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Nonylphenol-based polybenzoxazine composites: hydrophobic coating, ultra-low-k and anticorrosion applications

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Abstract

For a broad range of purposes, including the water-repellent fabrics, low-k and anticorrosion applications, four unique series of benzoxazines based on nonylphenol were synthesized and utilized. Different mono and diamines were used for making variety of nonylphenol-based benzoxazines. The chemical structure of benzoxazines was determined by spectroscopic methods. The characteristic properties related to thermal studies of benzoxazines have been evaluated using TGA and DSC. Among the benzoxazines investigated, poly(NP-oda) had an excellent water-repellent nature than the other benzoxazines studied. NP-oda-coated cotton fabrics have water contact angle (WCA) value of 162°, indicating superhydrophobic behavior. Poly(NP-ffa) and poly(NP-ddm) had char residue values of 29% and 30%, respectively, greater than rest of the polybenzoxazines. Dielectric (k) studies of BG-silica incorporated poly(NP-ffa) composites made from Bermuda grass provide the k value 1.76 (ultra-low-k) with loss factor 0.0029. Similarly, the composites made of 5 wt% of SBA-15 incorporated poly(NP-ddm) lower the k value to 1.69 with loss value of 0.0082. Furthermore, benzoxazine with inbuilt catalytic amines exhibits superior corrosion resistance on mild steel specimen surfaces. Data from several investigations suggested that nonylphenol-based benzoxazine and composites can be employed as useful materials for applications such as corrosion resistance, water repellency and microelectronic insulation.

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References

  1. de Araujo FG, Bauerfeldt GF, Cid YP (2018) Nonylphenol: properties, legislation, toxicity and determination. An Acad Bras Cienc 90:1903–1918. https://doi.org/10.1590/0001-3765201720170023

    Article  CAS  Google Scholar 

  2. Kassotis CD, Lefauve MK, Chiang YT, et al (2022) Developmentally Exposed Zebrafish. 1–20

  3. Field JA, Reed RL (1996) Nonylphenol polyethoxy carboxylate metabolites of nonionic surfactants in U.S. paper mill effluents, municipal sewage treatment plant effluents, and river waters. Environ Sci Technol 30:3544–3550. https://doi.org/10.1021/es960191z

    Article  CAS  Google Scholar 

  4. Ho H, Watanabe T (2017) Distribution and removal of nonylphenol ethoxylates and nonylphenol from textile wastewater—a comparison of a cotton and a synthetic fiber factory in Vietnam. Water 9:386. https://doi.org/10.3390/w9060386

    Article  CAS  Google Scholar 

  5. Marcomini A, Stelluto S, Pavoni B (1989) Determination of linear alkylbenzenesulphonates and alkylphenol polyethoxylates in commercial products and marine waters by reversed-and normal-phase hplc. Int J Environ Anal Chem 35:207–218. https://doi.org/10.1080/03067318908028395

    Article  CAS  Google Scholar 

  6. Ying GG, Williams B, Kookana R (2002) Environmental fate of alkylphenols and alkylphenol ethoxylates—a review. Environ Int 28:215–226. https://doi.org/10.1016/S0160-4120(02)00017-X

    Article  CAS  Google Scholar 

  7. Wang T, Guo ZY, Wang JY et al (2021) Modification of traditional benzoxazine by blending with polyfunctional benzoxazines containing aromatic group and fluorene group. High Perform Polym 33:615–622. https://doi.org/10.1177/0954008320974089

    Article  CAS  Google Scholar 

  8. Ishida H, Agag T (2011) Overview and historical background of polybenzoxazine research. Elsevier B.V. https://doi.org/10.1016/C2010-0-66598-9

  9. Ishida H, Sanders DP (2000) Improved thermal and mechanical properties of polybenzoxazines based on alkyl-substituted aromatic amines. J Polym Sci Part B Polym Phys 38:3289–3301. https://doi.org/10.1002/1099-0488(20001215)38:24%3c3289::aid-polb110%3e3.0.co;2-x

    Article  CAS  Google Scholar 

  10. Zhang X, Liu L, Yu Y, Weng L (2018) Flame-retardant mechanism of benzoxazine resin with triazine structure. Adv Polym Technol 37:384–389. https://doi.org/10.1002/adv.21677

    Article  CAS  Google Scholar 

  11. Aishwarya D, Balaji K, Hariharan A (2021) Effective low temperature cure cardanol based mono-functional benzoxazines: a comparison. Polym Sci Ser B 63:727–736. https://doi.org/10.1134/S1560090421060014

    Article  Google Scholar 

  12. Yan H, Zhan Z, Wang H et al (2021) Synthesis, curing, and thermal stability of low-temperature-cured benzoxazine resins based on natural renewable resources. ACS Appl Polym Mater 3:3392–3401. https://doi.org/10.1021/acsapm.1c00361

