Skip to main content
SpringerLink
Log in

Time-resolved synchrotron X-ray scattering studies on crystallization behaviors of poly(ethylene terephthalate) copolymers containing 1,4-cyclohexylenedimethylene units

  • Articles
  • Published:
Macromolecular Research Aims and scope Submit manuscript

Abstract

Time-resolved small-angle X-ray scattering (SAXS) analysis was performed on a series of poly(ethyleneco-1,4-cyclohexyldimethylene terephthalate)s (PECT copolymers) containing 1.6, 5.3, and 9.8 mol% 1,4-cyclohexyldimethylene (CHDM) units during isothermal crystallization and subsequent melting processes. The measured SAXS data were quantitatively analyzed to yield detailed information (scattering invariant quantity, Q; long period, L p ; lamellar crystal layer thickness, d c ; and amorphous layer thickness, d a ) about the crystal structure evolution and melting devolution behaviors. The Q value was found to be a very sensitive powerful probe for monitoring the crystallization and crystal melting processes. The structural evolution of the copolymers was dominated by the primary crystallization transition. The secondary crystallization effects contributed little to the structural evolution. The few secondary crystals present most likely formed fringed micelle structures that were very small and included a high degree of imperfections. The poor secondary crystal formation was attributed to the presence of bulky, kinked CHDM units, which introduced a high degree of steric hindrance. The high steric hindrance of the CHDM units resulted in their exclusion from the lamellar crystal layers and secondary crystals, and in their insertion into amorphous regions and layers. Overall, the CHDM comonomer units strongly perturbed the crystallization process and the morphological structure of the PECT copolymer. The effects of CHDM as a chemical modifier of poly(ethylene terephthalate)-based polymers may potentially be optimized in an effort to enhance the properties and processability of the polymer.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. N. J. Brozenic, Modern Plastics Encyclopedia, McGraw-Hill, New York, 1986.

    Google Scholar 

  2. S. Ainsworth, Chem. Eng. News, 72, 11 (1994).

    Google Scholar 

  3. B. Lee, J.W. Lee, S.W. Lee, J. Yoon, and M. Ree, Polym. Eng. Sci., 44, 1682 (2004).

    Article  CAS  Google Scholar 

  4. J. Yu, D. Zhou, W. Chai, B. Lee, S.W. Lee, J. Yoon, and M. Ree, Macromol. Res., 11, 25 (2003).

    Article  CAS  Google Scholar 

  5. J. W. Lee, S. W. Lee, B. Lee, and M. Ree, Macromol. Chem. Phys., 202, 3072 (2001).

    Article  CAS  Google Scholar 

  6. C. K. Cho, J. D. Kim, K. Cho, C. E. Park, S. W. Lee, and M. Ree, J. Adhes. Sci. Technol., 14, 1145 (2000).

    Article  CAS  Google Scholar 

  7. C. K. Cho, J. D. Kim, K. Cho, C. E. Park, S. W. Lee, and M. Ree, J. Adhes. Sci. Technol., 14, 1131 (2000).

    Article  CAS  Google Scholar 

  8. S. W. Lee, B. Lee, and M. Ree, Macromol. Chem. Phys., 201, 453 (2000).

    Article  CAS  Google Scholar 

  9. J. Y. Yu, B. Z. Li, S. W. Lee, and M. Ree, J. Appl. Polym. Sci., 73, 1191 (1999).

    Article  CAS  Google Scholar 

  10. S. W. Lee, M. Ree, C. E. Park, C. S. Park, and Y. S. Jin, Polymer, 40, 7137 (1999).

    Article  CAS  Google Scholar 

  11. B. Lee, T. J. Shin, S. W. Lee, J. Yoon, J. Kim, and M. Ree, Macromolecules, 37, 4174 (2004).

    Article  CAS  Google Scholar 

  12. B. Lee, T. J. Shin, S. W. Lee, J. Yoon, J. Kim, H. S. Youn, K.-B. Lee, and M. Ree, Polymer, 44, 2509 (2003).

    Article  CAS  Google Scholar 

  13. B. Lee, T. J. Shin, S. W. Lee, J. W. Lee, and M. Ree, Macromol. Symp., 190, 173 (2002).

    Article  CAS  Google Scholar 

  14. H. Y. Yoo, S. Umemoto, T. Kikutani, and N. Okui, Polymer, 35, 117 (1994).

    Article  CAS  Google Scholar 

  15. B. D. Rebecca and C. B. Mary, Polymer, 46, 4827 (2005).

    Article  Google Scholar 

  16. T. Grossetete, A. Rivaton, J. L. Gardette, C. E. Hoyle, M. Ziemer, D. R. Fagerburg, and H. Clauberg, Polymer, 41, 3541 (2000).

