Citation: Xi-xi Wang, Lu Dai, Su-yun Jie, Bo-geng Li. Synthesis of Carboxyl-terminated Polyolefins via Metathesis Degradation-hydrogenation of Diene Rubbers[J]. Acta Polymerica Sinica, ;2020, 51(3): 277-286. doi: 10.11777/j.issn1000-3304.2019.19171 shu

Synthesis of Carboxyl-terminated Polyolefins via Metathesis Degradation-hydrogenation of Diene Rubbers

State Key Laboratory of Chemical Engineering, College of Chemical Engineering and Biological Engineering, Zhejiang University, Hangzhou 310027

Corresponding author: Su-yun Jie, jiesy@zju.edu.cn
Received Date: 18 September 2019
Revised Date: 21 October 2019

The carboxyl-terminated polydiene is a kind of widely used telechelic liquid rubber, which is commonly used as adhesive for solid rocket propellant, material bonding, sealant, electric insulation or as modifier of epoxy resins. Taking diene rubbers as raw materials, the carboxyl-terminated polydienes were synthesized via olefin metathesis degradation of diene rubbers catalyzed by Grubbs II catalyst ( G2 ) in the presence of maleic acid as a chain transfer agent (CTA). The carboxyl-terminated polyolefins were further prepared by the subsequent chemical hydrogenation with p-toluenesulfonyl hydrazide/tri(n-propyl)amine reagents. The influences of reaction conditions on the molecular weight and molecular weight distribution of products, including reaction time, reaction temperature, molar ratios of C＝C/catalyst and C＝C/chain transfer agent, were investigated. The results indicated that the molecular weight of products could be controlled by varying the molar ratio of C＝C/catalyst or C＝C/chain transfer agent. It turned out that the catalyst was highly active for the metathesis degradation of diene rubbers even if there was no existence of chain transfer agents. The structures of carboxyl-terminated polydienes and polyolefins were characterized by nuclear magnetic resonance spectroscopy (¹H-NMR) and carbon spectrum (¹³C-NMR), infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) and their thermal properties were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). It’s worth noting that the trans-1,4 content of carboxyl-terminated polybutadiene via metathesis degradation greatly increased and the corresponding cis-1,4 content decreased, thus affecting the properties of polymers. After hydrogenation, the carboxyl-terminated polyolefins had better thermal stability than the carboxyl-terminated polydienes.
- Diene rubber,
- Olefin metathesis,
- Hydrogenation,
- Carboxyl-terminated polyolefin
1. [1]
  Sturzel M, Mihan S, Mulhaupt R. Chem Rev, 2016, 116(3): 1398 − 1433 doi: 10.1021/acs.chemrev.5b00310
2. [2]
  Kaminsky W. Macromol Chem Phys, 2008, 209(5): 459 − 466 doi: 10.1002/macp.200700575
3. [3]
  Chen Jianzhuang(陈健壮), Cui Kun(崔崑), Zhang Shuyuan(张淑媛), Ma Zhi(马志). Progress in Chemistry(化学进展), 2008, 20(11): 1740 − 1750
4. [4]
  Wang Huanxin(汪焕心). Guangzhou Chemical Industry(广州化工), 2012, 40(3): 1 − 3 doi: 10.3969/j.issn.1001-9677.2012.03.002
5. [5]
  Jian Zhongbao(简忠保). Acta Polymerica Sinica(高分子学报), 2018, (11): 1359 − 1371 doi: 10.11777/j.issn1000-3304.2018.18146
6. [6]
  Zou Tingting(邹婷婷), Jiang Bin(蒋斌), Lin Shaohui(林韶晖), Pan Qinmin(潘勤敏). Acta Polymerica Sinica(高分子学报), 2016, (10): 1374 − 1382
7. [7]
  Smith R F, Boothroyd S C, Thompson R L, Khosravi E. Green Chem, 2016, 18(11): 3448 − 3455 doi: 10.1039/C5GC03075G
8. [8]
  Michel X, Fouquay S, Michaud G, Simon F, Brusson J M, Carpentier J F, Guillaume S M. Eur Polym J, 2017, 96: 403 − 413 doi: 10.1016/j.eurpolymj.2017.09.027
9. [9]
  Saetung N, Campistron I, Pascua S, Pilard J F, Fontaine L. Macromolecules, 2011, 44(4): 784 − 794 doi: 10.1021/ma102406w
10. [10]
  Chen Min(陈敏), Chen Changle(陈昶乐). Acta Polymerica Sinica(高分子学报), 2018, (11): 1372 − 1384 doi: 10.11777/j.issn1000-3304.2018.18155
11. [11]
  Dong J Y, Hu Y. Coord Chem Rev, 2006, 250(1-2): 47 − 65 doi: 10.1016/j.ccr.2005.05.008
