Properties of bio-based thermosetting composites synthesized from epoxidized soybean oil and azo-cardanol benzoxazine

Abstract

In this study, a new type of bio-based azobenzene-containing benzoxazine (Bza) was synthesized using p-aminoazobenzene, paraformaldehyde, and cardanol the raw materials, and the resulting Bza was mixed with bio-based epoxy soybean oil (ESO) in different composition ratios in the presence of adipic acid as a reaction curing agent, affording a bio-based thermosetting composite thermosets. The chemical structure of the synthesized Bza was characterized by Fourier transform infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy. The thermal curing behavior in the absence of any catalyst was investigated by differential scanning calorimetry, indicating that the synthesized Bza exhibits certain liquid crystalline characteristics during heating. The existence of liquid crystal state was further confirmed by the polarizing microscope studies. The mechanical and thermal properties of the composite thermosets with different proportions of Bza were studied. The results show that the addition of increasing amount of Bza to ESO improved its performance to a certain extent; however, further addition beyond a certain range deteriorated the performance. Attributing to excellent processability and high performance of soybean oil-based thermosetting materials and photochromism of azobenzene compounds, the resulting composite materials endowing the characteristics of their components will have a wide range of applications in many fields.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Scheme 2
Scheme 3
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

References

  1. 1.

    Liu W, Xie T, Qiu R (2017) Biobased Thermosets Prepared from Rigid Isosorbide and Flexible Soybean Oil Derivatives. ACS Sustain Chem Eng 5(1):774–783

    CAS  Article  Google Scholar 

  2. 2.

    Li YT, Yang LT, Zhang H et al (2017) Synthesis and curing performance of a novel bio-based epoxy Monomer from soybean oil. Eur J Lipid Sci Technol 119(8):1438–7697

    Article  CAS  Google Scholar 

  3. 3.

    Dai JY, Yang SM, Teng N et al (2018) Synthesis of Eugenol-Based Silicon-Containing Benzoxazines and Their Applications as Bio-Based Organic Coatings. Coatings 8(3):2079–6412

    Google Scholar 

  4. 4.

    Gandini A (2008) Polymers from renewable resources: A challenge for The future of macromolecular materials. Macromolecules 41(24):9491–9504

    CAS  Article  Google Scholar 

  5. 5.

    Mosiewick MA, Aranguren MI (2013) Short Review on Novel Biocomposites Based on Plant Oil Precursors. Eur Polym J 49(6):1243–1256

    Article  CAS  Google Scholar 

  6. 6.

    Meier MAR, Metzger JO, Schubert US (2007) Plant Oil Renewable Resources as Green Alternatives in Polymer Science. Chem Soc Rev 36(11):1788–1802

    CAS  PubMed  Article  Google Scholar 

  7. 7.

    Díez-Pascual AM, Díez-Vicente AL (2014) Epoxidized Soybean Oil/ZnO Biocomposites for Soft Tissue Applications: Preparation and Characterization. ACS Appl Mater Interfaces 6(19):17277–17288

    PubMed  Article  CAS  Google Scholar 

  8. 8.

    Raqueza JM, Deleglisea M, Lacrampea MF, Krawczaka P (2010) Thermosetting (Bio) materials Derived from Renewable Resources: A Critical Review. Prog Polym Sci 35(4): 487−509

  9. 9.

    Trin K, Hunt AJ, Nontipa S (2018) Development of hyperbranched crosslinkers from bio-derived platform molecules for the synthesis of epoxidised soybean oil based thermosets. RSC Adv 8(65):37267–37276

    Article  Google Scholar 

  10. 10.

    Kumar S, Mohanty S, Nayak SK (2020) Nanocomposites of epoxidized soybean oil (ESO)-based epoxy (DGEBA) blends and clay platelets: cured with methylhexahydrophthalic anhydride crosslinker. J Macromol Sci, Part A 57(9):1060–1325

    Article  CAS  Google Scholar 

  11. 11.

    Samper M, Fombuena V, Boronat T et al (2012) Thermal and mechanical characterization of epoxy resins (ELO and ESO) cured with anhydrides. J Am Oil Chem Soc 89(8):1521–1528

    CAS  Google Scholar 

  12. 12.

    Ammar S, Iling AWM, Ramesh K et al (2020a) Development of fully organic coating system modified with epoxidized soybean oil with superior corrosion protection performance. Prog Org Coat 140:0300–9440

    Google Scholar 

  13. 13.

    Sushanta KS, Smita M, Sanjay KN (2015) Synthesis and Characterization of Bio-based Epoxy Blends from Renewable Resource Based Epoxidized Soybean Oil as Reactive Diluent. Chin J Polym Sci 33(1):137–152

    Article  CAS  Google Scholar 

  14. 14.

    Narita K, Chahinez A, Hélène F et al (2019) Bio-based flexible epoxy foam synthesized from epoxidized soybean oil andepoxidized mangosteen tannin. Ind Crops Prod 128:0926–6690

    Google Scholar 

  15. 15.