    Article  CAS  Google Scholar 

  17. L. P. Chen and A. F. Yee, Macromolecules, 31, 5371 (1998).

    Article  CAS  Google Scholar 

  18. L. P. Chen and A. F. Yee, Macromolecules, 32, 5944 (1999).

    Article  CAS  Google Scholar 

  19. K. Karger-Kocsis, E. J. Moskala, and P. P. Shang, J. Therm. Anal. Calorim., 63, 671 (2001).

    Article  CAS  Google Scholar 

  20. A. J. Hill, S. WeinHold, G. M. Stack, and M. R. Tant, Eur. Polym. J., 32, 843 (1996).

    Article  CAS  Google Scholar 

  21. A. S. Merenga, C. M. Papadais, F. Kremer, J. Liu, and A. F. Yee, Colloid Polym. Sci., 279, 1064 (2001).

    Article  CAS  Google Scholar 

  22. M. Kattan, E. Dargent, J. Ledru, and J. Grenet, J. Appl. Polym. Sci., 81, 3405 (2001).

    Article  CAS  Google Scholar 

  23. Y. Q. Rao, J. Greener, C. A. Avila-Orta, B. S. Hsiao, and T. N. Blanton, Polymer, 49, 2507 (2008).

    Article  CAS  Google Scholar 

  24. C. A. Avila-Orta, F. J. Medellin-Rodriguez, Z. Wang, D. Navarro- Rodriguez, B. S. Hsiao, and F. Yeh, Polymer, 44, 1527 (2003).

    Article  CAS  Google Scholar 

  25. F. J. Medellin-Rodriguez, P. J. Phillips, J. S. Lin, and C. A. Avila-Orta, J. Polym. Sci. Part B: Polym. Phys., 36, 763 (1998).

    Article  CAS  Google Scholar 

  26. 2012 Tecnical Brochure of SK Chemicals Products, SK Chemicals, Suwon, 2012.

  27. K. Heo, J. Yoon, K. S. Jin, S. Jin, H. Sato, Y. Ozaki, M. M. Satkowski, I. Noda, and M. Ree, J. Phys. Chem. B, 112, 4571 (2008).

    Article  CAS  Google Scholar 

  28. J. Bolze, J. Kim, J. Y. Huang, S. Rah, H. S. Youn, B. Lee, T. J. Shin, and M. Ree, Macromol Res., 10, 2 (2002).

    Article  CAS  Google Scholar 

  29. J. Yoon, K.-W. Kim, J. Kim, K. Heo, K. S. Jin, S. Jin, T. J. Shin, B. Lee, Y. Rho, B. Ahn, and M. Ree, Macromol. Res., 16, 575 (2008).

    Article  CAS  Google Scholar 

  30. Y. Rho, J. Min, J. Yoon, B. Ahn, S. Jung, K. Kim, P. Shah, J.-S. Lee, and M. Ree, NPG Asia Materials, 4, e29 (2012).

    Article  Google Scholar 

  31. W. Kwon, Y. Rho, K. Kamoshida, K. H. Kwon, Y. C. Jeong, J. Kim, H. Misaka, T. J. Shin, J. Kim, K.-W. Kim, K. S. Jin, T. Chang, H. Kim, T. Satoh, T. Kakuchi, and M. Ree, Adv. Funct. Mater., 22, 5194 (2012).

    Article  CAS  Google Scholar 

  32. W. Kwon, B. Ahn, D. M. Kim, Y.-G. Ko, S. G. Hahm, Y. Kim, H. Kim, and M. Ree, J. Phys. Chem. C, 115, 19355 (2011).

    Article  CAS  Google Scholar 

  33. B. Ahn, T. Hirai, S. Jin, Y. Rho, K.-W. Kim, M.-A. Kakimoto, P. Gopalan, T. Hayakawa, and M. Ree, Macromolecules, 43, 10568 (2010).

    Article  CAS  Google Scholar 

  34. T. J. Shin, B. Lee, B. S. Seong, Y. S. Han, C.-H. Lee, H. H. Song, R. S. Stein, and M. Ree, Polymer, 51, 5799 (2010).

    Article  CAS  Google Scholar 

  35. S. Jin, T. Higashihara, K. S. Jin, J. Yoon, K. Heo, J. Kim, K.-W. Kim, A. Hirao, and M. Ree, J. Phys. Chem. B, 114, 6247 (2010).

