Cardanol-Imidazole Based Benzoxazine Blends and Bio-silica Reinforced Composites with Enhanced Surface, Thermal and Dielectric Properties

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In the present work, imidazole core mono-amine (ima) was synthesized and used with cardanol (C) and bisphenol-F (BF) to obtain corresponding benzoxazines (C-ima and BF-ima) respectively. Similarly aniline (a) was used as amine precursor for synthesis of benzoxazines (C-a and BF-a) of cardanol (C) and bisphenol-F (BF) respectively for the purpose of blending and comparative studies with ima based benzoxazines. Benzoxazines (C-ima, C-a, BF-ima and BF-a) matrices and blends were prepared using both monofunctional and bifunctional benzoxazines in different weight percent (25/75 wt%, 50/50 wt% and 75/25 wt%) ratios and were characterized using different analytical techniques. From DSC analysis, it was observed that the curing temperature obtained for imidazole based benzoxazines (C-ima and BF-ima) was significantly lower than that of benzoxazines (C-a and BF-a) made using conventional aniline. Similarly, the blends prepared using ima based benzoxazine possess the lower curing temperature, with enhanced thermal stability and char yield than those of conventional cardanol-aniline benzoxazines to an appreciable extent. Hybrid blend composites were developed by reinforcing varying weight percentages (1, 3, 5, 7 and 10 wt%) of GPTMS functionalized bio-silica with selected blends (50:50) of imidazole based benzoxazines (C-ima and BF-ima) and their properties were studied. Data obtained from different studies, suggest that these hybrid composites possess an enhanced thermal stability, higher values of Tg, improved hydrophobic behavior, higher value of char yield and lower dielectric constant than those of neat matrices and blended matrices. It is concluded that the imidazole amine based benzoxazines (C-ima and BF-ima) blends and hybrid composites developed in the present work possess better properties than those of conventional benzoxazine based materials, hence it is suggested that these blends and composites can be used for high performance thermal and dielectric applications.

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  1. 1.

    Chen S, Zhang J, Zhou J, Zhang D, Zhang A (2018) Dramatic toughness enhancement of benzoxazine/epoxy thermosets with a novel hyperbranched polymeric ionic liquid. Chem Eng J 334:1371–1382

  2. 2.

    Chen CH, Lin CH, Hon JM, Wang MW, Juang TY (2018) First halogen and phosphorus-free, flame-retardant benzoxazine thermosets derived from main-chain type bishydroxydeoxybenzoin-based benzoxazine polymers. Polymer 154:35–41

  3. 3.

    Yan H, Sun C, Fang Z, Liu X, Zhu J, Wang H (2016) Synthesis of an intrinsically flame retardant bio-based benzoxazine resin. Polymer 97:418–427

  4. 4.

    Zhang X, Liu L, Yu Y, Weng L (2018) Flame-retardant mechanism of benzoxazine resin with triazine structure. Adv Polym Technol 37(2):384–389

  5. 5.

    Lin CH, Chang SL, Shen TY, Shih YS, Lin HT, Wang CF (2012) Flexible polybenzoxazine thermosets with high glass transition temperatures and low surface free energies. Polymer Chemistry 3(4):935–945

  6. 6.

    Skledar DG, Mašič LP (2016) Bisphenol A and its analogs: Do their metabolites have endocrine activity. Environ Toxicol Pharmacol 47:182–199

  7. 7.

    Hariharan A, Srinivasan K, Murthy C, Alagar M (2017) A novel imidazole-core-based benzoxazine and its blends for high-performance applications. Ind Eng Chem Res 56(33):9347–9354

  8. 8.

    Muthukaruppan A, Arumugam H, Krishnan S, Kannan K, Chavali M (2018) A low cure thermo active polymerization of chalcone based benzoxazine and cross linkable olefin blends. J Polym Res 25(8):163

  9. 9.

