DOI QR코드

DOI QR Code

Study on the Graft Effect in Emulsion Polymerization of Poly(vinyl acetate-co-ethylene) Using Poly(vinyl alcohol) as Emulsifier

Poly(vinyl alcohol)를 이용한 Poly(vinyl acetate-co-ethylene) 에멀젼 중합에서 그라프트 연구

  • Choi, Yong-Hae (Wacker Chemicals Korea Inc. No 419, Gyeonggi R&DB Center)
  • 최용해 ((주)바커 케미칼 코리아 기술연구소)
  • Received : 2010.11.14
  • Accepted : 2010.11.18
  • Published : 2011.03.30

Abstract

An automated reaction calorimeter was used to directly monitor the rate of emulsion polymerization of vinyl acetate using poly(vinyl alcohol) (PVAs) having different degrees of blockiness. By using this technique in conjunction with other off-line measurements of the evolution of particle size distributions, important details of the process were observed. No constant graft rate period was observed for both low and high initial monomer-water ratios. The gel effect was observed for the low monomer-water ratio recipe. The particle size distributions were broad (particle diameter 40~100 nm) and bimodal. Continuous nucleation was observed to be accompanied by 'limited aggregation' and flocculation during the particle growth stages. It was speculated to be due to the occurrence of the extensive 'limited aggregation' and chain transfer to PVA leading to grafting.

자동화된 반응 열량계를 이용하여 중합비율을 관찰하면서 blockiness가 다른 PVOH를 이용하여 VAE 에멀젼을 합성하였다. 입자 분포도를 관찰 결과 단량체와 물과 비율에 따른 일정한 그라프트율은 없었다. 초기 단량체-물의 비율이 낮은 곳에서 겔 효과가 관찰되었다. 또한 입자 분포는 넓고 이중 피크가 관찰되었다. 지속적으로 제한적으로 응징집되면서 입자성장이 이루어지는 것이 관찰되었다. 이것은 제한적인 응집현상과 사슬이 PVOH로 그라프팅되어 발생한 결과로 판단된다.

Keywords

References

  1. D. J. Shaw, Introduction to Colloid and Surface Chemistry, 3rd Ed., Butter-worth, Stoneham, MA (1980).
  2. D. H. Napper, Polymeric Stabilization of Colloidal Dispersions, Academic Press, San Diego (1983)
  3. N. Pramojaney, Ph.D Dissertation, Lehigh University (1982)
  4. C. A. Finch, Polyvinyl Alcohol: Properties and Applications, John Wiley & Sons, New York (1973).
  5. A. S. Dunn, in emulsion Polymerization of Vinyl Acetate, M. S. El-Aasser, and J. W. Vanderhoff, Eds., Applied Science Publishers, New York, p.11 (1981)
  6. F. D. Hartley, J. Polym. Sci., 34, 397 (1959). https://doi.org/10.1002/pol.1959.1203412731
  7. C. M. Gilmore, G. W Poehlein, and F. J. Schork, J. Appl. Polym. Sci., 48, 1449 (1993). https://doi.org/10.1002/app.1993.070480814
  8. A. S. Dunn, The Pecularities of Polyvinyl Alcohol in M.S. El-Aasser, Ed., 11th Annual Short Course Notes: Advances in the emulsion Polymerization and Latex Technology, Vol II, emulsion Polymers Institute, Lehigh University (1980).
  9. J. T. O'Donnell, R. B. Mesobrian, and A. E. Woodward, J. Polym. Sci., 28, 171 (1958). https://doi.org/10.1002/pol.1958.1202811615
  10. E. V. Gulbekian and G. E. J. Reynolds, Polyvinyl Alcohol in emulsion Polymeri-zation, in Finch, C.A., Ed, Polyvinyl Alcohol: Properties and Applications, p. 427, John Wiley & Sons, New York (1973).
  11. W. V. Smith and R. H. Ewart, J. Chem. Phys., 16, 592 (1948). https://doi.org/10.1063/1.1746951
  12. H. De Bruyn, R. G. Gilbert, and M. J. Ballard, Macromolecules, 29, 8666 (1996). https://doi.org/10.1021/ma961303+
  13. V. Stannett, A. Klein, and M. Litt, Br. Polym. J., 7, 139 (1975). https://doi.org/10.1002/pi.4980070303
  14. N. Friis and L. Nyhagen, J. Appl. Polym. Sci., 17, 2311 (1973). https://doi.org/10.1002/app.1973.070170802
  15. N. Friis and A. E. Hamielec, Gel Effect in emulsion Polymerization of Vinyl Monomers; in Piirma, I. and Gardon, J. L., Eds., emulsion Polymerization: ACS Symp. Ser. No. 24, p. 102, ACS, Washington D.C. (1976).
  16. R. L. Zollars, J. Appl. Polym. Sci., 24, 1353 (1979). https://doi.org/10.1002/app.1979.070240519
  17. V. Dimonie, D. Donescu, M. Munteanu, C. Hagiopol, and I. Gavat, Rev. Romaine Chimie, 19:5, 903 (1974).
  18. M. Litt, R. Patsiga, and V. Stannett, J. Polym. Sci., Part A 1, 8, 3607 (1970). https://doi.org/10.1002/pol.1970.150081221
  19. C. S. Chern and G. W. Poehlein, J. Appl. Polym. Sci., 33, 2117 (1987). https://doi.org/10.1002/app.1987.070330623
  20. M. Nomura, M. Harada, W. Eguchi, and S. Nagata, Kinetics and Mechanisms of the emulsion Polymerization of Vinyl Acetate; in Piirma, I. and Gardon, J.L., Eds., emulsion Polymerization: ACS Symp. Ser. No. 24, p. 102, ACS, Washington D.C. (1976).
  21. D. M. French, J. Polym. Sci., 32, 395 (1961).
  22. J. T. O'Donnell, R. B. Mesrobian, and A. E. Woodward, J. Polym. Sci., 28, 171 (1958). https://doi.org/10.1002/pol.1958.1202811615
  23. D. J. Shaw, Introduction to Colloid and Surface Chemistry, 3rded., Butter-worth, Stoneham, N.Y., USA (1980).
  24. C. M. Gilmore, G. W. Poehlein, and F. J. Schork, J. Appl. Polym. Sci., 48, 1449 (1993). https://doi.org/10.1002/app.1993.070480814
  25. A. S. Dunn, The Pecularities of Polyvinyl Alcohol in M.S. El-Aasser, Ed., 11th Annual Short Course Notes : Advances in the emulsion Polymerization and Latex Technology, Vol II, emulsion Polymers Institute, Lehigh University (1980).
  26. J. T. O'Donnell, R. B. Mesobrian, and A. E. Woodward, J. Polym. Sci., 28, 171 (1958). https://doi.org/10.1002/pol.1958.1202811615
  27. E. V. Gulbekian and G. E. Reynolds, Polyvinyl Alcohol in emulsion Polymerization, John Wiley and Sons., N.Y., USA, 427 (1973).