    Chow WS, Tan SG, Ahmad Z et al (2014) Biodegradability of Epoxidized Soybean Oil Based Thermosets in Compost Soil Environment. J Polym Environ 22(1):140–147

    CAS  Article  Google Scholar 

  16. 16.

    Tan SG, Chow WS (2011) Curing characteristics and thermal properties of epoxidized soybean oil based thermosetting resin. J Am Oil Chem Soc 88(7):915–923

    CAS  Article  Google Scholar 

  17. 17.

    Ammar S, Iling AWM, Ramesh K et al (2020b) Development of fully organic coating system modified with epoxidized soybeanoil with superior corrosion protection performance. Prog Org Coat 140:0300–9440

    Google Scholar 

  18. 18.

    Espinoza-Perez JD, Nerenz BA, Haagenson DM et al (2011) Comparison of curing agents for epoxidized vegetable oils applied to composites. Polym Compos 32(11):1806–1816

    CAS  Article  Google Scholar 

  19. 19.

    Tan SG, Ahmad Z, Chow WS (2012) Relationships of cure kinetics and processing for epoxidized soybean oil bio-thermoset. Ind Crops Prod 43:378–385

    Article  CAS  Google Scholar 

  20. 20.

    Sudheer K, Sushanta KS, Smita M et al (2017) Epoxidized Soybean Oil-Based Epoxy Blend Cured with Anhydride-Based Cross-Linker: Thermal and Mechanical Characterization. Ind Eng Chem Res 56(3):687–698

    Article  CAS  Google Scholar 

  21. 21.

    Tan K, Luo J, Zhu Y et al (2019) Tannic acid functionalized UV-curable carbon nanotube: Effective reinforcement of acrylated epoxidized soybean oil coating. Prog Org Coat 130:214–220

    CAS  Article  Google Scholar 

  22. 22.

    Bach QV, Vu CM, Vu HT et al (2019) Epoxidized soybean oil grafted with CTBN as a novel toughener for improving the fracture toughness and mechanical properties of epoxy resin. Polym J 0032−3869

  23. 23.

    Zhan G, Tang X, Yu Y et al (2011) Biobased Cyanate Ester Composites with Epoxidized Soybean Oil and in Situ Generated Nano-Silica. Polym Eng Sci 51(3):426–433

    CAS  Article  Google Scholar 

  24. 24.

    Zhang J, Hu S, Zhan G et al (2013) Biobased Nanocomposites from Clay Modified Blend of Epoxidized Soybean Oil and Cyanate Ester Resin. Prog Org Coat 76(11):1683–1690

    CAS  Article  Google Scholar 

  25. 25.

    Lakho DA, Yao DG, Cho KH et al (2017) Study of the Curing Kinetics toward Development of Fast-Curing Epoxy Resins. Polym-Plast Technol Eng 56(2):161–170

    CAS  Article  Google Scholar 

  26. 26.

    Zhang K, Liu YQ, Han MC et al (2020) Smart and sustainable design of latent catalyst-containing benzoxazine-bio-resins and application studies. Green Chem 22(4):1209–1219

    CAS  Article  Google Scholar 

  27. 27.

    Yan HQ, Sun C, Fang ZP et al (2016) Synthesis of an intrinsically flame retardant bio-based benzoxazine resin. Polymer 97:418–427

    CAS  Article  Google Scholar 

  28. 28.

    Zhang K, Han M, Liu Y et al (2019) Design and Synthesis of Bio-Based High-Performance Trioxazine Benzoxazine Resin via Natural Renewable Resources. ACS Sustain Chem Eng 7(10):9399–9407

    CAS  Article  Google Scholar 

  29. 29.

    Li SL, Zhao CX, Wang YN et al (2018) Synthesis and electrochemical properties of electroactive aniline-dimer-based benzoxazines for advanced corrosion-resistant coatings. J Mater Sci 53(10):7344–7356

    CAS  Article  Google Scholar 

  30. 30.

    Hao B, Han L, Liu Y, Zhang K et al (2020) An apigenin-based bio-benzoxazine with three polymerizable functionalities: sustainable synthesis, thermal latent polymerization, and excellent thermal properties of its thermosets. Polym Chem 11(36): 5800−5809

  31. 31.

    Kiskan B, Dogan F, Durmaz YY et al (2009) Synthesis, characterization and thermally-activated curing of azobenzene-containing benzoxazines. Des Monomers Polym 11(5):473–482

    Article  Google Scholar 

  32. 32.

    Kiskan B, Demirel AL, Kamer O et al (2008) Synthesis and characterization of nanomagnetite thermosets based on benzoxazines. J Polym Sci, Part A: Polym Chem 46(20):6780–6788

    CAS  Article  Google Scholar 

  33. 33.

    Mohamed MG, Hsiao CH, Hsu KC et al (2015) Supramolecular functionalized polybenzoxazines from azobenzene carboxylic acid/azobenzene pyridine complexes: synthesis, surface properties, and specific interactions. RSC Adv 5(17):12763–12772

    CAS  Article  Google Scholar 

  34. 34.

