Skip to main content

Self-healing polymers synthesized by ring opening metathesis polymerization (ROMP) of bio-derived furanic molecules

Journal of Materials Science volume 56, pages 8900–8909 (2021)Cite this article

Abstract

Novel bio-derivable tricyclic oxanorbornene polymers, based upon secondary furfurylamine and maleic anhydride derived monomers, prepared via ring opening metathesis polymerization (ROMP) are reported. The tricyclic oxanorbornenes with fused lactam ring are exo Diels–Alder adducts. DFT calculations support the cycloaddition is the first step, followed by lactamization. The polymerizations are rapid and deliver polymers with targeted molar mass and low dispersity (Đ). The prepared polymers with furanyl pendant groups have reactivity towards maleimide-bearing compounds to form thermally induced crosslinked networks through thermoreversible Diels–Alder reactions. The thermoreversible (self-healing) behavior is confirmed by sol gel transition. This new class of bio-derived polymer could be further modified with different active moieties as pendant groups and hence be tailored for more applications in the future.

Graphical abstract

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

USD 39.95

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Figure 1
Scheme 1
Scheme 2
Scheme 3
Scheme 4
Figure 2
Scheme 5
Figure 3

References

  1. Mülhaupt R (2013) Green polymer chemistry and bio-based plastics: dreams and reality. Macromol Chem Phys 214:159–174. https://doi.org/10.1002/macp.201200439

    Article  CAS  Google Scholar 

  2. Voirin C, Caillol S, Sadavarte NV et al (2014) Functionalization of cardanol: towards biobased polymers and additives. Polym Chem 5:3142–3162. https://doi.org/10.1039/c3py01194a

    Article  CAS  Google Scholar 

  3. Isikgor FH, Becer CR (2015) Lignocellulosic biomass: a sustainable platform for the production of bio-based chemicals and polymers. Polym Chem 6:4497–4559. https://doi.org/10.1039/c5py00263j

    Article  CAS  Google Scholar 

  4. Iwata T (2015) Biodegradable and bio-based polymers: future prospects of eco-friendly plastics. Angew Chemie Int Ed 54:3210–3215. https://doi.org/10.1002/anie.201410770

    Article  CAS  Google Scholar 

  5. Della Monica F, Kleij AW (2020) From terpenes to sustainable and functional polymers. Polym Chem 11:5109–5127

    Article  CAS  Google Scholar 

  6. Terzopoulou Z, Papadopoulos L, Zamboulis A et al (2020) Tuning the properties of furandicarboxylic acid-based polyesters with copolymerization: a review. Polymers (Basel) 12:1209–1260

    Article  CAS  Google Scholar 

  7. John G, Nagarajan S, Vemula PK et al (2019) Natural monomers: a mine for functional and sustainable materials—occurrence, chemical modification and polymerization. Prog Polym Sci 92:158–209

    Article  CAS  Google Scholar 

  8. Soetedjo JNM, van de Bovenkamp HH, Deuss PJ, Heeres HJ (2017) Biobased furanics: kinetic studies on the acid catalyzed decomposition of 2-hydroxyacetyl furan in water using Brönsted acid catalysts. ACS Sustain Chem Eng 5:3993–4001. https://doi.org/10.1021/acssuschemeng.6b03198

    Article  CAS  Google Scholar 

  9. Li X, Jia P, Wang T (2016) Furfural: a promising platform compound for sustainable production of C4 and C5 chemicals. ACS Catal 6:7621–7640. https://doi.org/10.1021/acscatal.6b01838

    Article  CAS  Google Scholar 

  10. Lange J-P, Van Der Heide E, Van Buijtenen J, Price R (2012) Furfural-A promising platform for lignocellulosic biofuels. ChemSusChem 5:150–166. https://doi.org/10.1002/cssc.201100648

    Article  CAS  Google Scholar 

  11. Kim ES, Liu S, Abu-Omar MM, Mosier NS (2012) Selective conversion of biomass hemicellulose to furfural using maleic acid with microwave heating. Energy Fuels 26:1298–1304. https://doi.org/10.1021/ef2014106

    Article  CAS  Google Scholar 

  12. Fang C, Wu W, Li H et al (2017) Production of bio-based furfural from xylose over a recyclable niobium phosphate (NbOPO3) catalyst. Energy Sources Part A Recover Util Environ Eff 39:2072–2077. https://doi.org/10.1080/15567036.2017.1402103

    Article  CAS  Google Scholar 

  13. Gürbüz EI, Gallo JMR, Alonso DM et al (2013) Conversion of hemicellulose into furfural using solid acid catalysts in γ-valerolactone. Angew Chem Int Ed 52:1270–1274. https://doi.org/10.1002/anie.201207334

    Article  CAS  Google Scholar 

  14. Sahu R, Dhepe PL (2012) A one-pot method for the selective conversion of hemicellulose from crop waste into C5 sugars and furfural by using solid acid catalysts. ChemSusChem 5:751–761. https://doi.org/10.1002/cssc.201100448

