Advertisement

Bio-based self-healing Eucommia ulmoides ester elastomer with damping and oil resistance

  • 32 Accesses

Abstract

Eucommia ulmoides gum (EUG) is an essential bio-based material with a similar chemical structure to natural rubber, but it is rigid plastic at room temperature due to crystallization, which limits its wide application. Herein, we report a new method for synthesis of functional Eucommia ulmoides ester (EUET) elastomer by chemical modification of EUG. First, EUG was epoxidized by performic acid formed from hydrogen peroxide and formic acid in situ in toluene solution and then subjected to ring-opening reaction with acetic acid. It was found that EUET contained both α-hydroxyl ester and β-hydroxyl ester in the molecular chain. Unlike EUG, EUET was no longer crystallized due to the reduction of regularity, and it has been successfully converted into elastomer, which was confirmed by the elastic strain recovery experiment. Furthermore, because of the presence of polar groups and the hydrogen bond between them, EUET could self-heal under the condition of 50 °C, and their vulcanizates possessed excellent mechanical properties, resilience, oil resistance and damping properties. This study may promote the application of EUG in the field of bio-based functional elastomers.

This is a preview of subscription content, log in to check access.

Access options

Buy single article

Instant unlimited access to the full article PDF.

US$ 39.95

Price includes VAT for USA

Subscribe to journal

Immediate online access to all issues from 2019. Subscription will auto renew annually.

US$ 199

This is the net price. Taxes to be calculated in checkout.

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9

References

  1. 1

    Sheldon RA (2014) Green and sustainable manufacture of chemicals from biomass: state of the art. Green Chem 16:950–963. https://doi.org/10.1039/c3gc41935e

  2. 2

    Sun Z, Li F, Du H et al (2013) A novel silvicultural model for increasing biopolymer production from Eucommia ulmoides Oliver trees. Ind Crops Prod 42:216–222. https://doi.org/10.1016/j.indcrop.2012.06.001

  3. 3

    Zhang X, Cheng C, Zhang M et al (2008) Effect of alkali and enzymatic pretreatments of Eucommia ulmoides leaves and barks on the extraction of gutta percha. J Agric Food Chem 56:8936–8943. https://doi.org/10.1021/jf800642y

  4. 4

    Sarina Zhang J, Zhang L (2012) Dynamic mechanical properties of Eucommia ulmoides gum with different degree of cross-linking. Polym Bull 68:2021–2032. https://doi.org/10.1007/s00289-012-0712-3

  5. 5

    Wang Y, Xia L, Xin Z (2018) Triple shape memory effect of foamed natural Eucommia ulmoides gum/high-density polyethylene composites. Polym Adv Technol 29:190–197. https://doi.org/10.1002/pat.4102

  6. 6

    Xia L, Wang Y, Ma Z et al (2017) Preparation of epoxidized Eucommia ulmoides gum and its application in styrene-butadiene rubber (SBR)/silica composites. Polym Adv Technol 28:94–101. https://doi.org/10.1002/pat.3863

  7. 7

    Yang F, Liu Q, Li X et al (2017) Epoxidation of Eucommia ulmoides gum by emulsion process and the performance of its vulcanizates. Polym Bull 74:3657–3672. https://doi.org/10.1007/s00289-017-1912-7

  8. 8

    Shao H, Yu Q, Xiao P et al (2012) Study on viscoelastic properties of epoxidized trans-1,4-polyisoprene by rubber process analyzer. Polym Sci Ser A 54:760–766. https://doi.org/10.1134/s0965545x1208010x

  9. 9

    Johnson T, Thomas S (1999) Nitrogen/oxygen permeability of natural rubber, epoxidised natural rubber and natural rubber/epoxidised natural rubber blends. Polymer (Guildf) 40:3223–3228. https://doi.org/10.1016/S0032-3861(98)00528-X

  10. 10

    Jeerupun J, Wootthikanokkhan J, Phinyocheep P (2004) Effects of epoxidation content of ENR on morphology and mechanical properties of natural rubber blended PVC. Macromol Symp 216:281–292. https://doi.org/10.1002/masy.200451226

  11. 11

    Pire M, Norvez S, Iliopoulos I et al (2010) Epoxidized natural rubber/dicarboxylic acid self-vulcanized blends. Polymer (Guildf) 51:5903–5909. https://doi.org/10.1016/j.polymer.2010.10.023

  12. 12

    Dahham OS, Hamzah R, Bakar MA et al (2017) NMR study of ring opening reaction of epoxidized natural rubber in presence of potassium hydroxide/isopropanol solution. Polym Test 59:55–66. https://doi.org/10.1016/j.polymertesting.2017.01.006

  13. 13

    Jayawardenab S, Reyx D, Durand D (1984) Synthesis of macromolecular antioxidants. Makromol Chem 185:2089–2097. https://doi.org/10.1002/macp.1984.021851004

  14. 14

    Xu T, Jia Z, Wang S et al (2017) Self-crosslinkable epoxidized natural rubber–silica hybrids. J Appl Polym Sci 134:1–10. https://doi.org/10.1002/app.44605

  15. 15

    Kwak MJ, Kim DH, You JB et al (2018) A sub-minute curable nanoadhesive with high transparency, strong adhesion, and excellent flexibility. Macromolecules 51:992–1001. https://doi.org/10.1021/acs.macromol.7b02102