12. [12]
  Martinez H, Hillmyer M A. Macromolecules, 2014, 47(2): 479 − 485 doi: 10.1021/ma402397b
13. [13]
  Xu Z, Jie S, Li B G. J Polym Sci, Part A: Polym Chem, 2014, 52(22): 3205 − 3212 doi: 10.1002/pola.27381
14. [14]
  Trzaskowski J, Quinzler D, Bahrle C, Mecking S. Macromol Rapid Commun, 2011, 32(17): 1352 − 1356 doi: 10.1002/marc.201100319
15. [15]
  Vilela C, Silvestre A J D, Meier M A R. Macromol Chem Phys, 2012, 213(21): 2220 − 2227 doi: 10.1002/macp.201200332
16. [16]
  Stempfle F, Ortmann P, Mecking S. Chem Rev, 2016, 116(7): 4597 − 4641 doi: 10.1021/acs.chemrev.5b00705
17. [17]
  Shiono T, Yoshida K, Soga K. Makromol Chem Rapid Commun, 1990, 11(4): 169 − 175 doi: 10.1002/marc.1990.030110405
18. [18]
  Shiono T, Kurosawa H, Soga K. Makromol Chem, 1992, 193(11): 2751 − 2761 doi: 10.1002/macp.1992.021931104
19. [19]
  Mazzolini J, Boyron O, Monteil V, Gigmes D, Bertin D, D Agosto F, Boisson C. Macromolecules, 2011, 44(9): 3381 − 3387 doi: 10.1021/ma200342y
20. [20]
  Zhang Yongjie(张勇杰), Li Huayi(李化毅), Dong Jinyong(董金勇), Hu Youliang(胡友良). Progress in Chemistry(化学进展), 2014, 26(1): 110 − 124
21. [21]
  Tasdelen M A, Kahveci M U, Yagci Y. Prog Polym Sci, 2011, 36(4): 455 − 567 doi: 10.1016/j.progpolymsci.2010.10.002
22. [22]
  Berenbaum M B, Bulbenko G F, Gobran R H, Hoffman R F. US Patent, 3235589, 1966-02-15
23. [23]
  Reed S F. J Polym Sci, Part A: Polym Chem, 1971, 9(8): 2147 − 2153 doi: 10.1002/pol.1971.150090804
24. [24]
  Norsic S, Thomas C, D' Agosto F, Boisson C. Angew Chem Int Ed, 2015, 54(15): 4631 − 4635 doi: 10.1002/anie.201411223
25. [25]
  Pitet L M, Hillmyer M A. Macromolecules, 2011, 44(7): 2378 − 2381 doi: 10.1021/ma102975r
26. [26]
  Morita T, Maughon B R, Bielawski C W, Grubbs R H. Macromolecules, 2000, 33(17): 6621 − 6623 doi: 10.1021/ma000013x
27. [27]
  Dai L, Wang X, Bu Z, Li B-G, Jie S. J Appl Polym Sci, 2019, 136(2): 46934 doi: 10.1002/app.46934
28. [28]
  Esteruelas M A, Gonzalez F, Herrero J, Lucio P, Olivan M, Ruiz-Labrador B. Polym Bull, 2007, 58(5-6): 923 − 931 doi: 10.1007/s00289-007-0734-4
29. [29]
  Lichtenheldt M, Wang D R, Vehlow K, Reinhardt I, Kuhnel C, Decker U, Blechert S, Buchmeiser M R. Chem Eur J, 2009, 15(37): 9451 − 9457 doi: 10.1002/chem.200900384
30. [30]
  Grubbs R H. Handbook of Metathesis. Weinheim: Wiley-VCH, 2003. 1 − 6
31. [31]
  Harwood H J, Russell D B, Verthe J A, Zymonas J. Makromol Chem, 1973, 163: 1 − 12 doi: 10.1002/macp.1973.021630101
32. [32]
  Mango L A, Lenz R W. Makromol Chem, 1973, 163: 13 − 36 doi: 10.1002/macp.1973.021630102
33. [33]
  Hahn F. J Polym Sci, Part A: Polym Chem, 1992, 30(3): 397 − 408 doi: 10.1002/pola.1992.080300307
34. [34]
  Zhou Q, Wang A, Dai L, Jie S, Li B G. Polymer, 2016, 107: 306 − 315 doi: 10.1016/j.polymer.2016.11.033
35. [35]
  Song S F, Fu Z S, Xu J T, Fan Z Q. J Appl Polym Sci, 2018, 135(7): 41586
36. [36]
  Carella J M, Graessley W W, Fetters L J. Macromolecules, 1984, 17(12): 2775 − 2786 doi: 10.1021/ma00142a059
37. [37]
  Rasid H M, Azhar N H A, Jamaluddin N, Yusoff S F M. Bull Korean Chem Soc, 2016, 37(6): 797 − 801 doi: 10.1002/bkcs.10767
38. [38]
  Samran J, Phinyocheep P, Daniel P, Kittipoom S. J Appl Polym Sci, 2005, 95(1): 16 − 27 doi: 10.1002/app.20811
39. [39]
  Mahittikul A, Prasassarakich P, Rempel G L. J Appl Polym Sci, 2007, 103(5): 2885 − 2895 doi: 10.1002/app.25449
40. [40]
  Azhar N H A, Jamaluddin N, Rasid H M, Yusof M J M, Yusoff S F M. Int J Polym Sci, 2015, 243038
41. [41]
  Hunig S, Muller H R. Angew Chem Int Ed, 1962, 74(6): 215 − 216
42. [42]
  Corey E J, Mock W Y, Pasto D J. Tetrahedron Lett, 1961, 2(11): 347 − 352 doi: 10.1016/S0040-4039(01)91637-5
43. [43]
  Brandrup J, Immergut E H, Grulke E A. Polymer Handbook, 4^th ed. New York: Wiley, 1999. 705 − 710
44. [44]
  Singha N K, De P P, Sivaram S J. J Appl Polym Sci, 1997, 66(9): 1674 − 1652
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