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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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
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
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
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
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
Skledar DG, Mašič LP (2016) Bisphenol A and its analogs: Do their metabolites have endocrine activity. Environ Toxicol Pharmacol 47:182–199
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
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
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. https://doi.org/10.1007/s10924-019-01629-2
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
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
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
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
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
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
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
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
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
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
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
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
Attanasi OA, Mele G, Filippone P, Mazzetto SE, Vasapollo G (2009) Synthesis and characterization of novel cardanol based fulleropyrrolidines. Arkivoc 8:69–84
Vaithilingam S, Jayanthi KP, Muthukaruppan A (2017) Synthesis and characterization of cardanol based fluorescent composite for optoelectronic and antimicrobial applications. Polymer 108:449–461
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
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
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
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
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
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
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
Chen S, Xu Z, Zhang D (2018) Synthesis and application of epoxy-ended hyperbranched polymers. Chem Eng J 343:283–302
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
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
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
Van Krevelen DW (1975) Some basic aspects of flame resistance of polymeric materials. Polymer 16(8):615–620
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
Padmanathan N, Alagar M (2015) Design of hydrophobic polydimethylsiloxane and polybenzoxazine hybrids for interlayer low k dielectrics. New J Chem 39(5):3995–4008
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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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). https://doi.org/10.1007/s10924-019-01649-y
- Hybrid blends and composites
- Thermal stability
- Low dielectric constant
- Hydrophobic behavior