Skip to main content
Log in

Kinetic study of styrene and methyl methacrylate emulsion polymerization induced by cumene hydroperoxide/tetraethylenepentamine

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

The redox initiator, cumene hydroperoxide/tetraethylenepentamine (CHPO/TEPA), was used to initiate the emulsion polymerizations of styrene and methyl methacrylate (MMA). The hydrophobic CHPO acting as oxidizer would interact with the hydrophilic TEPA employed as the reducer at the particle-water interface where the vinyl monomer is present. The kinetics of the styrene and MMA polymerizations were studied under a temperature range of 30–70 °C. The polymerization rate, the concentration of monomer in the particles, the average number of latex particles and the number of radicals per particle were investigated to evaluate the propagation rate constant during interval II of the polymerization. With increasing temperature, the number of latex particles increases while the monomer concentration in the particles slightly decreases. The observed number of radicals per particle, calculated from the number average volume of the particles and the relation between the entry rate coefficients of free radicals into the particles and the exit rate coefficients of free radicals from the particle, was found to be approximately 0.47 and 0.5 in case of styrene and MMA polymerization, respectively. The calculation shows that the propagation rate constant, k p = 6.84 × 107e−37.65/RT and k p = 3.4 × 107e−31.05/RT L/mol∙s for styrene and MMA polymerizations over the temperature range studied, respectively.

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

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Farías-Cepeda L, Herrera-Ordonez J, Saldívar-Guerra E (2010) On the kinetics and particle size polydispersity of the styrene emulsion polymerization using aerosol MA80 and sodium dodecyl sulfate as surfactants. Colloid Polym Sci 288:1401–1409

    Article  Google Scholar 

  2. Wang X, Huang L (2010) Kinetics and latex particles analysis on styrene emulsion polymerization induced by 60Co γ rays in presence of anionic polymerizable emulsifier. J Polym Res 17:241–246

    Article  CAS  Google Scholar 

  3. Palma MSA (2007) Effect of monomer feed rate on the properties of copolymer butyl acrylate/vinyl acetate in semi-batch emulsion polymerization. Indian J Chem Technol 14:515–522

    CAS  Google Scholar 

  4. Chu HH, Yeo YS, Chuang KS (2007) Entry in emulsion polymerization using a mixture of sodium polystyrene sulfonate and sodium dodecyl sulfate as the surfactant. Polymer 48:2298–2305

    Article  CAS  Google Scholar 

  5. Matsusaka N, Suzuki T, Okubo M (2012) Effects of stirring prior to starting emulsion polymerization of styrene with nonionic emulsifier on particle formation and its incorporation. Colloid Polym Sci 290:561–567

    Article  CAS  Google Scholar 

  6. Yamamoto T (2013) Synthesis of nearly micron-sized particles by soap-free emulsion polymerization of methacrylic monomer using an oil-soluble initiator. Colloid Polym Sci 291:2741–2744

    Article  CAS  Google Scholar 

  7. Grishin DF, Lazarev MA, Semenycheva LL, Nikolaev EY (2005) Emulsion polymerization of styrene in the presence of C-phenyl-N-tert-butylnitrone. Russ J Appl Chem 78:815–819

  8. Chu HH, Lin CS (2003) The effect of initiators on the emulsion polymerization of 2-hydroxyethyl methacrylate. J Polym Res 10:283–287

    Article  CAS  Google Scholar 

  9. Chen CW, Chen CY, Lin CL (2011) Preparation of monodisperse poly(methyl methacrylate) microspheres: effect of reaction parameters on particle formation, and optical performances of its diffusive agent application. J Polym Res 18:587–594

    Article  CAS  Google Scholar 

  10. Hutchison RA, Aronson MT, Richards JR (1993) Analysis of pulsed-laser-generated molecular weight distributions for the determination of propagation rate coefficients. Macromolecules 26:6410–6415

    Article  Google Scholar 

  11. Chu HH, Wu JD (2007) Free-radical propagation rate coefficients for hydroxyalkyl methacrylates and cyclohexyl methacrylate. J Polym Res 14:201–206