    Article  CAS  Google Scholar 

  15. Chatterjee M, Ishizaka T, Kawanami H (2016) Reductive amination of furfural to furfurylamine using aqueous ammonia solution and molecular hydrogen: an environmentally friendly approach. Green Chem 18:487–496. https://doi.org/10.1039/c5gc01352f

    Article  CAS  Google Scholar 

  16. Alonso-Fagúndez N, Granados ML, Mariscal R, Ojeda M (2012) Selective conversion of furfural to maleic anhydride and furan with VOx/Al2O3 catalysts. ChemSusChem 5:1984–1990. https://doi.org/10.1002/cssc.201200167

    Article  CAS  Google Scholar 

  17. Lou Y, Marinkovic S, Estrine B et al (2020) Oxidation of furfural and furan derivatives to maleic acid in the presence of a simple catalyst system based on acetic acid and TS-1 and hydrogen peroxide. ACS Omega. https://doi.org/10.1021/acsomega.9b02141

    Article  Google Scholar 

  18. Liu Y-L, Chuo T-W (2013) Self-healing polymers based on thermally reversible Diels–Alder chemistry. Polym Chem 4:2194–2205. https://doi.org/10.1039/c2py20957h

    Article  CAS  Google Scholar 

  19. Syrett JA, Becer CR, Haddleton DM (2010) Self-healing and self-mendable polymers. Polym Chem 1:978–987. https://doi.org/10.1039/c0py00104j

    Article  CAS  Google Scholar 

  20. 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

    Article  CAS  Google Scholar 

  21. Arunbabu D, Noh SM, Nam JH, Oh JK (2016) Thermoreversible self-healing networks based on a tunable polymethacrylate crossslinker having pendant maleimide groups. Macromol Chem Phys 217:2191–2198. https://doi.org/10.1002/macp.201600330

    Article  CAS  Google Scholar 

  22. Burattini S, Colquhoun HM, Greenland BW, Hayes W (2009) A novel self-healing supramolecular polymer system. Faraday Discuss 143:251–264. https://doi.org/10.1039/b900859d

    Article  CAS  Google Scholar 

  23. Kavitha AA, Singha NK (2009) “Click chemistry” in tailor-made polymethacrylates bearing reactive furfuryl functionality: a new class of self-healing polymeric material. ACS Appl Mater Interfaces 1:1427–1436. https://doi.org/10.1021/am900124c

    Article  CAS  Google Scholar 

  24. Yoshie N, Yoshida S, Matsuoka K (2019) Self-healing of biobased furan polymers: recovery of high mechanical strength by mild heating. Polym Degrad Stab 161:13–18. https://doi.org/10.1016/j.polymdegradstab.2019.01.007

    Article  CAS  Google Scholar 

  25. Naguib M, Schiller TL, Keddie DJ (2018) Rapid, regioselective living ring-opening metathesis polymerization of bio-derivable asymmetric tricyclic oxanorbornenes. Macromol Rapid Commun 39:1700794–1700798. https://doi.org/10.1002/marc.201700794

    Article  CAS  Google Scholar 

  26. Bielawski CW, Grubbs RH (2007) Living ring-opening metathesis polymerization. Prog Polym Sci 32:1–29. https://doi.org/10.1016/j.progpolymsci.2006.08.006

    Article  CAS  Google Scholar 

  27. Bai Y, De Bruyn M, Clark JH et al (2016) Ring opening metathesis polymerisation of a new bio-derived monomer from itaconic anhydride and furfuryl alcohol. Green Chem 18:3945–3948. https://doi.org/10.1039/c6gc00623j

    Article  CAS  Google Scholar 

  28. Nomura K, Abdellatif MM (2010) Precise synthesis of polymers containing functional end groups by living ring-opening metathesis polymerization (ROMP): efficient tools for synthesis of block/graft copolymers. Polymer (Guildf) 51:1861–1881

    Article  CAS  Google Scholar 

  29. Parker KA, Sampson NS (2016) Precision synthesis of alternating copolymers via ring-opening polymerization of 1-substituted cyclobutenes. Acc Chem Res 49:408–417. https://doi.org/10.1021/acs.accounts.5b00490

    Article  CAS  Google Scholar 

  30. Li X, Zhao Y, Feng Z et al (2017) Ring-opening metathesis polymerization for the preparation of polynorbornene-based proton exchange membranes with high proton conductivity. J Memb Sci 528:55–63. https://doi.org/10.1016/j.memsci.2016.12.050

    Article  CAS  Google Scholar 

  31. Yu X, Mu C, Dai D et al (2016) Well-defined magnetic responsive polymers containing ammonium FeCl4 from ROMP. Macromol Chem Phys 217:2700–2707. https://doi.org/10.1002/macp.201600435

