화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Macromolecular Research, Vol.29, No.8, 543-550, August, 2021
DOI10.1007/s13233-021-9063-y  Export Citation
Thermoreversible and Recycling Properties of Ethylene Propylene Diene Rubber Based on Diels-Alder Reaction
Chong Sun1, Yehua Jiang1, Zhifei Zhang1, 2, †, Shugao Zhao1, †, and Laina Guo3
  • 1Key Laboratory of Rubber-plastics, Ministry of Education/Shandong Provincial Key Laboratory of Rubber-Plastics, Qingdao University of Science & Technology, Qingdao 266042, P. R. China
  • 2College of Chemical Engineering and Safety, Binzhou University, Binzhou 256601, P. R. China
  • 3Hutchinson, research center, Rue Gustave Nourry, Chalette sur Loing, 45120, France
E-mail:,
The preparation and properties of thermoreversible ethylene propylene diene rubber (EPDM) based on reversible Diels-Alder reaction were investigated. The reversible cross-linking ethylene propylene diene rubber was prepared by a two-step method. The EPDM which was grafted with maleic anhydride (MA) was firstly modified by furfurylamine to graft furan groups on rubber backbone, and then crosslinked with bismaleimide (BMI) via a Diels-Alder reaction. At room temperature, thermoreversible cross-linking EPDM exhibited excellent mechanical properties. The molar ratio between BMI and MA was studied, and it was found that too high and too low ratios were not conducive to the formation of high cross-linking density network. When the molar ratio between BMI and MA was 0.9, the cross-linking EPDM had the best mechanical property, with tensile strength of 2.3 MPa and the elongation at break of 312%. The dynamic mechanical analysis and dissolution experiments showed that the reversible Diels-Alder reaction at high temperatures led to the de-crosslinking of rubber networks. Despite the presence of a small number of side effects, the EPDM obtained by Diels-Alder reaction showed a better reshaping ability, and it could be recycled several times.
Keywords:cross-linking network;Diels-Alder reaction;ethylene propylene diene rubber;recycling properties;thermoreversible
  1. Vieyres A, Perez-Aparicio R, Albouy PA, Sanseau O, Saalwachter K, Long DR, Sotta P, Macromolecules, 46(3), 889 (2013)
  2. Velez JS, Velasquez S, Giraldo D, Polym. Test, 56, 1 (2016)
  3. Hosseini SM, Razzaghi-Kashani M, Polymer, 133, 8 (2017)
  4. Rabiei S, Shojaei A, Eur. Polym. J., 81, 98 (2016)
  5. Smith RF, Boothroyd SC, Thompson RL, Khosravi E, Green Chem., 18, 3448 (2016)
  6. Noordermeer J, Myhre M, Saiwari S, Dierkes W, Rubber Chem. Technol., 85, 408 (2012)
  7. Fukumori K, Matsushita M, Okamoto H, Sato N, Suzuki Y, Takeuchi K, JSAE Rev., 23, 259 (2002)
  8. Molanorouzi M, Mohaved SO, Polym. Degrad. Stabil., 128, 115 (2016)
  9. Movahed SO, Ansarifar A, Zohuri G, Ghaneie N, Kermany Y, J. Elastom. Plast., 48, 122 (2014)
  10. Mangun CL, Mader AC, Sottos NR, White SR, Polymer, 51(18), 4063 (2010)
  11. Zuev VV, Lee J, Kostromin SV, Bhattacharyya D, Mater. Lett., 94, 79 (2013)
  12. Such GK, Johnston APR, Liang K, Caruso F, Prog. Polym. Sci, 37, 985 (2012)
  13. Kloxin CJ, Scott TF, Adzima BJ, Bowman CN, Macromolecules, 43(6), 2643 (2010)
  14. Hansen CJ, Wu W, Toohey KS, Sottos NR, White SR, Lewis JA, Adv. Mater., 21(41), 4143 (2009)
