Skip to main content
SpringerLink
Log in

Thermodynamics of Aromatic Cyclic Ester Polymerization in Bulk

  • Article
  • Published:
Chinese Journal of Polymer Science Aims and scope Submit manuscript

Abstract

We present here the thermodynamic investigation of in situ cascade polycondensation-coupling ring-opening polymerization (PROP) for three cyclic aromatic ester monomers, i.e., cyclic oligo(2-methyl-1,3-propylene terephthalate)s (COMPTs), cyclic oligo(neopentylene terephthalate)s (CONTs) and cyclic oligo(2-methyl-2-propyl-1,3-propylene terephthalate)s (COMPPTs). The equibrium monomer to polymer weight ratio in bulk at different polymerization temperatures for each monomer was estimated by the size exclusion chromatography (SEC), and the thermodynamic parameters were estimated by Dainton equation. Quite different from the thermodynamics of aliphatic lactones polymerization, which is an exothermic process with entropy reduction, our results showed the polymerization thermodynamics for three cyclic aromatic ester monomers was a weak exothermic process with slight entropy increment, i.e., a both enthalpy and entropy driving process. Among them, CONTs showed the largest value of enthalpy change, due to its symmetric dimethyl substitution on β-position of propandiol segments.

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. Zhao, W.; Cui, D.; Liu, X.; Chen, X. Facile synthesis of hydroxyl-ended, highly stereoregular, star-shaped poly(lactide) from immortal ROP of rac-lactide and kinetics study. Macromolecules 2010, 43(16), 6678–6684

    Article  CAS  Google Scholar 

  2. Pascual, A.; Sardon, H.; Ruipérez, F.; Gracia, R.; Sudam, P.; Veloso, A.; Mecerreyes, D. Experimental and computational studies of ring-opening polymerization of ethylene brassylate macrolactone and copolymerization with e-caprolactone and TBD-guanidine organic catalyst. J. Polym. Sci., Part A: Polym. Chem. 2015, 53(4), 552–561

    Article  CAS  Google Scholar 

  3. Jitonnom, J.; Meelua, W. Cationic ring-opening polymerization of cyclic carbonates and lactones by group 4 metallocenes: a theoretical study on mechanism and ring-strain effects. J. Theor. Comput. Chem. 2016, 16(01), 1750003

    Article  CAS  Google Scholar 

  4. Lu, M.; Zhu, X.; Li, X.; Yang, X.; Tu, Y. Synthesis of cyclic oligo(ethylene adipate)s and their melt polymerization to poly(ethylene adipate). Chinese J. Polym. Sci. 2017, 35(9), 1051–1060

    Article  CAS  Google Scholar 

  5. Song, Q.; Hu, S.; Zhao, J.; Zhang, G. Organocatalytic copolymerization of mixed type monomers. Chinese J. Polym. Sci. 2017, 35(5), 581–601

    Article  CAS  Google Scholar 

  6. Pascual, A.; Sardon, H.; Veloso, A.; Ruipérez, F.; Mecerreyes, D. Organocatalyzed synthesis of aliphatic polyesters from ethylene brassylate: a cheap and renewable macrolactone. ACS Macro Lett. 2014, 3(9), 849–853

    Article  CAS  Google Scholar 

  7. Pascual, A.; Sardon, H.; Ruipérez, F.; Gracia, R.; Sudam, P.; Veloso, A.; Mecerreyes, D. Experimental and computational studies of ring-opening polymerization of ethylene brassylate macrolactone and copolymerization with e-caprolactone and TBD-guanidine organic catalyst. J. Polym. Sci., Part A: Polym. Chem. 2015, 53(4), 552–561

    Article  CAS  Google Scholar 

  8. Ofstead, E. A.; Calderon, N. Equilibrium ring-opening polymerization of mono-and multicyclic unsaturated monomers. Makromol. Chem. 1972, 154(1), 21–34

    Article  CAS  Google Scholar 

  9. Duda, A.; Kowalski, A.; Libiszowski, J.; Penczek, S. Thermodynamic and kinetic polymerizability of cyclic esters. Macromol. Symp. 2005, 224(1), 71–84

