Article
  • Synthesis and Characterization of Polystyrene-b-Poly(acrylic acid) Block Ionomer via Atom Transfer Radical Polymerization
  • Park KR, An SG, Cho CG
  • 원자 이동 라디칼 중합을 이용한 Polystyrene-b-Poly(acrylic acid) 블록 이오노머의 합성 및 분석
  • 박계리, 안성국, 조창기
Abstract
Using atom transfer radical polymerization (ATRP), polystyrene macroinitiators and polystyrene-b-poly(t-butyl acrylate) (PS-b-P(tBA)) block copolymers were synthesized by CuBr/PMDETA catalyst system in solution. After hydrolysis, polystyrene-b-poly(acrylic acid), amphiphilic block copolymers, were formed. Subsequent neutralization of polyacid block led to the block ionomers. The molecular weight of the synthesized PS-b-P(tBA) block copolymers was easily-controlled to 5000-10000 and their distributions were less than 1.2. The chemical structures of the synthesized block copolymers were characterized by 1H-NMR and FT-IR. In the DSC thermograms, Tg appeared in the vicinity of 100 ℃ because of higher styrene content. In addition, the phase separation of the block ionomers was observed by TEM.

원자 이동 라디칼 중합(ATRP)을 이용하여 CuBr/N,N,N',N'',N''-pentamethyldiethylene triamine 촉매 시스템하에서 용액중합으로 polystyrene 거대 개시제와 polystyrene-b-t-poly(butyl acrylate) (PS-b-P(tBA)) 블록 공중합체를 합성한 후, 가수분해를 통해 polystyrene-b-poly(acrylic acid) 양친매성 블록 공중합체를 얻었다. 또한, 이를 중화하여 블록 이오노머를 제조하였다. 합성된 PS-b-P(tBA) 블록 공중합체는 분자량이 5000-10000 정도로 조절되었고, 분자량 분포도 1.2 이하로 비교적 좁게 나타났다. 공중합체는 1H-NMR, FT-IR로 분석하였으며, DSC로 열적 성질을 측정한 결과, styrene의 비율이 더 많기 때문에 100 ℃ 근처에서 Tg가 나타났으며, TEM을 통해 이온 그룹의 상분리를 확인하였다.

Keywords: ionomer; ATRP; block copolymer; polystyrene; poly(acrylic acid)

References
  • 1. Eisenberg A, Kim JSIntroduction to Ionomers, Wiley-Interscience, New York (1998)
  •  
  • 2. Tant MR, Mauritz KA, Wilkes GLIonomers: Synthesis, Structure, Properties and Applications, Chapman & Hall, New York (1997)
  •  
  • 3. Schlick SIonomers: Chracterization, Theory, and Applications, CRC Press, Boca Raton, p. 1 (1996)
  •  
  • 4. Kabanov AV, Alakhov VYAmphiphilic Block Copolymers: Self-Assembly and Applications, Elsevier Science, Amsterdam, p. 347 (2000)
  •  
  • 5. Kim JS, Wu GM, Eisenberg A, Macromolecules, 27(3), 814 (1994)
  •  
  • 6. Kim JS, Nah YH, Jarng SS, Polymer, 42(13), 5567 (2001)
  •  
  • 7. Galas KS, Eur. Polym. J., 34(1), 127 (1998)
  •  
  • 8. Wang Y, Pan C, Eur. Polym. J., 37, 699 (2001)
  •  
  • 9. Galas KS, Slusarczyk C, Wlochowicz A, Eur. Polym. J., 36, 2167 (2000)
  •  
  • 10. Galas KS, Slusarczyk C, Wlochowicz A, Eur. Polym. J., 36, 2175 (2000)
  •  
  • 11. Zhang G, Liu L, Wang H, Jiang M, Eur. Polym. J., 36, 61 (2000)
  •  
  • 12. Dejardins A, Eisenberg A, Macromolecules, 24, 5779 (1991)
  •  
  • 13. Zhou ZK, Pfeiffer DG, Chu B, Macromolecules, 27(6), 1428 (1994)
  •  
  • 14. Bronich TK, Popov AM, Eisenberg A, Kabanov VA, Kabanov AV, Langmuir, 16(2), 481 (2000)
  •  
  • 15. Shen HW, Eisenberg A, Macromolecules, 33(7), 2561 (2000)
  •  
  • 16. Zhong XF, Varshney SK, Eisenberg A, Macromolecules, 25, 7160 (1992)
  •  
  • 17. Zhang G, Jiang M, Wu C, Macromol. Chem. Phys., 202, 1750 (2001)
  •  
  • 18. Lysenko EA, Bronich TK, Eisenberg A, Kabanov VA, Kabanov AV, Macromolecules, 31(14), 4511 (1998)
  •  
  • 19. Plante M, Bazuin CG, Macromolecules, 30(9), 2613 (1997)
  •  
  • 20. Bazuin CG, Plante M, Varshney SK, Macromolecules, 30(9), 2618 (1997)
  •  
  • 21. Recard DH, Eastmond GC, Stewart MJTelechelic Polymers: Synthesis and Application, CRC Press, Boca Raton, Chap. 3 (1989)
  •  
  • 22. Hautekeer JP, Varshney SK, Fayt R, Jacobs C, Jerome R, Macromolecules, 23, 3893 (1990)
  •  
  • 23. Varshney SK, Jacobs C, Hautekeer JP, Bayard P, Jerome R, Macromolecules, 24, 4997 (1991)
  •  
  • 24. Long TE, Allen RD, McGrath JE, ACS Polym. Prepr.(Am. Chem. Soc., Div. Polym. Chem.), 27, 54 (1986)
  •  
  • 25. Deporter CD, ACS Polym. Prepr.(Am. Chem. Soc., Div. Polym. Chem.), 30, 201 (1989)
  •  
  • 26. Davis KA, Matyjaszewski K, Macromolecules, 33(11), 4039 (2000)
  •  
  • 27. Davis KA, Charleux B, Matyjaszewski K, J. Polym. Sci. A: Polym. Chem., 38(12), 2274 (2000)
  •  
  • 28. Davis KA, Matyjaszewski K, Macromolecules, 34(7), 2101 (2001)
  •  
  • 29. Ma QG, Wooley KL, J. Polym. Sci. A: Polym. Chem., 38(S), 4805 (2000)
  •  
  • 30. Xia JH, Matyjaszewski K, Macromolecules, 30(25), 7697 (1997)
  •  
  • 31. Sawamoto M, Enoki T, Higashimura T, Macromolecules, 20, 1 (1987)
  •  
  • 32. Ziegler MJ, Paik HJ, Davis KA, Gaynor SG, Matyjaszewski K, ACS Polym. Prepr.(Am. Chem. Soc., Div. Polym. Chem.), 40, 432 (1999)
  •  
  • 33. Wang XS, Jackson RA, Armes SP, Macromolecules, 33(2), 255 (2000)
  •  
  • 34. Davis KA, Matyjaszewski K, ACS Polym. Prepr.(Am. Chem. Soc., Div. Polym. Chem.), 40, 430 (1999)
  •  
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This Article

  • 2003; 27(1): 17-25

    Published online Jan 25, 2003

  • Received on Sep 11, 2002
  • Accepted on Dec 5, 2002