    Article  CAS  Google Scholar 

  12. Ballard MJ, Gilbert RG, Napper DH, Pomery PJ, O’Donnell JH (1984) Application of electron spin resonance spectroscopy to emulsion polymerization. Macromolecules 17:504–506

    Article  CAS  Google Scholar 

  13. Burnett GM, Lehrle RS (1959) Emulsion polymerization of styrene. Proc R Soc Lond A 253:331–348

    Article  CAS  Google Scholar 

  14. Morton M, Salatiello PP, Landfield H (1952) Absolute propagation rates in emulsion polymerization. III. styrene and isoprene. J Polym Sci 8:279–287

    Article  CAS  Google Scholar 

  15. Soh SK (1980) Measurements of propagation rate constant from emulsion polymerization. J Appl Polym Sci 25:2993–2998

    Article  CAS  Google Scholar 

  16. Harkins WD (1947) A general theory of the mechanism of emulsion polymerization. J Am Chem Soc 69:1428–1444

    Article  CAS  Google Scholar 

  17. Dan A, Chakraborty I, Ghosh S, Moulik SP (2007) Interfacial and bulk behavior of sodium dodecyl sulfate in isopropanol-water and in isopropanol-poly(vinylpyrrolidone)-water media. Langmuir 23:7531–7538

  18. Ramirez JC, Herrera-Ordonez J, Maldonado-Textle H (2005) Kinetics of the styrene emulsion polymerization above cmc. II. agitation effect on molecular weight. Polym Bull 53:333–337

    Article  CAS  Google Scholar 

  19. Kao CI, Gundlach DP, Nelsen RT (1984) Kinetics of emulsion polymerization of styrene simulation model with varying free radical capture efficiency. J Polym Sci 22:3499–3519

    CAS  Google Scholar 

  20. Herzfeld SH, Roginsky A, Corrin ML, Harkins WD (1949) Monomer-polymer ratio in emulsion polymerization of styrene. J Polym Sci 5:207–215

  21. Góral M, Shaw DG (2010) IUPAC-NIST solubility data series. 88. Esters with water—revised and updated. Part 2. C5 and C6 esters. J Phys Chem Ref Data 39:1–58

    Google Scholar 

  22. Shaw DG, Maczynski A (2005) IUPAC-NIST solubility data series. 81. Hydrocarbons with water and seawater—revised and updated. Part 6. C8H8–C8H10 hydrocarbons with water. J Phys Chem Ref Data 34:1489–1553

    Article  CAS  Google Scholar 

  23. Ugelstad J, Hansen FK (1976) Kinetics and mechanism of emulsion polymerization. Rubber Chem Technol 49:536–609

    Article  CAS  Google Scholar 

  24. Imoto M, Otsu T, Ota T (1955) Kinetics of the polymerization of styrene catalyzed by benzoyl peroxide and dimethylaniline. VIII. On vinyl polymerization. Die Makromol Chem 16:10–20

    Article  CAS  Google Scholar 

  25. Morton M, Salatiello PP, Landfield H (1952) Absolute propagation rates in emulsion polymerization. II. Butadiene in hydroperoxide-polyamine systems. J Polym Sci 8:215–224

    Article  CAS  Google Scholar 

  26. Morton M, Kaizerman S, Altier MW (1954) Swelling of latex particles. J Colloid Sci 9:300–312

    Article  CAS  Google Scholar 

  27. Van der Hoff BME (1960) On the mechanism of emulsion polymerization of styrene. II. polymerizations in soap solutions below and above the critical micelle concentration and some remarks on the kinetics of emulsion polymerization. J Polym Sci 44:241–259

    Article  Google Scholar 

  28. Harada M, Nomura M, Kojima H, Eguchi W, Nagata S (1972) Rate of emulsion polymerization of styrene. J Appl Polym Sci 16:811–833

    Article  CAS  Google Scholar 

  29. Ballard MJ, Napper DH, Robert G (1984) Kinetics of emulsion polymerization of methyl methacrylate. J Polym Sci Polym Chem Ed 22:3225–3253