    Hariharan A, Prabunathan P, Subramanian SS, Kumaravel.M, Alagar M (2019) Blends of chalcone benzoxazine and bio-benzoxazines coated cotton fabrics for oil–water separation and bio-silica reinforced nanocomposites for low-k applications. J Polym Environ.

  10. 10.

    Hariharan A, Srinivasan K, Murthy C, Alagar M (2018) Synthesis and characterization of a novel class of low temperature cure benzoxazines. J Polym Res 25(1):20

  11. 11.

    Chernykh A, Liu J, Ishida H (2006) Synthesis and properties of a new crosslinkable polymer containing benzoxazine moiety in the main chain. Polymer 47(22):7664–7669

  12. 12.

    Zeng M, Pang T, Chen J, Huang Y, Xu Q, Gu Y (2018) Facile preparation of the novel castor oil-based benzoxazine–urethane copolymer with improved high-frequency dielectric properties. J Mater Sci: Mater Electron 29(7):5391–5400

  13. 13.

    Arumugam H, Krishnan S, Chavali M, Muthukaruppan A (2018) Cardanol based benzoxazine blends and bio-silica reinforced composites: thermal and dielectric properties. New J Chem 42(6):4067–4080

  14. 14.

    Devaraju S, Krishnadevi K, Sriharshitha S, Alagar M (2019) Design and development of environmentally friendly polybenzoxazine–silica hybrid from renewable bio-resource. J Polym Environ 27(1):141–147

  15. 15.

    Shukla S, Yadav N, Lochab B (2017) Cardanol-based benzoxazines and their applications. In: Ishida H, Froimowicz P (eds) Advanced and emerging polybenzoxazine science and technology. Elsevier, New York, pp 451–472

  16. 16.

    Krishnan S, Arumugam H, Chavali M, Muthukaruppan A (2019) High dielectric, low curing with high thermally stable renewable eugenol-based polybenzoxazine matrices and nanocomposites. J Appl Polym Sci 136(6):47050

  17. 17.

    Dumas L, Bonnaud L, Olivier M, Poorteman M, Dubois P (2015) Eugenol-based benzoxazine: from straight synthesis to taming of the network properties. J Mater Chem A 3(11):6012–6018

  18. 18.

    Dai J, Yang S, Teng N, Liu Y, Liu X, Zhu J, Zhao J (2018) Synthesis of eugenol-based silicon-containing benzoxazines and their applications as bio-based organic coatings. Coatings 8(3):88

  19. 19.

    Wang C, Sun J, Liu X, Sudo A, Endo T (2012) Synthesis and copolymerization of fully bio-based benzoxazines from guaiacol, furfurylamine and stearylamine. Green Chem 14(10):2799–2806

  20. 20.

    Sini NK, Bijwe J, Varma IK (2014) Renewable benzoxazine monomer from Vanillin: Synthesis, characterization, and studies on curing behavior. J Polym Sci Part A: Polym Chem 52(1):7–11

  21. 21.

    Lomonaco D, de Oliveira JR, da Silva JB, Mazzetto SE, Ishida H (2018) Development of fully bio-based high-performance bisbenzoxazine under environmentally friendly conditions, ACS Sustain Chem Eng 6:5485–5494

  22. 22.

    Attanasi OA, Mele G, Filippone P, Mazzetto SE, Vasapollo G (2009) Synthesis and characterization of novel cardanol based fulleropyrrolidines. Arkivoc 8:69–84

  23. 23.

    Vaithilingam S, Jayanthi KP, Muthukaruppan A (2017) Synthesis and characterization of cardanol based fluorescent composite for optoelectronic and antimicrobial applications. Polymer 108:449–461

  24. 24.

    Li S, Zou T, Feng L, Liu X, Tao M (2013) Preparation and properties of cardanol-based polybenzoxazine/SiO2 hybrids by sol‐gel technique. J AppPolym Sci 128(6):4164–4171

  25. 25.

