화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of the Korean Industrial and Engineering Chemistry, Vol.15, No.2, 176-182, April, 2004
Export Citation
디일렉트로메트리법을 이용한 아세틸렌 말단기를 갖는 과불소 폴리(아릴렌 에테르) 화합물의 경화거동 연구
The Studies on the Curing Behaviors of Perfluorinated Poly(arylene ether) Bearing Acetylenic End Groups by Dielectrometry
제갈영순, 이형종1, †, 윤남균2, 장상희3, 이원철4, 진성호5
  • 경일대학교 교양학부, 하양 712-701
  • 1젠포토닉스, 대전 305-380
  • 2국방과학연구소, 대전 305-380
  • 3구미1대학 식품과학과, 구미 730-711
  • 4경일대학교 섬유패션학부, 하양 712-701
  • 5부산대학교 과학교육학부, 부산 609-735
Yeong-Soon Gal, Hyong-Jong Lee1, †, Nam-Gyun Yoon2, Sang Hee Jang3, Won-Chul Lee4, and Sung-Ho Jin5
  • Polymer Chemistry Laboratory, College of Generall Education, Kyungil University, Hayang 712-701, Korea
  • 1Zenphotonics, Daejeon 305-380, Korea
  • 2Composite Materials Laboratory, Agency for Defense Development, Daejeon 305-600, Korea
  • 3Department of Food & Nutrition Science, Kumi College, Kumi 730-711, Korea
  • 4Department of Textile and Fashion Technology, Kyungil University, Hayang 712-701, Korea
  • 5Department of Chemical Education, School of Education, Pusan National University, Busan 609-735, Korea
E-mail:
초록
4,4'-(헥사플로로이소프로필리덴)디페놀과 과량의 데카플로로비페닐과의 반응, 그리고 m-에티닐페놀과의 반응을 통하여 사슬 말단에 가교화가 가능한 에티닐기를 갖는 불소화 에테르 올리고머(FPAE-EP)를 합성하였다. 이 FPAE-EP의 수평균 분자량과 다분산도는 각각 7800과 1.79였다. FPAE-EP의 경화거동을 디일렉트로메트리, 시차주사열분석, 적외선 분광분석과 같은 분석법으로 연구하였다. FPAE-EP는 202 ℃ 부근에서 가장 낮은 이온 점도를 보였으며, 이 온도 이후에서 이온점도가 점차 증가하는 경향을 보이는데, 이것은 이 온도 부근에서 가교화반응이 시작되고, 말다 ㄴ아세틸렌 기의 열가속화반응에 의한 분자량 증가를 의미한다. 경화시 재료의 유동성과 밀접한 관계가 있는 loss factor 거동은 이온점도 거동과 매우 유사하였다.
Fluorinated ether oligomer with a crosslinkable ethynyl group at the chain end (FPAE-EP) was synthesized by the reaction of 4,4'-(hexafluoroisopropylidene)diphenol with an excess decafluorobiphenyl, followed by reaction with m-ethynylphenol. The molecular weight (Mn) and polydispersit (Mw/Mn) of FPAE-EP were 7800 and 1.79, respectively. The studies on the curing behaviors of FPAE-EP were performed by such instrumental methods as dielectrometry, differential scanning calorimetry, and FT-IR spectroscopies. The FPAE-EP showed the lowest ionic viscosity around 202 ℃, and then the ionic viscosity was gradually increased up to 271 ℃. This means that the crosslinking reaction of FPAE-EP started at 202 ℃ and the molecular weight was increased by the accelerated thermal crosslinking reaction of the terminal acetylene functions. The loss factor behaviors of FPAE-EP, which is related to the fluidity of matrix, were found to be similar to that of ionic viscosity.