  15. Peterson AM, Jensen RE, Palmese GR, ACS Appl. Mater. Interfaces, 2, 2169 (2010)
  16. Tian Q, Rong MZ, Zhang MQ, Yuan YC, Polym. Int., 59, 1339 (2010)
  17. Polgar LM, Criscitiello F, van Essen M, Araya-Hermosilla R, Migliore N, Lenti M, Raffa P, Picchioni F, Pucci A, Nanomaterials, 8 (2018)
  18. Kuang X, Liu GM, Dong X, Wang DJ, Macromol. Mater. Eng., 301, 535 (2016)
  19. Canadell J, Goossens H, Klumperman B, Macromolecules, 44(8), 2536 (2011)
  20. Hernandez M, Grande AM, Dierkes W, Bijleveld JC, van der Zwaag S, Garcia SJ, ACS Sustain. Chem. Eng., 4, 5776 (2016)
  21. Xiang HP, Rong MZ, Zhang MQ, ACS Sustain. Chem. Eng., 4, 2715 (2016)
  22. Xiang HP, Rong MZ, Zhang MQ, Polymer, 108, 339 (2017)
  23. Cordier P, Tournilhac F, Soulie-Ziakovic C, Leibler L, Nature, 451, 977 (2008)
  24. Chen Y, Kushner AM, Williams GA, Guan Z, Nat. Chem., 4, 467 (2012)
  25. Kang J, Son D, Wang GN, Liu Y, Lopez J, Kim Y, Oh JY, Katsumata T, Mun J, Lee Y, Jin L, Tok JB, Bao Z, Adv. Mater., 30, e17068 (2018)
  26. Huang Y, Zhong M, Huang Y, Zhu M, Pei Z, Wang Z, Xue Q, Xie X, Zhi C, Nat. Commun., 6, 10310 (2015)
  27. Zhang ZF, Liu XT, Yang K, Zhao SG, Macromol. Res., 27(8), 803 (2019)
  28. Yu D, Zhao XX, Zhou CJ, Zhang CJ, Zhao SG, Macromol. Chem. Phys., 218, 160051 (2017)
  29. Han YY, Wu XD, Zhang XX, Lu CH, ACS Appl. Mater. Interfaces, 9, 20106 (2017)
  30. Jia XY, Mei JF,, Lai JC, Li CH, You XZ, Chem. Commun., 51, 8928 (2015)
  31. Miwa Y, Kurachi J, Kohbara Y, Kutsumizu S, Commun. Chem., 1 (2018)
  32. Zhang ZF, Yang K, Zhao SG, Guo LN, Chinese J. Polym. Sci., 37, 700 (2019)
  33. Khimi SR, Syamsinar SN, Najwa TNL, Mater. Today Proceedings, 17, 1064 (2019)
  34. Das A, Sallat A, Bohme F, Sarlin E, Vuorinen J, ennemann NV, Heinrich G, Stockelhube KW, Polymers, 10 (2018)
  35. Gandini A, Prog. Polym. Sci, 38, 1 (2013)
  36. Toncelli C, De Reus DC, Picchioni F, Broekhuis AA, Macromol. Chem. Phys., 213, 157 (2012)
  37. Moustafa MMA, Gillies ER, Macromolecules, 46(15), 6024 (2013)
  38. Turkenburg DH, Fischer HR, Polymer, 79, 187 (2015)
  39. Liu YL, Chuo TW, Polym. Chem., 4 (2013)
  40. Chen X, Dam MA, Ono K, Mal A, Shen H, Nutt SR, Sheran K, Wudl F, Science, 295, 1698 (2002)
  41. Chen XX, Wudl F, Mal AK, Shen HB, Nutt SR, Macromolecules, 36(6), 1802 (2003)
  42. Gamlin CD, Dutta NK, Choudhury NR, Polym. Degrad. Stabil., 80, 525 (2003)
  43. Polgar LM, van Duin M, Broekhuis AA, Picchioni F, Macromolecules, 48(19), 7096 (2015)
  44. Wang A, Niu H, He Z, Li Y, Polym. Chem., 8, 4494 (2017)
  45. Polgar LM, Kingma A, Roelfs M, van Essen M, van Duin M, Picchioni F, Eur. Polym. J., 90, 150 (2017)
  46. Van der Mee MAJ, Goossens JGP, Van Duin M, J. Polym. Sci. A: Polym. Chem., 46(5), 1810 (2008)
  47. Flory PJ, J. Chem. Phys., 18, 108 (1950)
  48. Mikroyannidis JA, J. Polym. Sci. A: Polym. Chem., 30, 125 (1992)
  49. van der Mee MAJ, Goossens JGP, van Duin M, Polymer, 49(5), 1239 (2008)
  50. Liu XX, Du PF, Liu L, Zheng Z, Wang XL, Joncheray T, Zhang YF, Polym. Bull., 70(8), 2319 (2013)
  51. Stamboliyska BA, Binev YI, Radomirska VB, Tsenov JA, Juchnovski IN, J. Mol. Struct., 516, 237 (2000)
  52. Orza RA, Magusin PCMM, Litvinov VM, van Duin M, Michels MAJ, Macromolecules, 40(25), 8999 (2007)