Article
  • Synthesis and Thermal Properties of Poly(Schiff bases) Containing Dicyanovinyl Group and Their Copolymers
  • Ha JH, Gong MS, Kim SY
  • Dicyanovinyl기를 가지는 Poly(Schiff bases)와 그들의 공중합체들의 합성과 열적 성질
  • 하정협, 공명선, 김상율
Abstract
Poly(Schlff bases) and their copolymers incorporating dicyanovinyl group in the main chain were prepared by the solution polymerization of a dicyanovlnyl-containing monormer, p-bis[1-(4-formylphenoxy)-2,2-dicyanovinyl]benzene (4), and terephthalaldehyde(TA) with 4-aminophenyl ether (ODA). The resulting polymers possess intrinsic viscosities 0.42∼0.20 dL/g in the case of polymer P(1/10)∼P(2/1). The homopolymer derived from 4 and ODA is easily soluble in polar aprotic solvents. However, the solubility of the polymers in NMP decreased apparently with the increase of the content of TA in the polymer chain. Attempts to prepare high-molecular weight polymers from higher content of TA were unsuccessful probably due to the precipitation of polymer during polymerization. The polymers show a large exotherm in differential scanning calorimetry and undergo a curing reaction around 350℃ to form insoluble material in solvent. Almost all the poly(Schiff bases) exhibited 10% weight loss between 480∼540℃ and 88∼95% residual weight at 500℃ in a nitrogen a mosphere.

주쇄에 dicyanovinyl기를 가진 새로운 poly(Schiff bases)와 그의 공중합체를 dicyanovinyl기를 포함한 단량체인 p-bis[1-(4-formylphenoxy)-2,2-dicyanovinyl]benzene (4)와 TA를 4-aminophenyl ether (ODA)와 용액 중합에 의하여 합성하였다. 생성된 중합체들 P(1/0)∼P(2/1)은 고유 점도가 0.42∼0.20dL/g이었다. ODA와 4의 호모 중합체의 경우 극성 비양자성 용매에 매우 잘 녹았으나 중합체에 TA의 비율이 증가하면 NMP에 대한 용해도가 현저히 감소하였다. TA가 많이 포함된 중합체들은 중합중에 용매에 침전되어 분자량이 증가하지 않는 것으로 보여진다. DSC 분석에서 중합체들은 350℃에서 커다란 발열 피이크를 보여주며 이온도에서 열경화 반응이 진행되어 용매에 불용성 물질이 형성되었다. 거의 모든 중합체들이 480∼540℃사이에서 10% 중량 감량을 나타내 주었으며, 500℃에서 잔사량은 88∼95%로서 열안정성을 보여주었다.

References
  • 1. Cass PEThermally Stable Polymers-Syntheses and Properties, Marcel Dekker Inc., New York (1981)
  •  
  • 2. Yang HHAromatic High Strength Fibers, John Wiley & Sons, N.Y. (1989)
  •  
  • 3. Spinolli HJ, Harris FWReactive Oligomers, ACS Symp. Ser. 282, American Chemical Society, Washington D.C. (1985)
  •  
  • 4. Butler GB, Cresta JECyclopolymerization and Polymers with Chain-Ring Structures, ACS Symp. Ser. 195, Am. Chem. Soc., Washington D.C. (1982)
  •  
  • 5. Robello DR, Moore JA, Macromolecules, 19, 2667 (1986)
  •  
  • 6. Robello DR, Moore JA, Macromolecules, 22, 1084 (1989)
  •  
  • 7. Mehta PG, Moore JA, Polym. Mater. Sci. Eng., 63, 351 (1990)
  •  
  • 8. Mehta PG, Moore JA, Macromolecules, 26, 916 (1993)
  •  
  • 9. Kim JH, Moore JA, Korea Polym. J., 1(2), 116 (1993)
  •  
  • 10. Moore JA, Mehta PG, Kim SY, Macromolecules, 26, 3504 (1993)
  •  
  • 11. Gong MS, Kim ST, Moon HS, Makromol. Chem. Rapid Commun., 12, 591 (1991)
  •  
  • 12. Gong MS, Moon HS, Kim JS, Kim CB, Polym. J., 25, 193 (1993)
  •  
  • 13. Kim ST, Moon HS, Gong MS, Macromolecules, 25, 7392 (1992)
  •  
  • 14. Gong MS, Kim JS, Choi SH, Kim ST, Polym. J., 25, 763 (1993)
  •  
  • 15. Gong MS, Cho HG, Kim BG, Choi SH, Macromolecules, 26, 6654 (1993)
  •  
  • 16. Moon SH, Lee SJ, Kim JB, Gong MS, Bull. Korean Chem. Soc., 15, 1809 (1994)
  •  
  • 17. Gong MS, Kim BG, Kim YS, Polym. J., 26, 1910 (1994)
  •  
  • 18. Shin JC, Kim TM, Gong MS, Macromolecules, 28(7), 2212 (1995)
  •  
  • 19. Gong MS, Han YG, Kim SG, Bull. Korean Chem. Soc., 16, 326 (1995)
  •  
  • 20. Gong MS, Ha JH, Kim BG, Kim C, Polym. J., 16, 326 (1995)
  •  
  • 21. Gong MS, Ha JH, Kim BG, Kim C, Polym. J., 27, 536 (1995)
  •  
  • 22. Kim BG, Gong MS, Kim JJ, Korea Polym. J., 2(2), 109 (1994)
  •  
  • 23. Kim SG, Lee SJ, Gong MS, Macromolecules, 28(16), 5638 (1995)
  •  
  • 24. Adams R, Bullock JE, Wilson WC, J. Am. Chem. Soc., 45, 521 (1923)
  •  
  • 25. Moore JA, Kaur S, Perry RJ, Polym. Prepr., 35(1), 385 (1994)
  •  
  • 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(1): 1-9

    Published online Jan 25, 1996