    Article  CAS  Google Scholar 

  36. K. S. Jin, S. R. Shin, B. Ahn, S. Jin, Y. Rho, H. Kim, S. J. Kim, and M. Ree, J. Phys. Chem. B, 114, 4783 (2010).

    Article  CAS  Google Scholar 

  37. W. Ruland, J. Appl. Cryst., 4, 70 (1971).

    Article  Google Scholar 

  38. J. T. Koberstein and R. S. Stein, J. Polym. Sci. Part B: Polym. Phys., 21, 2181 (1983).

    CAS  Google Scholar 

  39. F. J. Medellin-Rodriguezx, P. J. Phillips, and J. S. Lin, Macromolecules, 29, 7491 (1996).

    Article  Google Scholar 

  40. U. Siemann and W. Ruland, Colloid Polym. Sci., 260, 999 (1982).

    Article  CAS  Google Scholar 

  41. C. G. Vonk and G. Kortleve, Colloid Polym. Sci., 220, 19 (1967).

    CAS  Google Scholar 

  42. B. Goderis, H. Reynaers, M. H. J. Koch, and V. B. F. Mathot, J. Polym. Sci. Part B: Polym. Phys., 37, 1715 (1999).

    Article  CAS  Google Scholar 

  43. G. R. Strobl and M. Schneider, J. Polym. Sci. Part B: Polym. Phys., 18, 1343 (1980).

    CAS  Google Scholar 

  44. J. J. Hermans, Recueil Trav. Chem. Pay-Bas, 63, 5 (1944).

    Google Scholar 

  45. R. Hoseman and S. N. Bagchi, Direct Analysis of Diffraction by Matter, North-Holland, Amsterdam, 1962.

    Google Scholar 

  46. B. Crist, J. Macromol. Sci., 39, 493 (2000).

    Article  Google Scholar 

  47. W. Ruland, Colloid Polym. Sci., 255, 417 (1977).

    Article  CAS  Google Scholar 

  48. N. Stribeck and W. Ruland, J. Appl. Crystallogr., 11, 535 (1978).

    Article  CAS  Google Scholar 

  49. T. Albrecht and G. Strobl, Macromolecules, 29, 783 (1996).

    Article  CAS  Google Scholar 

  50. R. Verma, H. Marrand, and B. S. Hsiao, Macromolecules, 29, 7767 (1996).

    Article  CAS  Google Scholar 

  51. C. Santa Cruz, N. Stribeck, and H. G. Zachmann, Macromolecules, 24, 5980 (1991).

    Article  Google Scholar 

  52. Z. Xia, H.-J. Sue, Z. Wang, C. A. Avila-Orta, and B. S. Hsiao, J. Macromol. Sci. Part B: Physics, 40, 625 (2001).

    Article  Google Scholar 

  53. R. Yamadera and M. Murano, J. Polym. Sci. Part A-1, 5, 2259 (1967).

    Article  CAS  Google Scholar 

  54. C. R. Choe and K. H. Lee, Polym. Eng. Sci., 29, 801 (1988).

    Article  Google Scholar 

  55. Y. Kitano, Y. Kinoshita, and T. Ashida, Polymer, 36, 1947 (1995).

    Article  CAS  Google Scholar 

  56. E. W. Fischer and S. Fakirov, J. Mater. Sci., 11, 1041 (1976).

    Article  CAS  Google Scholar 

  57. B. Wunderlich, Polym. Eng. Sci., 18, 431 (1978).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Division of Advanced Materials Science, Department of Chemistry, Center for Electro-Photo Behaviors in Advanced Molecular Systems, Pohang Accelerator Laboratory, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and Technology, Gyeongbuk, 790-784, Korea

    Young Yong Kim, Kyuyoung Heo, Kwang-Woo Kim, Jehan Kim, Tae Joo Shin & Moonhor Ree

  2. SK Chemicals, Chemical Research Institute, Gyeonggi, 463-400, Korea

    Jong Ryang Kim & In Sun Yoon

Authors
  1. Young Yong Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kyuyoung Heo
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kwang-Woo Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jehan Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Tae Joo Shin
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jong Ryang Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. In Sun Yoon
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Moonhor Ree
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jong Ryang Kim or Moonhor Ree.

Additional information

Y. Y. Kim and K. Heo equally contributed to this study.

The image from this article is used as the cover image of the Volume 22, Issue 2.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Cite this article

Kim, Y.Y., Heo, K., Kim, KW. et al. Time-resolved synchrotron X-ray scattering studies on crystallization behaviors of poly(ethylene terephthalate) copolymers containing 1,4-cyclohexylenedimethylene units. Macromol. Res. 22, 194–202 (2014). https://doi.org/10.1007/s13233-014-2020-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13233-014-2020-2

Keywords

Search

Navigation