Textile Science and Engineering (한국섬유공학회지)

The Korean Fiber Society (한국섬유공학회)
권호 표지

Studies on the Transesterification of Poly(trimethylene terephthalate)/Poly(trimethylene naphthalate) (50/50) Blends Using $^1H-NMR$ and WAXS

$^1H-NMR$과 WAXS를 이용한 폴리(트리메틸렌 테레프탈레이트)/폴리(트리메틸렌 나프탈레이트) (50/50) 블렌드의 에스터 교 환반응 연구

  • 최재원 (인하대학교 스포츠 레저섬유연구센터) ;
  • 오태환 (㈜휴비스 연구소) ;
  • 김영호 (숭실대학교 공과대학 섬유공학과)
  • Published : 2005.10.01
⟨ Previous Next ⟩

Abstract

Poly(trimethylene terephthalate) (PIT) and poly(trimethylene naphthalate) (PTN) blends of 50/50 weight ratio, T5N5, were prepared by solution blending-precipitation method, and the effect of melting time on the degree of randomness, sequence length, and crystalline structure of melt-pressed blends obtained by melting T5N5 on a hot stage at $260^{\circ}C$ for different times and quenching into liquid nitrogen was studied using DSC, $^1H-NMR$ and WAXS. The T5N5 blend showed two $T_gs$ corresponding to that of PTT and PTN, which indicated that PTT and PTN were immiscible. But the melt-pressed blends melted at $260^{\circ}C$ for 2 minutes or more showed single $T_g$ indicating that the system became miscible. $^1H-NMR$ analysis confirmed that the blends became block copolymers and that the degree of randomness increased as melting time increased. The sequence length of PTT component was larger than that of PTN in the resultant copolymer. Although PTT and PTN were present in the same amount in the blend, PTT component crystallized more easily than the PTN component due to the larger block length of PTT. The crystalline structure of the component polymers was the same as that of homopolymers. The WAXS patterns showed that the crystalline structure of PTN in the melt-pressed blends was $\beta-form$ when they were annealed at $180^{\circ}C$ but it was a-form when annealed at $140^{\circ}C$, exhibiting the same behavior as homo PTN.

Keywords

References

  1. C. Belti, V. Bonora, F. Pilati, and M. Fiorini, 'Reactive Blending of Poly(ethylene terephthalate) and Polycarbonate, 1. A Reappraisal of the Reactions Occurring During Meltmixing', Makromol Chem, 1992, 193, 1665-1677 https://doi.org/10.1002/macp.1992.021930710
  2. C. Berti, V. Bonora, F. Pilati, and M. Fiorini, 'Reactive Blending of Poly(ethylene terephthalate) and Polycarbonate, 2. A Novel Route to Copoly(ester-ether)s', Makromol Chem, 1992, 193, 1679-1686 https://doi.org/10.1002/macp.1992.021930711
  3. M. Guo and W. J. Brittain, 'Structure and Properties of Naphthalene-Containing Polyesters. 4. New Insight into the Relationship of Transesterification and Miscibility', Macromolecules, 1998, 31, 7166-7171 https://doi.org/10.1021/ma9716903
  4. E. Andresen and H. G. Zachmann, 'Studies of Miscibility, Transesterification and Crystallization in Blends of Poly (ethylene terephthalate) and Poly(ethylene-2,6-naphthalene dicarboxylate)', Colloid Polym Sci, 1994, 272, 1352-1362 https://doi.org/10.1007/BF00654165
  5. B. Jacques, J. Devaux, R. Legras, and E. Nield, 'Reactions Induced by Triphenyl Phosphite Addition During Melt Mixing of Poly(ethylene terephthalate)/Poly(butylene terephthalate) Blends: Influence on Polyester Molecular Structure and Thermal Behaviour', Polymer, 1996, 37, 1189-1200 https://doi.org/10.1016/0032-3861(96)80846-9
  6. Z. H. Huang and L. H. Wang, 'Infrared Studies of Transesterification in Poly(ethylene terephthalate)lPolycarbonate Blends', Makromol Chem, Rapid Commun, 1986, 7, 255-259 https://doi.org/10.1002/marc.1986.030070504
  7. R. Yamadera and M. Murano, 'The Determination of Randomness in Copolyesters by High Resolution Nuclear Magnetic Resonance', J Polym Sci: Polym Chem, 1967, 5, 2259-2268 https://doi.org/10.1002/pol.1967.150050905
  8. S. C. E. Backson, A. M. Kenwright, and R. W. Richards, 'A $^{13}C$ NMR Study of Transesterification in Mixtures of Poly(ethylene terephthalate) and Poly(butylene terephthalate)', Polymer, 1995, 36, 1991-1998
  9. Y. Aoki, L. Li, T. Amari, K. Nishimura, and Y. Arashiro, 'Dynamic Mechanical Properties of Poly(ethylene terephthalate)/Poly(ethylene 2,6-naphthalate) Blends', Macromolecules, 1999, 32, 1923-1929 https://doi.org/10.1021/ma981657w
  10. N. Avramova, 'Amorphous Poly(ethylene terephthalate)/Poly(butylene terephthalate) Blends: Miscibility and Properties', Polymer, 1995, 36, 801-808 https://doi.org/10.1016/0032-3861(95)93111-X
  11. D. W. Ihm, S. Y. Park, C. G. Chang, Y. S. Kim, and H. K. Lee, 'Miscibility of Poly(ethylene terephthalate)/Poly (ethylene 2,6-naphthalate) Blends by Transesterification', J Polym Sci: Polym Chem, 1996, 34, 2841-2850 https://doi.org/10.1002/(SICI)1099-0518(199610)34:14<2841::AID-POLA1>3.0.CO;2-U
  12. S. S. Park, I. K. Kim, and S. S. Im, 'Sequence Distribution and Thermal behaviour of Poly(ethylene 2,6-naphthalate-cohexamethylene 2,6-naphthalate) Copolyesters', Polymer, 1996, 37, 2165-2171 https://doi.org/10.1016/0032-3861(96)85861-7
  13. Y. H. Kim and J. W. Choi, 'Synthesis and Characterization of Poly(trimethylene terephthalate/Poly(trimethylene naphthalate) Blends', J Korean Fiber Soc, 2003, 40, 321-329
  14. Y. Shi and S. A. Jabarin, 'Transesterification Reaction Kinetics of Poly(ethylene terephthalate)/Polytethylene 2,6-naphthalate Blends)', J Appl Polym Sci, 2001, 80, 2422-2436 https://doi.org/10.1002/app.1349
  15. Y. G. Jeong, W. H. Jo, and S. C. Lee, 'Melting and Crystallization behavior of Poly(trimethylene 2,6-naphthalate)', Polymer, 2003, 44, 3259-3267 https://doi.org/10.1016/S0032-3861(03)00270-2