Citation: Chong He, Xiang Zhu, Xiao-Hong Li, Xiao-Ming Yang, Ying-Feng Tu. Thermodynamics of Aromatic Cyclic Ester Polymerization in Bulk[J]. Chinese Journal of Polymer Science, ;2019, 37(1): 89-93. doi: 10.1007/s10118-018-2161-4 shu

Thermodynamics of Aromatic Cyclic Ester Polymerization in Bulk

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

Corresponding author: Ying-Feng Tu, tuyingfeng@suda.edu.cn
Received Date: 19 April 2018
Revised Date: 11 May 2018
Accepted Date: 19 May 2018
Available Online: 14 June 2018

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.
- Lactone,
- Polyester,
- Polycondensation-coupling ring-opening polymerization,
- Thermodynamic parameters
1. [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. doi: 10.1021/ma101202g
2. [2]
  Pascual, A.; Sardón, 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 ε-caprolactone and TBD-guanidine organic catalyst. J. Polym. Sci., Part A: Polym. Chem. 2015, 53(4), 552-561. doi: 10.1002/pola.v53.4
3. [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.
4. [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. doi: 10.1007/s10118-017-1951-4
5. [5]
  Song, Q.; Hu, S.; Zhao, J.; Zhang, G. Organocatalytic copolymerization of mixed type monomers. Chinese J. Polym. Sci. 2017, 35(5), 581-601. doi: 10.1007/s10118-017-1925-6
6. [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. doi: 10.1021/mz500401u
7. [7]
  Pascual, A.; Sardón, 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 ε-caprolactone and TBD-guanidine organic catalyst. J. Polym. Sci., Part A: Polym. Chem. 2015, 53(4), 552-561. doi: 10.1002/pola.v53.4
8. [8]
  Ofstead, E. A.; Calderon, N. Equilibrium ring-opening polymerization of mono- and multicyclic unsaturated monomers. Makromol. Chem. 1972, 154(1), 21-34. doi: 10.1002/macp.1972.021540102
9. [9]
  Duda, A.; Kowalski, A.; Libiszowski, J.; Penczek, S. Thermodynamic and kinetic polymerizability of cyclic esters. Macromol. Symp. 2005, 224(1), 71-84. doi: 10.1002/(ISSN)1521-3900
10. [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. doi: 10.1039/C5PY00762C
11. [11]
  Schneiderman, D. K.; Hillmyer, M. A. Aliphatic polyester block polymer design. Macromolecules 2016, 49(7), 2419-2428. doi: 10.1021/acs.macromol.6b00211
12. [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. [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. doi: 10.1021/ma00069a031
14. [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. doi: 10.1021/ja00162a049
15. [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. doi: 10.1021/ma971491j
16. [16]
  Brunelle, D. J. Cyclic oligomer chemistry. J. Polym. Sci., Part A: Polym.Chem. 2008, 46(4),1151-1164. doi: 10.1002/pola.v46:4
17. [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. doi: 10.1007/s10965-008-9182-6
18. [18]
  Conzatti, L.; Utzeri, R.; Hodge, P.; Stagnaro, P. A novel tin-based 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. doi: 10.1039/C4RA12983K
19. [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. doi: 10.1021/acs.macromol.6b00744
20. [20]
  Carlos Morales-Huerta, J.; Martínez de Ilarduya, A.; Muñoz-Guerra, S. Poly(alkylene 2,5-furandicarboxylate)s (PEF and PBF) by ring opening polymerization. Polymer 2016, 87, 148-158. doi: 10.1016/j.polymer.2016.02.003
21. [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. doi: 10.1039/C7PY01627A
22. [22]
  Morales-Huerta, J. C.; Ilarduya, A.; Muñoz-Guerra, S. Blocky poly(ε-caprolactone-co-butylene 2,5-furandicarboxylate) copolyesters via enzymatic ring opening polymerization. J. Polym. Sci., Part A: Polym. Chem. 2018, 56(3), 290-299. doi: 10.1002/pola.v56.3
23. [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. doi: 10.1039/C6RA21135F
24. [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. doi: 10.1039/C7GC02521A
25. [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-b-PTMO-b-PTT)n multiblock copolymers. Macromolecules 2013, 46(18), 7274-7281. doi: 10.1021/ma400969a
26. [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. doi: 10.1016/j.polymer.2016.11.001
27. [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. doi: 10.1039/C7PY00068E
28. [28]
  Zhang, M.; Gu, J.; Zhu, X.; Gao, L.; Li, X.; Yang, X.; Tu, Y.; Li, C. Y. Synthesis of poly(butylene terephthalate)-block-poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) multiblock terpolymers via a facile PROP method. Polymer 2017, 130, 199-208. doi: 10.1016/j.polymer.2017.10.010
29. [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. doi: 10.1016/j.polymer.2013.10.043
30. [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. doi: 10.1021/acs.macromol.6b00744
31. [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.
32. [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. doi: 10.1021/ma000457t
33. [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. doi: 10.1021/ma0501287
34. [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. doi: 10.1021/ma000278b
35. [35]
  Scheirs, J. and Long, T. E. in Modern Polyesters: Chemistry and Technology of Polyesters and Copolyesters, John Wiley & Sons, 2005.
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