    Article  CAS  Google Scholar 

  30. Gardon JL (1968) Emulsion polymerization. VI. concentration of monomers in latex particles. J Polym Sci Part A-1 Polym Chem 6:2859–2879

    Article  CAS  Google Scholar 

  31. Smith WV (1948) The kinetics of styrene emulsion polymerization. J Am Chem Soc 70(11):3695–3702

    Article  CAS  Google Scholar 

  32. Banerjee M, Konar RS (1986) Mechanism of the emulsion polymerization of methyl acrylate: 2. Kinetics and growth of the polymers. Polymer 27:147–157

    Article  CAS  Google Scholar 

  33. Zimmt WS (1959) The emulsion polymerization of methyl methacrylate. J Appl Polym Sci 1(3):323–328

    Article  CAS  Google Scholar 

  34. Yildiz U, Capek I (2003) Microemulsion polymerization of styrene in the presence of macroinimer. Polymer 44:2193–2200

    Article  CAS  Google Scholar 

  35. Chen SA, Wu KW (1990) Emulsion polymerization: determination of the average number of free radicals per particle by use of the number average volume of the particles. J Polym Sci Part A Polym Chem 28:2857–2866

    Article  CAS  Google Scholar 

  36. Lichti G, Gilbert RG, Napper DH (1977) The growth of polymer colloids. J Polym Sci Polym Chem Ed 15:1957–1971

    Article  CAS  Google Scholar 

  37. Lichti G, Hawkett BS, Gilbert RG, Napper DH (1981) Styrene emulsion polymerization: particle-size distributions. J Polym Sci Polym Chem Ed 19:925–938

    Article  CAS  Google Scholar 

  38. Lichti G, Gilbert RG, Napper DH (1983) The Mechanisms of latex particle formation and growth in the emulsion polymerization of styrene using the surfactant sodium dodecyl sulfate. J Polym Sci Polym Chem Ed 21:269–291

    Article  CAS  Google Scholar 

  39. Hawkett BS, Napper DH, Gilbert RG (1980) Seeded emulsion polymerization of styrene. JCS Faraday I 76:1323–1343

    Article  CAS  Google Scholar 

  40. Smith WV, Ewart RH (1948) Kinetics of emulsion polymerization. J Chem Phys 16(6):592–599

    Article  CAS  Google Scholar 

  41. Davis TP, O’Driscoll KF (1990) Copolymerization propagation kinetics of styrene with alkyl methacrylates. Macromolecules 23:2113–2119

    Article  CAS  Google Scholar 

  42. Gilbert RG (1996) Critically-evaluated propagation rate coefficients in free radical polymerizations I. Styrene and methyl methacryzlate. Pure Appl Chem 68:1491–1494

    Article  CAS  Google Scholar 

  43. Zou W, Han R, Chen Z, Jinghua Z, Shi J (2006) Kinetic study of adsorption of Cu (II) and Pb (II) from aqueous solutions using manganese oxide coated zeolite in batch mode. Colloids Surface A 279:238–246

    Article  CAS  Google Scholar 

  44. Anirudhan TS, Rijith S, Bringle CD (2010) Iron (III) complex of an amino-functionalized poly(acrylamide)-grafted lignocellulosic residue as a potential adsorbent for the removal of chromium (VI) from water and industry effluents. J Polym Res 17:289–299

Download references

Acknowledgments

We gratefully acknowledge the financial support of Thailand Research fund through the Royal Golden Jubilee Ph.D. Program grant # PHD/0098/2551, and are thankful for the support of the Natural Sciences and Engineering Research Council of Canada (NSERC) and Chemical Engineering Department, Faculty of Engineering, Kasetsart University and Chemical Engineering Department of the University of Waterloo.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Wanvimon Arayapranee.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sirirat, T., Vatanatham, T., Hansupalak, N. et al. Kinetic study of styrene and methyl methacrylate emulsion polymerization induced by cumene hydroperoxide/tetraethylenepentamine. J Polym Res 22, 16 (2015). https://doi.org/10.1007/s10965-014-0643-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-014-0643-9

Keywords

Navigation