
  31. K. Lee, S. E. Shim, H. Jung, S. Y. Kim, and S. Choe, "Synthesis and Characterization of Polyurethane-Derived Telechelic Macromonomer Cross-Linkable Stabilizer (TMCS)", Macromolecules, 38, 2686 (2005).
  32. S. Y. Kim, K. Lee, H. Jung, S. Shim, B. H. Lee, and S. Choe, "Macromonomers having different molecular weights of polyethylene glycol and end group functionalities in dispersion polymerization of styrene", Polymer, 46, 7974 (2005).


Grant : BK21플러스

Supported by : 인하대학교