    EL-Mahdy AF, Lin FW, Su WH, Chen T, Kuo SW et al (2019) Photoresponsive Azobenzene Materials Based on Pyridine-Functionalized Benzoxazines as Surface Relief Gratings. ACS Appl Polym Mater 2(2): 791−804

  35. 35.

    Lou C, Zhang R, Zhou CL et al (2019) Facile fabrication of epoxy/polybenzoxazine based superhydrophobic coating with enhanced corrosion resistance and high thermal stability. Colloids Surf A: Phys Eng Asp 562:8–15

    CAS  Article  Google Scholar 

  36. 36.

    Li XD, Xia YQ, Xu WL et al (2012) The curing procedure for Abenzoxazine-cyanate-epoxy system and the properties of the terpolymer. Polym Chem 3(6):1629–1633

    CAS  Article  Google Scholar 

  37. 37.

    Hao B, Yang R, Zhang K (2020) A naringenin-based benzoxazine with an intramolecular hydrogen bond as both a thermal latent polymerization additive and property modifier for epoxy resins. RSC Adv 10(43):25629–25638

    CAS  Article  Google Scholar 

  38. 38.

    Kimura H, Matsumoto A, Ohtsuk K (2008) Studies on new type of phenolic resin−Curing reaction of bisphenol-A-based benzoxazine with epoxy resin using latent curing agent and the properties of the cured resin. J Appl Polym Sci 109(2):1248–1256

    CAS  Article  Google Scholar 

  39. 39.

    Thirukumaran P, Parveen AS, Sarojadevi M (2014) Synthesis and Copolymerization of fully biobased benzoxazines from renewable resources. ACS Sustain Chem Eng 2(12):2790–2801

    CAS  Article  Google Scholar 

  40. 40.

    Vitae MFA, Vitae BBA, Vitae SCA (2015) Vanillin, a key-intermediate of biobased polymers. Eur Polym J 68:488–502

    Article  CAS  Google Scholar 

  41. 41.

    Alev T, Gerard L, Ronda JC et al (2016) Castor oil-derived benzoxazines: Synthesis, self-metathesis and properties of the resulting thermosets. Eur Polym J 75:56–66

    Article  CAS  Google Scholar 

  42. 42.

    Zhang CX, Ling H, Gu Y (2011) Curing characteristics of cardanolbenzoxazine. Polym Mater Sci Eng 27(5):92–95

    CAS  Google Scholar 

  43. 43.

    Kurihara M, Hirooka A, Kume S et al (2002) Redox-conjugated reversible isomerization ferrocenylazobenzene with a single green light. J Am Chem Soc 124(30):8800–8801

    CAS  PubMed  Article  Google Scholar 

  44. 44.

    Dinda S, Patwardhan AV, Goud VV et al (2008) Epoxidation of Cottonseed Oil by Aqueous Hydrogen Peroxide Catalysed by Liquid Inorganic Acids. Bioresour Technol 99(9):3737–3744

    CAS  PubMed  Article  Google Scholar 

  45. 45.

    Ma SQ, Jiang YH, Liu XQ et al (2014) Bio-based tetrafunctional crosslink agent from gallic acid and its enhanced soybean oil-based UV-cured coatings with high performance. RSC Adv 4(44):23036–23042

    CAS  Article  Google Scholar 

  46. 46.

    Lin CH, Shih YS, Wang MW et al (2014) Pyridinyl-containing benzoxazine: Unusual curing behaviors with epoxy resins. Polymer 55(7):1666–1673

    CAS  Article  Google Scholar 

  47. 47.

    Liu H, Wang XD, Wu DZ (2015) Preparation, isothermal kinetics, and performance of a novel epoxy thermosetting system based on phosphazene-cyclomatrix network for halogen-free flame retardancy and high thermal stability. Thermochim Acta 607:60–73

    CAS  Article  Google Scholar 

  48. 48.

    Ma SQ, Liu XQ, Jiang YH et al (2013) Bio-based epoxy resin from itaconic acid and its thermosets cured with anhydride and comonomers. Green Chem 15(1):245–254

    CAS  Article  Google Scholar 

  49. 49.

    Zeng RT, Wu Y, Li YD et al (2017) Curing behavior of epoxidized soybean oil with biobased dicarboxylic acids. Polym Test 57:281–287

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (51703191), the Science and Technology Plan Project in Sichuan Province (2019YFG0242).

Author information

Affiliations

Authors

Corresponding author

Correspondence to Chunxia Zhao.

Ethics declarations

Conflict of interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article

Additional information

Publisher’s Note

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

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Wu, J., Zhao, C., Li, Y. et al. Properties of bio-based thermosetting composites synthesized from epoxidized soybean oil and azo-cardanol benzoxazine. J Polym Res 28, 77 (2021). https://doi.org/10.1007/s10965-021-02442-z

Download citation

Keywords

  • Benzoxazine
  • Azo compounds
  • Epoxy soybean oil
  • bio-based
  • Composite thermosets