Citation: Min Lu, Xiang Zhu, Xiao-hong Li, Xiao-ming Yang, Ying-feng Tu. Synthesis of Cyclic Oligo(ethylene adipate)s and Their Melt Polymerization to Poly(ethylene adipate)[J]. Chinese Journal of Polymer Science, ;2017, 35(9): 1051-1060. doi: 10.1007/s10118-017-1951-4 shu

Synthesis of Cyclic Oligo(ethylene adipate)s and Their Melt Polymerization to Poly(ethylene adipate)

Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China

Corresponding author: Ying-feng Tu, tuyingfeng@suda.edu.cn
Received Date: 8 March 2017
Revised Date: 5 April 2017
Accepted Date: 6 April 2017

Fund Project: the National Natural Science Foundation of China 21474067

We present here the first synthesis of cyclic oligo(ethylene adipate)s (COEAs) via pseudo-high dilution condensation reaction of adipoyl chloride with ethylene glycol, and the synthesis of corresponding poly(ethylene adipate) (PEA) via the melt polymerization of COEAs. The structure of COEAs was characterized and proved by ¹H-NMR and MALDI-TOF mass measurements. The effects of organic base, reaction temperature and the ratio of adipoyl chloride to ethylene glycol on the yield of COEAs were studied, and the optimum reaction condition was revealed. PEA, a diacid and diol based semi-crystalline green aliphatic polyester, was synthesized by the melt polymerization of COEAs using Ti(n-C₄H₉O)₄ as catalyst and 1, 10-decanediol as initiator at 200℃, which follows the polycondensation-coupling ring-opening polymerization method. Our strategy should be applicable to the synthesis of versatile aliphatic polyesters based on diacid and diol monomers, which have potential applications as biocompatible and biodegradable materials.
- Cyclic oligoesters,
- Pseudo-high dilution reaction condition,
- Polycondensation-coupling ring-opening polymerization,
- Aliphatic polyesters
1. [1]
  Bari, S.S., Chatterjee, A. and Mishra, S., Polym. Rev., 2016, 56(2): 287 doi: 10.1080/15583724.2015.1118123
2. [2]
  Lu, L., Yaszemski, M.J. and Mikos, A.G., Biomaterials, 2001, 22(24): 3345 doi: 10.1016/S0142-9612(01)00172-7
3. [3]
  Lim, S.T., Hyun, Y.H., Choi, H.J. and Jhon, M.S., Chem. Mater., 2002, 14(4): 1839 doi: 10.1021/cm010377j
4. [4]
  Surnar, B. and Jayakannan, M., Biomacromolecules, 2016, 17(12): 4075 doi: 10.1021/acs.biomac.6b01608
5. [5]
  Kasuya, K.I., Takagi, K.I., Ishiwatari, S.I., Yoshida, Y. and Doi, Y., Polym. Degrad. Stab., 1998, 59(1-3): 327 doi: 10.1016/S0141-3910(97)00155-9
6. [6]
  He, Y.S., Zeng, J.B., Li, S.L. and Wang, Y.Z., Thermochim. Acta, 2012, 529: 80 doi: 10.1016/j.tca.2011.11.031
7. [7]
  Qiu, S., Su, Z. and Qiu, Z., Ind. Eng. Chem. Res., 2016, 55(39): 10286 doi: 10.1021/acs.iecr.6b02654
8. [8]
  Lv, A., Cui, Y., Du, F.S. and Li, Z.C., Macromolecules, 2016, 49(22): 8449 doi: 10.1021/acs.macromol.6b01325
9. [9]
  Kuhl, N., Abend, M., Bode, S., Schubert, U.S. and Hager, M.D., J. Appl. Polym. Sci., 2016, 133(44): 44168
10. [10]
  Vandesteene, M., Jacquel, N., Saint-Loup, R., Boucard, N., Carrot, C., Rousseau, A. and Fenouillot, F., Chinese J. Polym. Sci., 2016, 34(7): 873 doi: 10.1007/s10118-016-1805-5
11. [11]
  Diaz, A., Katsarava, R. and Puiggali, J., Int. J. Mol. Sci., 2014, 15(5): 7064 doi: 10.3390/ijms15057064
12. [12]
  Zhao, J.B., Wu, X.F. and Yang, W.T., J. Appl. Polym. Sci., 2004, 92(5): 3333 doi: 10.1002/(ISSN)1097-4628
13. [13]
  Huang, C.Q., Luo, S.Y., Xu, S.Y., Zhao, J.B., Jiang, S.L. and Yang, W.T., J. Appl. Polym. Sci., 2009, 115(3): 1555
