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Unusual Spherulitic Morphology of Poly(propylene fumarate)

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Abstract

Spherulites are the most common crystalline morphology and thus the visual expression of crystal structures for polymers. The diversified patterns have provided intuitive morphology probes for various crystallization behaviors, while the correlations between them are still needed to be enriched. In this work, the complicated spherulitic morphology of poly(propylene fumarate) (PPF), which is sensitive to crystallization temperature, is investigated. PPF melt, respectively, crystallizes into rough spherulites, regularly banded spherulites, and spherulites containing both two kinds of morphology at low, high, and mediate temperatures. By systematically assaying, it is clear that the growth axis along the radial direction changes from a-axis to b-axis as the crystallization temperature increases, which leads to the formation of unique crystallization-temperature-dependent spherulites. Based on detailed characterization of Fourier transform infrared spectroscopy, the packing state of the specific hydrogen bonds of “C=C-H⋯O=C-C=C” in PPF crystal lattices is determined, and furthermore, the mechanism for temperature-dependent selection of growth axes for PPF spherulites in melt is reasonably speculated.

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References

  1. Shtukenberg, A. G.; Punin, Y. O.; Gunn, E.; Kahr, B. Spherulites. Chem. Rev. 2012, 112, 1805–1838.

    Article  CAS  Google Scholar 

  2. Crist, B.; Schultz, J. M. Polymer spherulites: a critical review. Prog. Polym. Sci. 2016, 56, 1–63.

    Article  CAS  Google Scholar 

  3. Gránásy, L.; Pusztai, T.; Tegze, G.; Warren, J. A.; Douglas, J. F. Growth and form of spherulites. Phys. Rev. E 2005, 72, 011605.

    Article  Google Scholar 

  4. Cheng, S. Z. D.; Lotz, B. Nucleation control in polymer crystallization: structural and morphological probes in different length- and time-scales for selection processes. Philos. Trans. R. Soc. A 2003, 361, 517–537.

    Article  CAS  Google Scholar 

  5. Xu, J.; Ye, H.; Zhang, S.; Guo, B. Organization of twisting lamellar crystals in birefringent banded polymer spherulites: a minireview. Crystals 2017, 7, 241.

    Article  CAS  Google Scholar 

  6. Lotz, B.; Miyoshi, T.; Cheng, S. Z. D. 50th Anniversary perspective: polymer crystals and crystallization: personal journeys in a challenging research field. Macromolecules 2017, 50, 5995–6025.

    Article  CAS  Google Scholar 

  7. Woo, E. M.; Lee, M. S. Crystallization in arylate polyesters to periodically ringed assembly. Polym. Cryst. 2018, 1, e10018.

    Google Scholar 

  8. Xu, J.; Guo, B. H.; Zhou, J. J.; Li, L.; Wu, J.; Kowalczuk, M. Observation of banded spherulites in pure poly(L-lactide) and its miscible blends with amorphous polymers. Polymer 2005, 46, 9176–9185.

    Article  CAS  Google Scholar 

  9. Wang, X.; Prud’homme, R. E. Differences between stereocomplex spherulites obtained in equimolar and non-equimolar poly(L-lactide)/poly(D-lactide) blends. Macromol. Chem. Phys. 2011, 212, 691–698.

    Article  CAS  Google Scholar 

  10. Ye, H. M.; Xu, J.; Freudenthal, J.; Kahr, B. On the circular birefringence of polycrystalline polymers: polylactide. J. Am. Chem. Soc. 2011, 133, 13848–13851.

    Article  CAS  Google Scholar 

  11. Point, J. J. Sphérolithes de polyadipate de glycol. Bull. Acad. R. Med. Belg 1953, 39, 455–441.

    Google Scholar 

  12. Keith, H. D.; Padden Jr, F. J. The optical behavior of spherulites in crystalline polymers. Part II. The growth and structure of the spherulites. J. Polym. Sci. 1959, 39, 123–138.