    Article  CAS  Google Scholar 

  10. Li, X.; Li, H.; Zhao, Y.; Tang, X.; Ma, S.; Gong, B.; Li, M. Facile synthesis of well-defined hydrophilic polyesters as degradable poly(ethylene glycol)-like biomaterials. Polym. Chem. 2015, 6(36), 6452–6456

    Article  CAS  Google Scholar 

  11. Schneiderman, D. K.; Hillmyer, M. A. Aliphatic polyester block polymer design. Macromolecules 2016, 49(7), 2419–2428

    Article  CAS  Google Scholar 

  12. Steele, R. in “Polyester: 50 years of achievement”, Brunnschweiler, D. and Hearle, J. S. (Eds), The Textile Institute, manchester, UK, 1993, pp. 48–51

  13. Turner, S. R.; Voit, B. I.; Mourey, T. H. All-aromatic hyperbranched polyesters with phenol and acetate end groups: synthesis and characterization. Macromolecules 1993, 26(17), 4617–4623

    Article  CAS  Google Scholar 

  14. Brunelle, D. J.; Boden, E. P.; Shannon, T. G. Remarkably selective formation of macrocyclic aromatic carbonates: versatile new intermediates for the synthesis of aromatic polycarbonates. J. Am. Chem. Soc. 1990, 112(6), 2399–2402

    Article  CAS  Google Scholar 

  15. Brunelle, D. J.; Bradt, J. E.; Serth-Guzzo, J.; Takekoshi, T.; Evans, T. L.; Pearce, E. J.; Wilson, P. R. Semicrystalline polymers via ring-opening polymerization: preparation and polymerization of alkylene phthalate cyclic oligomers. Macromolecules 1998, 31(15), 4782–4790

    Article  CAS  PubMed  Google Scholar 

  16. Brunelle, D. J. Cyclic oligomer chemistry. J. Polym. Sci., Part A: Polym. Chem. 2008, 46(4), 1151–1164

    Article  CAS  Google Scholar 

  17. Monvisade, P.; Loungvanidprapa, P. Synthesis of poly(ethylene terephthalate-co-isophthalate) via ring-opening polymerization of their cyclic oligomers. J. Polym. Res. 2008, 15(5), 381–387

    Article  CAS  Google Scholar 

  18. Conzatti, L.; Utzeri, R.; Hodge, P.; Stagnaro, P. A novel tinbased imidazolium-modified montmorillonite catalyst for the preparation of poly(butylene terephthalate)-based nanocomposites using in situ entropically-driven ring-opening polymerization. RSC Adv. 2015, 5(8), 6222–6231

    Article  CAS  Google Scholar 

  19. Pepels, M. P. F.; van der Sanden, F.; Gubbels, E.; Duchateau, R. Catalytic ring-opening (co)polymerization of semiaromatic and aliphatic (macro)lactones. Macromolecules 2016, 49(12), 4441–4451

    Article  CAS  Google Scholar 

  20. Carlos Morales-Huerta, J.; Martinez de Ilarduya, A.; Munoz-Guerra, S. Poly(alkylene 2, 5-furandicarboxylate)s (PEF and PBF) by ring opening polymerization. Polymer 2016, 87, 148–158

    Article  CAS  Google Scholar 

  21. Sousa, A. F.; Guigo, N.; Pozycka, M.; Delgado, M.; Soares, J.; Mendonca, P. V.; Coelho, J. F. J.; Sbirrazzuoli, N.; Silvestre, A. J. D. Tailored design of renewable copolymers based on poly(1, 4-butylene 2, 5-furandicarboxylate) and poly(ethylene glycol) with refined thermal properties. Polym. Chem. 2018, 9(6), 722–731

    Article  CAS  Google Scholar 

  22. Morales-Huerta, J. C.; Ilarduya, A.; Munoz-Guerra, S. Blocky poly(e-caprolactone-co-butylene 2, 5-furandicarboxylate) copolyesters via enzymatic ring opening polymerization. J. Polym. Sci., Part A: Polym. Chem. 2018, 56(3), 290–299

    Article  CAS  Google Scholar 

  23. Wu, J.; Xie, H.; Wu, L.; Li, B.; Dubois, P. DBU-catalyzed biobased poly(ethylene 2, 5-furandicarboxylate) polyester with rapid melt crystallization: synthesis, crystallization kinetics and melting behavior. RSC Adv. 2016, 6(103), 101578–101586

