화학공학소재연구정보센터
Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.3, 454-462, June, 1997
열방성 블록 코폴리에스테르와 Poly(ethylene 2,6-naphthalate)의 복합재료 연구(I)
On the Composites of poly(ethylene 2,6-naphthalate) with a Thermotropic Block Copolyester(I)
초록
새로운 poly(tetramethylene 2,6-(naphthaloyldioxy)dibenzoates)(TLCP) 블록과 poly (butylene 2,6-naphthalate)(PBN) 블록으로 구성된 열방성 블록공중합체(TLCP-b-PBN)를 용액중합에 의하여 합성하였고, in-situ 복합재료를 제조하기 위해서 poly(ethylene 2,6-naphthalate) (PEN)과 용응블렌드하였다. TLCP domain은 용융상태에서 네마틱 상을 보여 주었다. 블록공중합체는 DSC 열곡선에서 PBN과 TLCP domain에 해당되는 두 개의 뚜렷한 용응전이점을 보여 주었다. 블렌드내의 PEN의 유리전이온도 (Tg)는 TLCP-b-PBN의 함량에 따라 감소하였으며, TLCP-b-PBN은 매트릭스 고분자에 대한 기핵제로 작용하였다. 편광현미경 관찰결과 20% TLCP-b-PBN 블렌드 경우 PEN의 용융점이상 온도에서 잘 배향된 TLCP fibril을 볼 수 있었다. 압출된 블렌드를 액체질소내에서 절단하여 전자현미경을 이용하여 모폴로지를 관찰한 결과 TLCP domain은 0.15㎛에서 0.2㎛ 크기로 균일하게 분포되어 있음을 확인하였다. 매트릭스 곡분자와 TLCP와의 계면접착력은 비교적 좋았으며, 매트릭스 고분자내의 TLCP domain은 중앙에서는 구형의 모양을, 표면에서는 가늘게 배향된 섬유 모양을 보였다.
Thermotropic block copolyester(TLCP-b-PBN) based on poly(tetramethylene 2,6-(naphthaloyldioxy)dibenzoates)(TLCP) and poly(butylene 2,6-naphthalate)(PBN) was synthesized by solution polycondensation and melt-blended with poly(ethylene 2,6-naphthalate)(PEN) for in-situ composites. The TLCP domains showed nematic behavior in melt. The composition of block copolymer was determined from 1H-NMR spectroscopy. The DSC thermogram of block copolymer revealed the presence of two major melting transitions, corresponding to the separete melting of PBN and TLCP domains. The glass transition temperature(Tg) of the PEN in the blends decreased with increasing the content of TLCP-b-PBN and the TLCP-b-PBN acted as a nucleating agent for the matrix polymers. In the 20% TLCP-b-PBN blend, well oriented TLCP fibriles were observed at temperature above the melting point of the PEN by optical microscopy. By scanning electron micrographs of cryogenically fractured surfaces of extruded blends, the TLCp domains were found to be finely and uniformely dispersed in 0.15 to 0.2㎛ size. Interfacial adhesion between the TLCP and matrix polymer was seemed to be good. Under certain condition TLCP formed a fiver structure in the PEN matrix, with thin oriented TLCP fibril in the skin region and spherical TLCP domains in the core.
  1. Kiss G, Polym. Eng. Sci., 27, 410 (1987) 
  2. Blizard KG, Baird DG, Polym. Eng. Sci., 27, 653 (1987) 
  3. Chang JH, Jo BW, J. Appl. Polym. Sci., 60(7), 939 (1996) 
  4. Shin BY, Chung IJ, Polym. Eng. Sci., 30, 22 (1990) 
  5. Weiss RA, Huh W, Nicolas L, Polym. Eng. Sci., 27, 684 (1987) 
  6. Kohli A, Chung N, Weiss RA, Polym. Eng. Sci., 29, 573 (1989) 
  7. Siegmann A, Dagan A, Kenig S, Polymer, 26, 1325 (1985) 
  8. Isayev AI, Modic MJ, Polym. Compos., 8, 158 (1987) 
  9. Joseph EG, Wilkes GL, Baird DG, Am. Chem. Sci. Div. Polym. Prepr., 25, 94 (1984)
  10. Takayanagi M, Ogata T, Morikawa M, Kai TJ, Macromol. Sci. Phys., B17, 591 (1980)
  11. Takayanagi M, Pure Appl. Chem., 55, 819 (1983)
  12. Joseph EG, Wilkes GL, Baird DG, "Polymer Liquid Crystal," A. Blumstein Ed., p. 197, Plenum Press, N.Y. (1984)
  13. Bang MS, Choi JK, Choi HH, Polym.(Korea), 20(5), 735 (1996)
  14. Lee WC, Dibenedetto T, Polymer, 34, 684 (1993) 
  15. Datta A, Chen HH, Baird DG, Polymer, 34, 759 (1992) 
  16. Chang JH, Lee SM, Park NJ, Jo BW, Bang MS, Polym.(Korea), 18(6), 966 (1994)
  17. Cakmak M, Wang YD, Polym. Eng. Sci., 30, 72 (1990)
  18. Park LS, Yoon JH, Polym.(Korea), 18(5), 700 (1994)
  19. Buchner S, Wiswe D, Iachmann HG, Polymer, 30, 480 (1989) 
  20. Ignatious F, Lenz RW, Kantor SW, Macromolecules, 27(19), 5248 (1994) 
  21. Yoon KH, Lee SC, Park OO, Polym. J., 26, 816 (1994) 
  22. Jo BW, Choi JK, Jin JI, Polym. Plast. Technol. Eng., 29, 521 (1990)
  23. Yoon KH, Lee SC, Park OO, Polym. Eng. Sci., 35, 1807 (1995) 
  24. Li JX, Silverstein MS, Hiltner A, Baer E, J. Appl. Polym. Sci., 44, 1531 (1992) 
  25. Qin Y, Brydon DL, Mather RR, Wardmann RH, Polymer, 34, 1202 (1993) 
  26. Jang SH, Kim BS, Polym. Eng. Sci., 35(6), 538 (1995)