    Article  CAS  Google Scholar 

  32. McLaughlin CK, Hamblin GD, Hänni KD et al (2012) Three-dimensional organization of block copolymers on “DNA-minimal” scaffolds. J Am Chem Soc 134:4280–4286. https://doi.org/10.1021/ja210313p

    Article  CAS  Google Scholar 

  33. Schwab P, Grubbs RH, Ziller JW (1996) Synthesis and applications of RuCl2(CHR‘)(PR3)2: the influence of the alkylidene moiety on metathesis activity. J Am Chem Soc 118:100–110. https://doi.org/10.1021/ja952676d

    Article  CAS  Google Scholar 

  34. Samojłowicz C, Bieniek M, Grela K (2009) Ruthenium-based olefin metathesis catalysts bearing N-heterocyclic carbene ligands. Chem Rev 109:3708–3742. https://doi.org/10.1021/cr800524f

    Article  CAS  Google Scholar 

  35. Louie J, Grubbs RH (2001) Highly active metathesis catalysts generated in situ from inexpensive and air-stable precursors. Angew Chem Int Ed 40:247–249. https://doi.org/10.1002/1521-3773(20010105)40:1%3c247::aid-anie247%3e3.0.co;2-4

    Article  CAS  Google Scholar 

  36. Murali R, Prakash Rao HS, Scheeren HW (2001) Intra-molecular Diels-Alder reactions of citraconamic acids from furfurylamines and citraconic anhydride: effects of substitution in the furan ring on regioselectivity. Tetrahedron 57:3165–3174. https://doi.org/10.1016/S0040-4020(01)00175-2

    Article  CAS  Google Scholar 

  37. Murali R, Scheeren HW (1999) Unexpected rearrangement of intramolecular Diels–Alder adducts of citraconic anhydride and secondary furfuryl amines. Tetrahedron Lett 40:3029–3032. https://doi.org/10.1016/S0040-4039(99)00316-0

    Article  CAS  Google Scholar 

  38. Takano S, Oshima Y, Ito F, Ogasawara K (1980) Diels–Alder reaction of furfurylamine derivatives with maleic anhydride and its stereochemistry. Yakugaku Zasshi 100:1194–1202. https://doi.org/10.1248/yakushi1947.100.12_1194

    Article  CAS  Google Scholar 

  39. Zaytsev VP, Mikhailova NM, Airiyan IK et al (2012) Cycloaddition of furfurylamines to maleic anhydride and its substituted derivatives. Chem Heterocycl Compd 48:505–513. https://doi.org/10.1007/s10593-012-1023-1

    Article  CAS  Google Scholar 

  40. Lacerda TM, Carvalho AJF, Gandini A (2014) Two alternative approaches to the Diels–Alder polymerization of tung oil. RSC Adv 4:26829–26837. https://doi.org/10.1039/C4RA03416C

    Article  CAS  Google Scholar 

  41. Brun P, Zylber J, Reboul J-P (1994) Intramolecular versus intermolecular Diels–Alder reaction in the cyclisation reaction of furfuryl amines with maleic anhydride. Heterocycl Commun 1:13–16. https://doi.org/10.1515/HC.1994.1.1.13

    Article  CAS  Google Scholar 

  42. Morita T, Maughon BR, Bielawski CW, Grubbs RH (2000) A ring-opening metathesis polymerization (ROMP) approach to carboxyl- and amino-terminated telechelic poly(butadiene)s. Macromolecules 33:6621–6623. https://doi.org/10.1021/ma000013x

    Article  CAS  Google Scholar 

Download references

Acknowledgements

M. Naguib would like to thank the Cultural Affairs & Missions Sector of Egypt for financial support. D.J.K. acknowledges the Royal Society of Chemistry and the Faculty of Science and Engineering at the University of Wolverhampton for funding.

Author information

Authors and Affiliations

  1. Polymer and Pigments Department, National Research Centre, Cairo, 12622, Egypt

    Mohamed Naguib

  2. Department of Chemistry, Faculty of Science, Alexandria University, Alexandria, Egypt

    Atteya Rashed

  3. School of Sciences, Faculty of Science and Engineering, University of Wolverhampton, Wolverhampton, WV1 1LY, UK

    Mohamed Naguib & Daniel J. Keddie

Authors
  1. Mohamed Naguib
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Atteya Rashed
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Daniel J. Keddie
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Mohamed Naguib or Daniel J. Keddie.

Ethics declarations

Conflict of interest

The authors have no conflict to declare.

Additional information

Handling Editor: Maude Jimenez.

Publisher's Note

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

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (PDF 1919 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Naguib, M., Rashed, A. & Keddie, D.J. Self-healing polymers synthesized by ring opening metathesis polymerization (ROMP) of bio-derived furanic molecules. J Mater Sci 56, 8900–8909 (2021). https://doi.org/10.1007/s10853-021-05853-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-021-05853-x