Article
  • Dispersion Copolymerization of Styrene and Acrylonitrile in Alcoholic Media
  • Lee KC
  • 수계 분산중합에 의한 단분산 Poly(styrene-co-acrylonitrile) 미립자 제조
  • 이기창
Abstract
Dispersion copolymerization of styrene-co-acrylonitrile (100/0∼0/100 in wt%) in ethanol medium was carried out at 55℃ in the presence of poly(vinyl pyrrolidone) and AIBN as steric stabilizer and initiator, respectively. The resulting poly(styrene-co-acrylonitrile) latexes, containing 100/0∼50/50 wt% in monomer compositions, were found to be all colloidally stable, smooth on their spherical particle surfaces, and almost the same particle diameter of 1.6∼ 1.7μm. On the other hand, the poly(styrene-co-acrylonitrile) latexes, containing more than 60 wt% of acrylonitrile in monomer compositions, were all colloidally unstable with occurrence of lots of small polyacrylonitrile particles precipitated on the primarily generated large particles, and of which particle diameter decreased with increasing acrylonitrile content in monomer composition. Dispersion polymerization in 3 different alcoholic media was also performed to investigate the effect of monomer concentration, ㏖ecular weight of PVP stabilizer and its concentration, AIBN concentration, and polymerization temperature on particle size and size distribution of the resulting latexes and how to control it. It was found that the average particle diameter is, in general, increased with increasing reaction temperature, and concentration of monomer and initiator, and with decreasing ㏖ecular weight of PVP stabilizer and its concentration, etc. Preferred polymerization conditions for making uniform-size particles of poly(styrene-co-acrylonitrile, 70/30 in wt% ) of 1.8∼3.7 μm range were also found in this study.

Ethanol 분산매하에서 styrene/acrylonitrile (100/0∼0/100 무게비)의 분산공중합을 poly(vinyl pyrrolidone)과 AIBN을 각각 안정제 및 개시제로 하여 55℃에서 행하였다. Styrene/acrylonitrile 단량체 조성이 100/0∼50/50wt% 범위에 걸쳐, 제조한 라텍스는 모두 1.6∼1.7μm의 평균입자경을 갖으며 콜로이드 안정성이 좋고 매끄러운 표면을 갖는 구상미립자가 제조되었다. 반면에, acrylonitrile함량이 60wt% 이상에서는 라텍스의 입자경은 감소하는 경향을 보이며, 입자들의 응집과 더불어 콜로이드 안정성이 불량하고, 일차로 생성한 기존입자에 polyacrylonitrile 극미세미립자가 쌓여있는 형상의 coagulum이 제조되었다. 또한, styrene/acrylonitrile (70/30 무계비)의 분산중합을 행하여 단량체 농도, 안정제의 분자량 및 농도, 개시제 농도, 중합온도, 중합 분산매 등의 중합조건에 따르는 poly(styrene-co-acrylonitrile) (70/30 무게비) 라텍스 입자의 입자경 및 입자경 분포를 조사하였다. 단량체 농도, 개시제의 농도 및 중합온도가 증가함에 따라 평균입자경은 증가하였으며, 안정제의 분자량 및 농도, 초기 중합계의 극성도가 증가함에 따라 감소하는 경향을 보였다. 또한, 본연구를 통해 1.8∼3.7μm의 입자경을 갖는 단분산의 poly(styrene/acrylonitrile) (70/30 무게비) 라텍스가 제조되었다.

Keywords: dispersion polymerization in alcoholic media; steric stabilizer; latex; solubility parameter; uniform-size particles