    Article  CAS  Google Scholar 

  13. Kiskan B (2018) Adapting benzoxazine chemistry for unconventional applications. React Funct Polym 129:76–88. https://doi.org/10.1016/j.reactfunctpolym.2017.06.009

    Article  CAS  Google Scholar 

  14. Tsotra P, Setiabudi F, Weidmann U (2008) Benzoxazine Chemistry: a new material to meet fire retardant challenges of aerospace interiors applications. Huntsman Adv Mater GmbH. In: Semantics Scholar. https://www.semanticscholar.org/paper/A-NEW-MATERIAL-TO-MEET-FIRE-RETARDANT-CHALLENGES-OF-Tsotra-Setiabudi/412f00446f189ebb29e4b4fc0e9553e832ef47f6#cited-papers

  15. Arumugam H, Mohamed Ismail AA, Govindraj L, Muthukaruppan A (2021) Development of bio-based benzoxazines coated melamine foam for oil-water separation. Prog Org Coat 153:106128. https://doi.org/10.1016/j.porgcoat.2020.106128

    Article  CAS  Google Scholar 

  16. Hariharan A, Prabunathan P, Subramanian SS et al (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 28:598–613. https://doi.org/10.1007/s10924-019-01629-2

    Article  CAS  Google Scholar 

  17. 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 42:4067–4080. https://doi.org/10.1039/c7nj04506a

    Article  CAS  Google Scholar 

  18. Zhang K, Zhuang Q, Zhou Y et al (2012) Preparation and properties of novel low dielectric constant benzoxazole-based polybenzoxazine. J Polym Sci Part A Polym Chem 50:5115–5123. https://doi.org/10.1002/pola.26344

    Article  CAS  Google Scholar 

  19. 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 136:1–11. https://doi.org/10.1002/app.47050

    Article  CAS  Google Scholar 

  20. Chen J, Zeng M, Feng Z et al (2019) Design and preparation of benzoxazine resin with high-frequency low dielectric constants and ultralow dielectric losses. ACS Appl Polym Mater 1:625–630. https://doi.org/10.1021/acsapm.8b00083

    Article  CAS  Google Scholar 

  21. Xu P, Yan X, Cong P et al (2017) Silane coupling agent grafted graphene oxide and its modification on polybenzoxazine resin. Compos Interfaces 24:635–648. https://doi.org/10.1080/09276440.2017.1254989

    Article  CAS  Google Scholar 

  22. Salahuddin N, Rehab A, El-Deeb IY, Elmokadem R (2022) Effect of graphene oxide on photo- and thermal curing of chalcone-based benzoxazine resins. Polym Bull 79:3175–3191. https://doi.org/10.1007/s00289-021-03590-4

    Article  CAS  Google Scholar 

  23. Jiang Y, Yan S, Chen Y, Li S (2019) Preparation, characterization, and properties of silanized graphene oxide reinforced biobased benzoxazine-bismaleimide resin composites. J Adhes Sci Technol 33:1974–1988. https://doi.org/10.1080/01694243.2019.1623434

    Article  CAS  Google Scholar 

  24. Wan L, Wang J, Xie L et al (2014) Nitrogen-enriched hierarchically porous carbons prepared from polybenzoxazine for high-performance supercapacitors. ACS Appl Mater Interfaces 6:15583–15596. https://doi.org/10.1021/am504564q

    Article  CAS  Google Scholar 

  25. Arumugam H, Krishnasamy B, Perumal G et al (2021) Bio-composites of rice husk and saw dust reinforced bio-benzoxazine/epoxy hybridized matrices: thermal, mechanical, electrical resistance and acoustic absorption properties. Constr Build Mater 312:125381. https://doi.org/10.1016/j.conbuildmat.2021.125381

    Article  CAS  Google Scholar 

  26. Krishnamoorthy K, Subramani D, Eeda N, Muthukaruppan A (2019) Development and characterization of fully bio-based polybenzoxazine-silica hybrid composites for low-k and flame-retardant applications. Polym Adv Technol 30:1856–1864. https://doi.org/10.1002/pat.4618

    Article  CAS  Google Scholar 

  27. Sasi Kumar R, Padmanathan N, Alagar M (2015) Design of hydrophobic polydimethylsiloxane and polybenzoxazine hybrids for interlayer low k dielectrics. New J Chem 39:3995–4008. https://doi.org/10.1039/c4nj02188f

    Article  CAS  Google Scholar 

  28. Vengatesan MR, Devaraju S, Dinakaran K, Alagar M (2012) SBA-15 filled polybenzoxazine nanocomposites for low-k dielectric applications. J Mater Chem 22:7559–7566. https://doi.org/10.1039/c2jm16566j

    Article  CAS  Google Scholar 

  29. Ariraman M, Sasi Kumar R, Alagar M (2014) Studies on FMCM-41 reinforced cyanate ester nanocomposites for low k applications. RSC Adv 4:57759–57767. https://doi.org/10.1039/c4ra09399b