Keywords:dielectrometry;fluornated ether oligomer;acetylene;crosslinking;ionic viscosity
  1. Chauser MG, Rodionov YM, Misin VM, Cherkashin MI, Russ. Chem. Rev., 45, 348 (1976) 
  2. Masuda T, Higashimura T, Adv. Polym. Sci., 81, 121 (1987)
  3. Choi SK, Gal YS, Jin SH, Kim HK, Chem. Rev., 100(4), 1645 (2000) 
  4. Baughman RH, Bredas JL, Chance RR, Elsenbaumer RL, Shacklwtte LW, Chem. Rev., 82, 209 (1982) 
  5. Lee CY, Kim HM, Park JW, Gal YS, Jin JI, Joo J, Synth. Met., 117, 109 (2001) 
  6. Kwak G, Masuda T, Macromolecules, 33(18), 6633 (2000) 
  7. Yashima E, Matsushima T, Nimura T, Okamoto Y, Korea Polym. J., 4(2), 139 (1996)
  8. Aoki T, Shinohara K, Kaneko T, Oikawa E, Macromolecules, 29(12), 4192 (1996) 
  9. Choi SK, Lee JH, Kang SJ, Jin SH, Prog. Polym. Sci., 22, 693 (1997) 
  10. Gui TL, Jin SH, Park JW, Ahn WS, Koh K, Kim SH, Gal YS, Opt. Mater., 21, 637 (2002) 
  11. Furlani A, Iucci G, Russo MV, Bearzotti A, D'Amico A, Sens. Actuators B-Chem., 7, 447 (1992) 
  12. Furlani A, Iucci G, Russo MV, Bearzotti A, D'Amico A, Sens. Actuators B-Chem., 8, 123 (1992) 
  13. Jin SH, Park JW, Choi SK, Cho HN, Park SY, Kim N, Wada T, Sasabe H, Mol. Cryst. Liq. Cryst., 247, 129 (1994)
  14. Lee HJ, Won YH, Kang SJ, Choi SK, Kim HK, J. Polym. Sci. A: Polym. Chem., 34(12), 2333 (1996) 
  15. Gal YS, Lee WC, Park JW, Kim BS, Jang SH, Jin SH, Mol. Cryst. Liq. Cryst., 371, 289 (2001)
  16. Gal YS, Gui TL, Jin SH, Park JW, Koh KN, Lee WC, Kim SH, Kim SY, Synth. Met., 135-136, 353 (2003) 
  17. Suh HJ, Jin SH, Ga YS, Koh K, Kim SH, Dyes Pigments, 58, 127 (2003) 
  18. Katzman HA, Mallon JJ, Barry WT, Polyarylacetylene-matrix Composites for Solid Rocket Motor Components, Aerospace Report No. TR-95(5936)-4, 1 September (1995)
  19. Moore JA, Lang CI, Lu TM, Yang GR, Vapor-depositable Polymers with Low Dielectric Constants, The 6th Workshop on Advanced Functional Polymer Materials, High Temperature Polymers for Electronics & Composites, pp. 105, KAIST, Taejon, Korea, August 13 (1998)
  20. Sarobe M, Jenneskens LW, J. Org. Chem., 62, 8247 (1997) 
  21. Connell JW, Hergenrother PM, Havens SJ, High Perform. Polym., 1, 119 (1989)
  22. Fang XM, Rogers DF, Scola DA, Stevens MP, J. Polym. Sci. A: Polym. Chem., 36(3), 461 (1998) 
  23. Gal YS, Jin SH, Polym. Sci. Technol., 11(6), 751 (2000)
  24. Lee HJ, Lee EM, Lee MH, Oh MC, Ahn JH, Han SG, Kim HG, J. Polym. Sci. A: Polym. Chem., 36(16), 2881 (1998) 
  25. Lee HJ, Lee MH, Oh MC, Ahn JH, Han SG, J. Polym. Sci. A: Polym. Chem., 37(14), 2355 (1999) 
  26. Kim JP, Lee WY, Kang JW, Kwon SK, Kim JJ, Lee JS, Macromolecules, 34(22), 7817 (2001) 
  27. Gal YS, Lee WC, Jin SH, Lee HJ, Korea Polym. J., 8(5), 231 (2000)
  28. Wetton RE, Foster GM, Smith VR, Dielectric Monitoring of Epoxy Cure: Detailed Analysis, 33th Int. Symp. March 7-10, pp. 603 (1988)
  29. Yun NG, Kim YC, Chung SK, Jung B, Polym.(Korea), 19(4), 438 (1995)
  30. Gal YS, Lee WC, Kwon OH, Yoon NG, Lhim KS, Ahn JK, Park KJ, J. Korean Soc. Comp. Mater., 14(2), 1 (2001)
  31. Daniel VV, Dielectric Relaxation, Academic Press, London and New York (1988)
  32. Day DR, Dielectric Properties of Polymeric Materials, Micromet Instruments, New York (1988)
  33. Senturia SD, Methods and Apparatus for Microdielectrometry, U.S. Patents, No. 4,423,371 (1983)
  34. Bonnet A, Pascault JP, Sautereau H, Rogozinski J, Kranbuehl D, Macromolecules, 33(10), 3833 (2000) 
  35. Kortaberria G, Arruti P, Mondragon I, Polym. Int., 50, 957 (2001) 
  36. Okamoto Y, Alia D, Chem. Ind., 1311 (1964)
  37. Amdur S, Cheng ATY, Wong CJ, Ehrlich P, Allendoerfer RD, J. Polym. Sci. A: Polym. Chem., 16, 407 (1978)
  38. Gal YS, Jin SH, Lee WC, Lee HS, Kim SY, J. Korean Ind. Eng. Chem., 13(7), 703 (2002)