    Article  CAS  Google Scholar 

  13. Keller, A. Investigations on banded spherulites. J. Polym. Sci. 1959, 39, 151–173.

    Article  CAS  Google Scholar 

  14. Price, F. P. On extinction patterns of polymer spherulites. J. Polym. Sci. 1959, 39, 139–150.

    Article  CAS  Google Scholar 

  15. Lotz, B.; Cheng, S. Z. D. Critical assessment of unbalanced surface stresses as the mechanical origin of twisting and scrolling of polymer crystals. Polymer 2005, 46, 577–610.

    Article  CAS  Google Scholar 

  16. Ye, H. M.; Wang, J. S.; Tang, S.; Xu, J.; Feng, X. Q.; Guo, B. H.; Xie, X. M.; Zhou, J. J.. Li L.; Wu, Q.; Chen, G. Q. Surface stress effects on the bending direction and twisting chirality of lamellar crystals of chiral polymer. Macromolecules 2010, 43, 5762–5770.

    Article  CAS  Google Scholar 

  17. Ye, H. M.; Xu, J.; Guo, B. H.; Iwata, T. Left- or right-handed lamellar twists in poly[(R)-3-hydroxyvalerate] banded spherulite: dependence on growth axis. Macromolecules 2009, 42, 694–701.

    Article  CAS  Google Scholar 

  18. Liu, J.; Ye, H. M.; Xu, J.; Guo, B. H. Formation of ring-banded spherulites of α and β modifications in poly(butylene adipate). Polymer 2011, 52, 4619–4630.

    Article  CAS  Google Scholar 

  19. Fraschini, C.; Jiménez, L.; Kalala, B.; Prud’homme, R. E. Polymorphism and cross-nucleation in poly(1,3-dioxolan). Polymer 2012, 53, 188–195.

    Article  CAS  Google Scholar 

  20. Cavallo, D.; Gardella, L.; Portale, G.; Müller, A. J.; Alfonso, G. C. On cross-and self-nucleation in seeded crystallization of isotactic poly(1-butene). Polymer 2013, 54, 4637–4644.

    Article  CAS  Google Scholar 

  21. Zhang, J.; Li, L.; Song, S.; Feng, H.; Chen, P.; Wang, Z.; Gu, Q. Synchronous architecture of ring-banded and non-ring-banded morphology within one spherulite based on in situ ring-opening polymerization of cyclic butylene terephthalate oligomers. RSC Adv. 2016, 6, 94524–94530.

    Article  CAS  Google Scholar 

  22. Fisher, J. P.; Vehof, J. W. M.; Dean, D.; van der Waerden, J. P. C. M.; Holland, T. A.; Mikos, A. G.; Jansen, J. A. Soft and hard tissue response to photocrosslinked poly(propylene fumarate) scaffolds in a rabbit model. J. Biomed. Mater. Res. 2002, 59, 547–556.

    Article  CAS  Google Scholar 

  23. Fisher, J. P.; Dean, D.; Mikos, A. G. Photocrosslinking characteristics and mechanical properties of diethyl fumarate/poly(propylene fumarate) biomaterials. Biomaterials 2002, 23, 4333–4343.

    Article  CAS  Google Scholar 

  24. Lee, K. W.; Wang, S.; Fox, B. C.; Ritman, E. L.; Yaszemski, M. J.; Lu, L. Poly(propylene fumarate) bone tissue engineering scaffold fabrication using stereolithography: effects of resin formulations and laser parameters. Biomacromolecules 2007, 8, 1077–1084.

    Article  CAS  Google Scholar 

  25. Ye, H. M.; Freudenthal, J. H.; Tan, M.; Yang, J.; Kahr, B. Chiroptical differentiation of twisted chiral and achiral polymer crystals. Macromolecules 2019, 52, 8514–8520.

    Article  CAS  Google Scholar 

  26. Ye, H. M.; Wang, R. D.; Liu, J.; Xu, J.; Guo, B. H. Isomorphism in poly(butylene succinate-co-butylene fumarate) and its application as polymeric nucleating agent for poly(butylene succinate). Macromolecules 2012, 45, 5667–5675.

    Article  CAS  Google Scholar 

  27. Kawashima, K.; Kawano, R.; Miyagi, T.; Umemoto, S.; Okui, N. Morphological changes in flat-on and edge-on lamellae of poly(ethylene succinate) crystallized from molten thin films. J. Macromol. Sci., Part B 2003, 42, 889–899.