14. [14]
  Xu, S.Y., Shi, Y.H., Zhao, J.B., Jiang, S.L. and Yang, W.T., Polym. Adv. Technol., 2011, 22(12): 2360 doi: 10.1002/pat.v22.12
15. [15]
  Morales-Huerta, J.C., Martínez de Ilarduya, A. and Muñoz-Guerra, S., ACS Sustainable Chem. Eng., 2016, 4(9): 4965 doi: 10.1021/acssuschemeng.6b01302
16. [16]
  Brunelle, D.J., Bradt, J.E., Serth-Guzzo, J., Takekoshi, T., Evans, T.L., Pearce, E.J. and Wilson, P.R., Macromolecules, 1998, 31(15): 4782 doi: 10.1021/ma971491j
17. [17]
  Youk, J.H., Kambour, R.P. and MacKnight, W.J., Macromolecules, 2000, 33(10): 3594 doi: 10.1021/ma991838d
18. [18]
  Pepels, M.P.F., van der Sanden, F., Gubbels, E. and Duchateau, R., Macromolecules, 2016, 49(12): 4441 doi: 10.1021/acs.macromol.6b00744
19. [19]
  Xu, Q.Z., Chen, J.Y., Huang, W.C., Qu, T.G., Li, X.H., Li, Y., Yang, X.M. and Tu, Y.F., Macromolecules, 2013, 48(18): 7274
20. [20]
  Chen, J.Y., Chen, D.X., Huang, W.C., Yang, X.M., Li, X.H., Tu, Y.F. and Zhu, X.L., Polymer, 2016, 107: 29 doi: 10.1016/j.polymer.2016.11.001
21. [21]
  Zhu, X., Gu, J.L., Li, X.H., Yang, X.M., Wang, L., Li, Y.J., Li, H. and Tu, Y.F., Polym. Chem., 2017, 8: 1953 doi: 10.1039/C7PY00068E
22. [22]
  Dell'Olio, C., Leonard, S., Dao, B., Varley, R.J. and Pingkarawat, K., J. Mater. Sci., 2015, 50(24): 8073 doi: 10.1007/s10853-015-9375-4
23. [23]
  Morales-Huerta, J.C., Martínez de Ilarduya, A. and Muñoz-Guerra, S., Polymer, 2016, 87: 148 doi: 10.1016/j.polymer.2016.02.003
24. [24]
  Nakayama, Y., Sakaguchi, K., Tanaka, R., Cai, Z. and Shiono, T., Macromol. Symp., 2015, 350(1): 7 doi: 10.1002/masy.v350.1
25. [25]
  Zhang, D., Hillmyer, M.A. and Tolman, W.B., Macromolecules, 2004, 37(22): 8198 doi: 10.1021/ma048092q
26. [26]
  Goodman, I. and Nesbitt, B.F., Polymer, 1960, 1: 384 doi: 10.1016/0032-3861(60)90048-3
27. [27]
  Siriphannon, P. and Monvisade, P., Bull. Mater. Sci., 2013, 36(1): 121 doi: 10.1007/s12034-013-0427-6
28. [28]
  Monvisade, P. and Loungvanidprapa, P., Eur. Polym. J., 2007, 43(8): 3408 doi: 10.1016/j.eurpolymj.2007.05.009
29. [29]
  Choi, W.J., Kim, S.H., Kim, Y.J. and Kim, S.C., Polymer, 2004, 45(17): 6045 doi: 10.1016/j.polymer.2004.06.033
30. [30]
  Wang, H.J., Feng, H.P., Wang, X.C., Du, Q.C. and Yan, C., Chinese J. Polym. Sci., 2015, 33(6): 823 doi: 10.1007/s10118-015-1627-x
31. [31]
  Taggi, A.E., Wack, H., Hafez, A.M., France, S. and Lectka, T., Org. Lett., 2002, 4(4): 627 doi: 10.1021/ol0172525
32. [32]
  Paull, D.H., Weatherwax, A. and Lectka, T., Tetrahedron, 2009, 65(34): 6771 doi: 10.1016/j.tet.2009.05.079
33. [33]
  Hyatt, J. A. and Raynolds, P. W. , "Organic reactions", John Wiley & Sons, 1994, p. 159
34. [34]
  Wu, J., Qu, T.G., Gao, L.F., Yang, X.M., Li, X.H., Tu, Y.F. and Zhu, X.L., Chinese J. Polym. Sci., 2015, 33(8): 1069 doi: 10.1007/s10118-015-1675-2
35. [35]
  Chen, D.X., Gao, L.F., Li, X.H. and Tu, Y.F., Chinese J. Polym. Sci., 2017, 35(5): 681 doi: 10.1007/s10118-017-1919-4
36. [36]
  Wu, H. and Qiu, Z., Ind. Eng. Chem. Res., 2012, 51(40): 13323 doi: 10.1021/ie301968f
37. [37]
  Lugito, G. and Woo, E.M., Soft matter, 2015, 11(5): 908 doi: 10.1039/C4SM02489C
38. [38]
  Rohindra, D., Kuboyama, K. and Ougizawa, T., Eur. Polym. J., 2012, 48(10): 1768 doi: 10.1016/j.eurpolymj.2012.07.013
39. [39]
  Liang, R., Chen, Y.C., Zhang, C.Q., Yin, J., Liu, X.L., Wang, L.K. and Yang, J.J., Chinese J. Polym. Sci., 2017, 35(4): 558 doi: 10.1007/s10118-017-1917-6
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