Article
  • Enhancement of Anti-hydrolysis of PBT with Reduced Carboxyl End Group by Solid State Polymerization
  • Lee KH, Huh PH, Kim BK
  • 고상중합을 통한 PBT의 카르복실 말단기 감소 및 내가수분해성 향상
  • 이관희, 허필호, 김병규
Abstract
Solid state polymerization (SSP) was carried out on commercially available PBT pre-synthesized from melt polymerization. The carboxyl end group of PBT decreased with increasing molecular weight of PBT during SSP. The changes of carboxyl end group and mechanical properties were measured under the pressure cooker test (PCT, @121 ℃/RH 100%) as a function of aging time. The carboxyl end groups increased with increasing PCT aging time and the increasing rate was proportional to the number of the initial carboxyl end group. PBT with less initial carboxyl end group had maintained its tensile strength, flexural strength, and impact strength for longer time. This study showed that the antihydrolysis of PBT could be improved by SSP due to reduced carboxyl end group.

용융중합에 의해 상업적으로 생산된 중점도급의 poly(butylene terephthalate)(PBT)를 이용하여 고상중합을 실시하였다. 고상중합에 따른 PBT의 분자량이 증가할수록 카르복실 말단기는 감소하였으며, 121 oC, 상대습도 100% 조건(PCT)에서 시간에 따른 카르복실 말단기의 변화 및 물성의 변화를 관찰하였다. PCT 시간에 따라 카르복실 말단기는 증가하였는데, 초기 카르복실 말단기가 적을수록 증가 기울기는 낮은 거동을 보였다. PCT 시간에 따른 인장강도, 충격강도, 및 굴곡강도는 일정 시간이 지나면 급격하게 감소하였는데, 초기 카르복실 말단기가 적을수록 급격히 감소하기 시작하는 시간이 길었다. 따라서 고상중합을 통하여 카르복실 말단기를 줄일 수 있으며 PBT의 내가수분해성을 향상시킬 수 있음을 확인하였다.

Keywords: poly(butylene terephthalate); carboxyl end group; solid state polymerization; pressure cooker test

References
  • 1. , Plastics Age, 74, 150 (2006)
  •  
  • 2. Marechal E, Handbook of Thermoplastic Polyesters, Wiley-VCH, Weinheim, 2002.
  •  
  • 3. Gallucci RR, Patel BR, “Poly(butylene terephthalate)”, in Modern Polyesters, Scheiris J, Long TE, Edtors, John Wiley & Sons Ltd., England (2003).
  •  
  • 4. Foltner W, “Solid State Polymerization of Polyester Resins”, in Modern Polyesters, Scheiris J, Long TE, Edtors, John Wiley & Sons Ltd., England (2003).
  •  
  • 5. Binsack R, “Thermoplastic Polyesters”, in Engineering Thermoplastics: Poly-carbonates, Polyacetals, Polyesters and Cellulose Esters, Bottenbruch L, Editor, Hanser Publishers, New York (1996).
  •  
  • 6. Jaquiss DBG, Borman WFH, Campbell RW, “Polyesters, Thermoplastic”, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Ed., Grayson M, Editor, Wiley, New York, Vol 18 (1982).
  •  
  • 7. Caldwell JR, Jackson WJ, Gray TF, “Polyesters, Thermoplastic”, in Encyclopedia of Polymer Science and Technology, Bikales NM, Editor, Wiley-Interscience, New York Vol 1, Suppl. 1 (1976).
  •  
  • 8. Kirsch MA, Williams DJ, Chemtech, 24, 40 (1994)
  •  
  • 9. Kiefer DM, “Polyesters end run round nylon, in Today’s Chemist at Work, p 71-74 (2000).
  •  
  • 10. Duh B, US Patent, 4,238,593 (1980).
  •  
  • 11. Montaudo G, Puglisi C, Samperi F, Polym. Degrad. Stabil., 42, 13 (1993)
  •  
  • 12. Samperi F, Puglisi C, Alicata R, Montaudo G, Polym. Degrad. Stabil., 83, 11 (2004)
  •  
  • 13. Rum RM, J. Polym. Sci. A: Polym. Chem., 17, 203 (1979)
  •  
  • 14. Flory P, US Patent 2,172,374 (1939).
  •  
  • 15. Monroe G, US Patent 3,031,433 (1962).
  •  
  • 16. Vouyiouka SN, Karakatsani EK, Papaspyrides C, Prog. Polym. Sci, 30, 10 (2005)
  •  
  • 17. Ravindranath K, Mashelkar R, J. Appl. Polym. Sci., 39, 1325 (1990)
  •  
  • 18. Weger F, Hagen R, US Patent 5,773,555 (1998).
  •  
  • 19. Fakirov S, Avramova N, Acta Polym., 33, 271 (1982)
  •  
  • 20. Shimizu K, Ise S, JP Patent 4-93323 (1992).
  •  
  • 21. Morawetz H, J. Polym. Sci. Part C, 12, 79 (1966)
  •  
  • 22. Bruck S, Ind. Eng. Chem. Prod. Res. Dev., 2, 119 (1963)
  •  
  • 23. Mizerovskii L, Kuznetsov A, Bazarov Y, Bykov A, Polym. Sci. USSR, 24, 1310 (1982)
  •  
  • 24. Srinivasan R, Desai P, Abhiraman AS, Knorr RS, J. Appl. Polym. Sci., 53(13), 1731 (1994)
  •  
  • 25. Fujimoto A, Mori T, Hiruta S, Nippon Kagaku Kaishi, 3, 337 (1988)
  •  
  • 26. Li L, Huang N, Liu Z, Tang Z, Yung W, Polym. Adv. Technol., 11, 242 (2000)
  •  
  • 27. Yao KZ, McAuley KB, Berg D, Marchildon EK, Chem. Eng. Sci., 56(16), 4801 (2001)
  •  
  • 28. Beaton D, US Patent 3,821,171 (1974).
  •  
  • 29. Blanchard E, Cohen J, Iwasyk J, Marks D, Stouffer J, Aslop A, Lin C, WO Patent 99/10408 (1999).
  •  
  • 30. Kampouris E, Papaspyrides C, Polymer, 26, 413 (1985)
  •  
  • 31. Papaspyrides C, Polymer, 29, 114 (1988)
  •  
  • 32. Papaspyrides C, “Solid state polyamidation”, in The polymeric materials encyclopedia, Salamone JC, Editor, CRC Press, Boca Raton, FL (1996).
  •  
  • 33. Jacquiss D, Borman WH, Campbell RW, “Polyester, Thermoplastic”, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Ed., Wiley, N.Y., Vol 18, 552 (1982).
  •  
  • 34. Kosky PG, McDonald RS, Guggenheim EA, Polym. Eng. Sci., 25, 389 (1985)
  •  
  • 35. Borman WFH, J. Appl. Polym. Sci., 22, 2119 (1978)
  •  
  • 36. Zimmerman J, J. Polym. Lett., 2, 955 (1964)
  •  
  • 37. Zimmerman J, Kohan MI, J. Polym. Sci. A: Polym. Chem., 39(15), 2565 (2001)
  •  
  • 38. Park CS, Lee KJ, Kim SW, Lee YK, Nam JD, J. Appl. Polym. Sci., 86(2), 478 (2002)
  •  
  • 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

  • 2016; 40(3): 341-346

    Published online May 25, 2016

  • 10.7317/pk.2016.40.3.1
  • Received on Apr 30, 2015
  • Accepted on Jan 7, 2016