    Li S, Yan S, Yu J, Yu B (2011) Synthesis and characterization of new benzoxazine-based phenolic resins from renewable resources and the properties of their polymers. J Appl Polym Sci 122(5):2843–2848

  26. 26.

    Shukla S, Mahata A, Pathak B, Lochab B (2015) Cardanol benzoxazines–interplay of oxazine functionality (mono to tetra) and properties. RSC Advances 5(95):78071–78080

  27. 27.

    Zhang C, Zhang Y, Zhou Q, Ling H, Gu Y (2014) Processability and mechanical properties of bisbenzoxazine modified by the cardanol-based aromatic diamine benzoxazine. J Polym Eng 34(6):561–568

  28. 28.

    Chen YP, Dayo AQ, Zhang HY, Wang AR, Wang J, Liu WB, Yang Y, Qin QR, Yang YG (2019) Synthesis of cardanol-based phthalonitrile monomer and its copolymerization with phenol–aniline‐based benzoxazine. J Appl Polym Sci 136(20):47505

  29. 29.

    Calò E, Maffezzoli A, Mele G, Martina F, Mazzetto SE, Tarzia A, Stifani C (2007) Synthesis of a novel cardanol-based benzoxazine monomer and environmentally sustainable production of polymers and bio-composites. Green Chem 9(7):754–759

  30. 30.

    Ručigaj A, Alič B, Krajnc M, Šebenik U (2015) Curing of bisphenol A-aniline based benzoxazine using phenolic, amino and mercapto accelerators. Express Polym Lett 9(7):647–657

  31. 31.

    Chen S, Xu Z, Zhang D (2018) Synthesis and application of epoxy-ended hyperbranched polymers. Chem Eng J 343:283–302

  32. 32.

    Belon C, Chemtob A, Croutxé-Barghorn C, Rigolet S, Schmitt M, Bistac S, Le Houérou V, Gauthier C (2010) Nanocomposite coatings via simultaneous organic–inorganic photo‐induced polymerization: synthesis, structural investigation and mechanical characterization. Polym Int 59(8):1175–1186

  33. 33.

    Kannan K, Krishnan S, Chavali M, Alagar M (2018) Studies on thermal behavior of imidazole diamine based benzoxazines. J Appl Polym Sci 135(32):46562

  34. 34.

    Prabunathan P, Thennarasu P, Song JK, Alagar M (2017) Achieving low dielectric, surface free energy and UV shielding green nanocomposites via reinforcing bio-silica aerogel with polybenzoxazine. New J Chem 41(13):5313–5321

  35. 35.

    Van Krevelen DW (1975) Some basic aspects of flame resistance of polymeric materials. Polymer 16(8):615–620

  36. 36.

    Selvi M, Prabunathan P, Kumar M, Alagar M (2014) Studies on polybenzoxazine/capron PK4/octakis (dimethylsiloxypropylglycidylether) silsesquioxane nanocomposites for radiation resistant applications. Int J Polym Mater Polym Biomater 63(13):651–656

  37. 37.

    Padmanathan N, Alagar M (2015) Design of hydrophobic polydimethylsiloxane and polybenzoxazine hybrids for interlayer low k dielectrics. New J Chem 39(5):3995–4008

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The authors thank the PSG management, the Principal and Vice-Principal of PSG institute of Technology and Applied Research Coimbatore for their moral and financial support.

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Correspondence to Muthukaruppan Alagar.

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Latha, G., Hariharan, A., Prabunathan, P. et al. Cardanol-Imidazole Based Benzoxazine Blends and Bio-silica Reinforced Composites with Enhanced Surface, Thermal and Dielectric Properties. J Polym Environ (2020).

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  • Cardanol
  • Imidazole
  • Benzoxazines
  • Hybrid blends and composites
  • Bio-silica
  • Thermal stability
  • Low dielectric constant
  • Hydrophobic behavior