    Article  CAS  Google Scholar 

  24. Rabnawaz, M.; Wyman, I.; Auras, R.; Cheng, S. A roadmap towards green packaging: the current status and future outlook for polyesters in the packaging industry. Green Chem. 2017, 19(20), 4737–4753

    Article  CAS  Google Scholar 

  25. Xu, Q.; Chen, J.; Huang, W.; Qu, T.; Li, X.; Li, Y.; Yang, X.; Tu, Y. One pot, one feeding step, two-stage polymerization synthesis and characterization of (PTT-è-PTMO-è-PTT)n multiblock copolymers. Macromolecules 2013, 46(18), 7274–7281

    Article  CAS  Google Scholar 

  26. Chen, J.; Chen, D.; Huang, W.; Yang, X.; Li, X.; Tu, Y.; Zhu, X. A one pot facile synthesis of poly(butylene terephthalate)- block-poly(tetramethylene oxide) alternative multiblock copolymers via PROP method. Polymer 2016, 107, 29–36

    Article  CAS  Google Scholar 

  27. Zhu, X.; Gu, J.; Li, X.; Yang, X.; Wang, L.; Li, Y.; Li, H.; Tu, Y. PROP: an in situ cascade polymerization method for the facile synthesis of polyesters. Polym. Chem. 2017, 8(12), 1953–1962

    Article  CAS  Google Scholar 

  28. Zhang, M.; Gu, J.; Zhu, X.; Gao, L.; Li, X.; Yang, X.; Tu, Y.; Li, C. Y. Synthesis of poly(butylene terephthalate)-blockpoly( ethylene oxide)-block-poly(propylene oxide)-blockpoly( ethylene oxide) multiblock terpolymers via a facile PROP method. Polymer 2017, 130, 199–208

    Article  CAS  Google Scholar 

  29. Chen, J.; Huang, W.; Xu, Q.; Tu, Y.; Zhu, X.; Chen, E. PBT-b- PEO-b-PBT triblock copolymers: Synthesis, characterization and double-crystalline properties. Polymer 2013, 54(25), 6725–6731

    Article  CAS  Google Scholar 

  30. Pepels, M. P.; van der Sanden, F.; Gubbels, E.; Duchateau, R. Catalytic ring-opening (co) polymerization of semiaromatic and aliphatic (macro) lactones. Macromolecules 2016, 49(12), 4441–4451

    Article  CAS  Google Scholar 

  31. Duda, A.; Penczek, S. Thermodynamics, kinetics, and mechanisms of cyclic esters polymerization. In “Polymers from Renewable Resources, American Chemical Society” 2001; Vol. 764, pp 160–198

    Article  CAS  Google Scholar 

  32. Nishida, H.; Yamashita, M.; Endo, T.; Tokiwa, Y. Equilibrium polymerization behavior of 1, 4-dioxan-2-one in bulk. Macromolecules 2000, 33(19), 6982–6986

    Article  CAS  Google Scholar 

  33. Hejl, A.; Scherman, O. A.; Grubbs, R. H. Ring-opening metathesis polymerization of functionalized low-strain monomers with ruthenium-based catalysts. Macromolecules 2005, 38(17), 7214–7218

    Article  CAS  Google Scholar 

  34. Burch, R. R.; Lustig, S. R.; Spinu, M. Synthesis of cyclic oligoesters and their rapid polymerization to high molecular weight. Macromolecules 2000, 33(14), 5053–5064

    Article  CAS  Google Scholar 

  35. Scheirs, J. and Long, T. E. “Modern Polyesters: Chemistry and Technology of Polyesters and Copolyesters”, John Wiley & Sons, 2005

    Google Scholar 

Download references

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Nos. 21474067, 21774090), and a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

Author information

Authors and Affiliations

  1. Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China

    Chong He, Xiang Zhu, Xiao-Hong Li, Xiao-Ming Yang & Ying-Feng Tu

Authors
  1. Chong He
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiang Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiao-Hong Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiao-Ming Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ying-Feng Tu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ying-Feng Tu.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

He, C., Zhu, X., Li, XH. et al. Thermodynamics of Aromatic Cyclic Ester Polymerization in Bulk. Chin J Polym Sci 37, 89–93 (2019). https://doi.org/10.1007/s10118-018-2161-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10118-018-2161-4

Keywords

Search

Navigation