    Article  Google Scholar 

  28. Ye, H. M.; Tang, Y. R.; Song, Y. Y.; Xu, J.; Guo, B. H.; Zhou, Q. Aliphatic copolyester with isomorphism in limited composition range. Polymer 2014, 55, 5811–5820.

    Article  CAS  Google Scholar 

  29. Ye, H. M.; Liu, P.; Wang, C. X.; Meng, X.; Zhou, Q. Polymorphism regulation in poly(hexamethylene succinate-co-hexamethylene fumarate): altering the hydrogen bonds in crystalline lattice. Polymer 2017, 108, 272–280.

    Article  CAS  Google Scholar 

  30. Ye, H. M.; Wang, J.; Wang, C. S.; Li, H. F. Unique Isodimorphism of poly(decamethylene succinate-ran-decamethylene fumarate): large pseudoeutectic region and fantastic crystallization/melting behavior. Macromolecules 2019, 52, 1447–1457.

    Article  CAS  Google Scholar 

  31. Qi, Z.; Ye, H.; Xu, J.; Chen, J.; Guo, B. Improved the thermal and mechanical properties of poly(butylene succinate-co-butylene adipate) by forming nanocomposites with attapulgite. Colloid. Surfaces A 2013, 421, 109–117.

    Article  CAS  Google Scholar 

  32. Yao, S. F.; Chen, X. T.; Ye, H. M. Investigation of structure and crystallization behavior of poly(butylene succinate) by Fourier transform infrared spectroscopy. J. Phys. Chem. B 2017, 121, 9476–9485.

    Article  CAS  Google Scholar 

  33. Mallapragada, S. K.; Narasimhan, B. Infrared spectroscopy in analysis of polymer crystallinity. Encyclopedia of analytical chemistry: applications, theory and instrumentation, 2006.

  34. Hu, J.; Wang, J.; Wang, M.; Ozaki, Y.; Sato, H.; Zhang, J. Investigation of crystallization behavior of asymmetric PLLA/PDLA blend using Raman Imaging measurement. Polymer 2019, 172, 1–6.

    Article  CAS  Google Scholar 

  35. Xu, Y.; Xu, J.; Sun, Y.; Liu, D.; Guo, B.; Xie, X. Crystallization behavior of poly(butylene succinate-co-propylene succinate)s. Acta Polymerica Sinica (in Chinese) 2006, 1000–1006.

  36. Ding, M.; Yu, J.; He, J.; Zhang, J. An unusual spherulite morphology induced by nano-fillers from a concentrated cellulose/ionic liquid solution. RSC Adv. 2015, 5, 44648–44651.

    Article  CAS  Google Scholar 

  37. Song, G.; Yu, J.; Ding, M.; Zhang, J. A novel cellulose/ionic liquid complex crystal. Cryst. Growth Des. 2018, 18, 4260–4264.

    Article  CAS  Google Scholar 

  38. Lai, Y.; Wang, Y.; Wang, L. L.; Li, X.; Zhao, J. B.; Dong, X.; Wang, D. J. Optical inversion characteristics of PA56 spherulites. Acta Polymerica Sinica (in Chinese) 2020, 51, 1267–1274.

    Google Scholar 

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 21674128) and Science Foundation of China University of Petroleum, Beijing (No. ZX20200097).

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Authors and Affiliations

  1. Department of Materials Science and Engineering, College of New Energy and Materials, China University of Petroleum, Beijing, 102249, China

    Xiao-Yu Meng, Yi Li, Shu-Fang Yao, Xue-Wei Wei & Hai-Mu Ye

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  1. Xiao-Yu Meng
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  2. Yi Li
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  3. Shu-Fang Yao
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Correspondence to Hai-Mu Ye.

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Meng, XY., Li, Y., Yao, SF. et al. Unusual Spherulitic Morphology of Poly(propylene fumarate). Chin J Polym Sci 39, 493–500 (2021). https://doi.org/10.1007/s10118-021-2518-y

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  • DOI: https://doi.org/10.1007/s10118-021-2518-y

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