References
  • 1. Barrett KEJDispersion Polymerization in Organic Media, Wiley, New York (1975)
  •  
  • 2. Backhouse AJ, J. Coat. Technol., 54(693), 83 (1982)
  •  
  • 3. Backhouse AJU.S. Patent, 4,403,003 (1983)
  •  
  • 4. 中村孝一, 고분자, 4, 309 (1995)
  •  
  • 5. Smigol V, Svec G, Hosoya K, Wang Q, Frechet JMJ, Angew. Makromol. Chem., 195, 151 (1992)
  •  
  • 6. Singer JMFuture Directions in Polymer Colloids, M.S. El-Aasser and R.M. Fitch, Eds., NATO Ser. E. 138, p. 371, Kluwer Academic Publishers, Netherlands (1987)
  •  
  • 7. Ugelstad J, Berge A, Ellingsen T, Schmid R, Nilsen TN, Mork PC, Stenstad P, Hornes E, Olsvik O, Prog. Polym. Sci., 17, 87 (1992)
  •  
  • 8. Kamiyama M, Koyama K, Matsuda H, Sano Y, J. Appl. Polym. Sci., 50, 107 (1993)
  •  
  • 9. Goodwin JW, Hearn J, Ho CC, Ottewill RH, Colloid Polym. Sci., 252, 464 (1974)
  •  
  • 10. Smigol V, Svec F, J. Appl. Polym. Sci., 48, 2033 (1993)
  •  
  • 11. Ugelstad J, Mork PC, Kaggerud KG, Ellingsen T, Berge A, Adv. Colloid Interface Sci., 13, 101 (1980)
  •  
  • 12. Vanderhoff JW, El-Aasser MS, Micale FJ, Sudol ED, Tseng CM, Silwanowitz A, Kornfeld DM, Vincente FA, J. Dispers Sci. Technol., 5, 231 (1984)
  •  
  • 13. Almog Y, Reich S, Levy M, Br. Polym. J., 14, 131 (1982)
  •  
  • 14. Tseng CM, Lu YY, El-Aasser MS, Vanderhoff JW, J. Polym. Sci. A: Polym. Chem., 24, 2995 (1986)
  •  
  • 15. Paine AJ, J. Polym. Sci. A: Polym. Chem., 28, 2485 (1990)
  •  
  • 16. Shen S, Sudol ED, El-Aasser MS, J. Polym. Sci., 31, 1393 (1993)
  •  
  • 17. Hu R, Dimonie VL, Sudol ED, Elaasser MS, J. Appl. Polym. Sci., 55(10), 1411 (1995)
  •  
  • 18. Tuncel A, Kahraman R, Piskin E, J. Polym. Sci., 50, 303 (1993)
  •  
  • 19. Saenz JM, Asua JM, J. Polym. Sci. A: Polym. Chem., 33(9), 1511 (1995)
  •  
  • 20. Ober CK, Lok KP, Macromolecules, 20, 268 (1987)
  •  
  • 21. Lok KP, Ober CK, Can. J. Chem., 63, 209 (1985)
  •  
  • 22. Antl L, Goodwin JN, Ottewill RH, Owens SM, Papworth S, Waters JW, Colloids Surf., 17, 67 (1986)
  •  
  • 23. Dawkins JV, Shakir SA, Croucher TG, Eur. Polym. J., 23, 173 (1987)
  •  
  • 24. Winnik MA, Lukas R, Chen F, Furlong P, Croucher MD, Makromol. Chem. Macromol. Symp., 10-11, 483 (1987)
  •  
  • 25. Willamson B, Lukas R, Winnik MA, Croucher MD, J. Colloid Interface Sci., 110, 559 (1987)
  •  
  • 26. Pekcan O, Winnik MA, Croucher MD, J. Polym. Sci. C: Polym. Lett., 21, 1011 (1983)
  •  
  • 27. Lee KC, Winnik MA, Korea Polym. J., 2(1), 40 (1994)
  •  
  • 28. Lee KC, Winnik MA, Jao TC, J. Polym. Sci. A: Polym. Chem., 32(12), 2333 (1994)
  •  
  • 29. Croucher MD, Winnik MAAn Introduction to Polymer Colloids, F. Candau and R.H. Ottewill, Eds., p. 35, Kluwer Academic Publishers, Netherlands (1990)
  •  
  • 30. Winnik MA, Croucher MDFuture Directions in Polymer Colloids, M.S. El-Aasser and R.M. Fitch., Eds., NATO Ser. E. 138, p. 277, Kluwer Academic Publishers, Netherlands (1987)
  •  
  • 31. Ziemba GPAcrylonitrile-Styrene Copolymers in Encyclopedia of Polymer Science and Technology, Interscience, Vol. 1, p. 425 (1964)
  •  
  • 32. Gordon JLCohesive Energy Density in Encyclopedia of Polymer Science and Technology, Interscience, Vol. 3, p. 833 (1964)
  •  
  • 33. Grulke EASolubility Parameter Values in Polymer Handbook, Third Ed.; J. Brandrup and E.H. Immergut Eds., Wiley Interscience, VII 519 (1989)
  •  
  • 34. 이국웅, 문홍국플라스틱 기술, 성안당, p. 122 (1989)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 1996; 20(3): 476-488

    Published online May 25, 1996