  16. 16

    Li C, Liu Y, Cao P et al (2014) Quaternary phosphonium modified epoxidized natural rubber: effect of reaction time, reaction mechanism, thermal property and antimicrobial activity. Polym Bull 71:2543–2557. https://doi.org/10.1007/s00289-014-1206-2

  17. 17

    Derouet D, Radhakrishnan N, Brosse JC, Boccaccio G (1994) Phosphorus modification of epoxidized liquid natural rubber to improve flame resistance of vulcanized rubbers. J Appl Polym Sci 52:1309–1316. https://doi.org/10.1002/app.1994.070520915

  18. 18

    Perera MCS (1990) Reaction of aromatic amines with epoxidized natural rubber latex. J Appl Polym Sci 39:749–758. https://doi.org/10.1002/app.1990.070390323

  19. 19

    Cheng B, Lu X, Zhou J et al (2019) Dual cross-linked self-healing and recyclable epoxidized natural rubber based on multiple reversible effects. ACS Sustain Chem Eng 7:4443–4455. https://doi.org/10.1021/acssuschemeng.8b06437

  20. 20

    Liu Y, Li Z, Liu R et al (2019) Design of self-healing rubber by introducing ionic interaction to construct a network composed of ionic and covalent cross-linking. Ind Eng Chem Res 58:14848–14858. https://doi.org/10.1021/acs.iecr.9b02972

  21. 21

    Saramolee P, Lopattananon N, Sahakaro K (2014) Preparation and some properties of modified natural rubber bearing grafted poly(methyl methacrylate) and epoxide groups. Eur Polym J 56:1–10. https://doi.org/10.1016/j.eurpolymj.2014.04.008

  22. 22

    Yang Z, Peng H, Wang W, Liu T (2010) Crystallization behavior of poly(ε-caprolactone)/layered double hydroxide nanocomposites. J Appl Polym Sci 116:2658–2667. https://doi.org/10.1002/app

  23. 23

    Meninno S, Lattanzi A (2016) Organocatalytic asymmetric reactions of epoxides: recent progress. Chem A Eur J 22:3632–3642. https://doi.org/10.1002/chem.201504226

  24. 24

    Hamzah R, Bakar MA, Dahham OS et al (2016) A structural study of epoxidized natural rubber (ENR-50) ring opening under mild acidic condition. J Appl Polym Sci. https://doi.org/10.1002/app.44123

  25. 25

    Chen X, Zhang K, Talley SJ et al (2019) Quadruple hydrogen bonding containing supramolecular thermoplastic elastomers: mechanical and morphological correlations. J Polym Sci, Part A: Polym Chem 57:13–23. https://doi.org/10.1002/pola.29272

  26. 26

    Faghihnejad A, Feldman KE, Yu J et al (2014) Adhesion and surface interactions of a self-healing polymer with multiple hydrogen-bonding groups. Adv Funct Mater 24:2322–2333. https://doi.org/10.1002/adfm.201303013

  27. 27

    Zhang A, Yang L, Lin Y et al (2013) Self-healing supramolecular elastomers based on the multi-hydrogen bonding of low-molecular polydimethylsiloxanes: synthesis and characterization. J Appl Polym Sci 129:2435–2442. https://doi.org/10.1002/app.38832

  28. 28

    Wu DY, Meure S, Solomon D (2008) Self-healing polymeric materials: a review of recent developments. Prog Polym Sci 33:479–522. https://doi.org/10.1016/j.progpolymsci.2008.02.001

  29. 29

    Zhao J, Zhang H, Ma C et al (2019) Binary modification of Eucommia ulmoides gum toward elastomer with tunable mechanical properties and good compatibility. J Polym Sci, Part A: Polym Chem 57:1247–1255. https://doi.org/10.1002/pola.29381

  30. 30

    Yang GW, Wu GP (2019) High-efficiency construction of CO2-based healable thermoplastic elastomers via a tandem synthetic strategy. ACS Sustain Chem Eng 7:1372–1380. https://doi.org/10.1021/acssuschemeng.8b05084

  31. 31

    Frick EM, Zalusky AS, Hillmyer MA (2003) Characterization of polylactide-b-polyisoprene-b-polylactide thermoplastic elastomers. Biomacromol 4:216–223. https://doi.org/10.1021/bm025628b

  32. 32

    Bolton JM, Hillmyer MA, Hoye TR (2014) Sustainable thermoplastic elastomers from terpene-derived monomers. ACS Macro Lett 3:717–720. https://doi.org/10.1021/mz500339h

  33. 33

    Liu B, Gao X, Zhao Y et al (2017) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-oxide-based oligosiloxane as a promising damping additive for methyl vinyl silicone rubber (VMQ). J Mater Sci 52:1–15. https://doi.org/10.1007/s10853-017-1085-7

Download references

Acknowledgements

This work was funded by State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology.

Author information

Correspondence to Dongmei Yue.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 667 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Qi, X., Zhang, J., Zhang, L. et al. Bio-based self-healing Eucommia ulmoides ester elastomer with damping and oil resistance. J Mater Sci 55, 4940–4951 (2020). https://doi.org/10.1007/s10853-019-04272-3

Download citation