    Article  CAS  Google Scholar 

  30. Sun J, Wei W, Xu Y et al (2015) A curing system of benzoxazine with amine: reactivity, reaction mechanism and material properties. RSC Adv 5:19048–19057. https://doi.org/10.1039/c4ra16582a

    Article  CAS  Google Scholar 

  31. Gungor FS, Bati B, Kiskan B (2019) Combining naphthoxazines and benzoxazines for non-symmetric curable oxazines by one-pot synthesis. Eur Polym J 121:109352. https://doi.org/10.1016/j.eurpolymj.2019.109352

    Article  CAS  Google Scholar 

  32. Sriharshitha S, Krishnadevi K, Devaraju S et al (2020) Eco-friendly sustainable poly(benzoxazine-co-urethane) with room-temperature-assisted self-healing based on supramolecular interactions. ACS Omega 5:33178–33185. https://doi.org/10.1021/acsomega.0c04840

    Article  CAS  Google Scholar 

  33. Van Krevelen DW (2009) Chapter 7 - Cohesive properties and solubility. In: Properties of Polymers Their Correlation with Chemical Structure; Their Numerical Estimation and Prediction from Additive Group Contributions. Elsevier B.V., pp.189-227

  34. van Krevelen DW (1975) Some basic aspects of flame resistance of polymeric materials. Polymer (Guildf) 16:615–620. https://doi.org/10.1016/0032-3861(75)90157-3

    Article  Google Scholar 

  35. Chen T, Wang X, Peng C et al (2020) Efficient flame retardancy, smoke suppression, and mechanical enhancement of β-FeOOH@Metallo-supramolecular polymer core–shell nanorod modified epoxy resin. Macromol Mater Eng 305:1–12. https://doi.org/10.1002/mame.202000137

    Article  CAS  Google Scholar 

  36. Pichaimani P, Arumugam H, Gopalakrishnan D et al (2020) Partially exfoliated α-ZrP reinforced unsaturated polyester nanocomposites by simultaneous Co-polymerization and Brønsted acid-base strategy. J Inorg Organomet Polym Mater 30:4095–4105. https://doi.org/10.1007/s10904-020-01558-x

    Article  CAS  Google Scholar 

  37. Zhang L, Mao J, Wang S et al (2019) Benzoxazine based high performance materials with low dielectric constant: a review. Curr Org Chem 23:809–822. https://doi.org/10.2174/1385272823666190422130917

    Article  CAS  Google Scholar 

  38. Li Y, Yu Q, Yin X et al (2018) Fabrication of superhydrophobic and superoleophilic polybenzoxazine-based cotton fabric for oil–water separation. Cellulose 25:6691–6704. https://doi.org/10.1007/s10570-018-2024-8

    Article  CAS  Google Scholar 

  39. Ocón P, Cristobal AB, Herrasti P, Fatas E (2005) Corrosion performance of conducting polymer coatings applied on mild steel. Corros Sci 47:649–662. https://doi.org/10.1016/j.corsci.2004.07.005

    Article  CAS  Google Scholar 

  40. Akbarian M, Olya ME, Mahdavian M, Ataeefard M (2014) Effects of nanoparticulate silver on the corrosion protection performance of polyurethane coatings on mild steel in sodium chloride solution. Prog Org Coatings 77:1233–1240. https://doi.org/10.1016/j.porgcoat.2014.03.023

    Article  CAS  Google Scholar 

  41. Krishnan S, Arumugam H, Kuppan C et al (2017) Silane-functionalized polybenzoxazines: a superior corrosion resistant coating for steel plates. Mater Corros 68:1343–1354. https://doi.org/10.1002/maco.201709587

    Article  CAS  Google Scholar 

  42. Bentiss F, Lagrenee M, Traisnel M, Hornez JC (1999) The corrosion inhibition of mild steel in acidic media by a new triazole derivative. Corros Sci 41:789–803. https://doi.org/10.1016/S0010-938X(98)00153-X

    Article  CAS  Google Scholar 

  43. Yao Z, Jiang Z, Wang F (2007) Study on corrosion resistance and roughness of micro-plasma oxidation ceramic coatings on Ti alloy by EIS technique. Electrochim Acta 52:4539–4546. https://doi.org/10.1016/j.electacta.2006.12.052

    Article  CAS  Google Scholar 

  44. Khun NW, Troconis BCR, Frankel GS (2014) Effects of carbon nanotube content on adhesion strength and wear and corrosion resistance of epoxy composite coatings on AA2024-T3. Prog Org Coat 77:72–80. https://doi.org/10.1016/j.porgcoat.2013.08.003

    Article  CAS  Google Scholar 

  45. Ranganathan S, Arumugam H, Krishnasamy B et al (2022) Bio-based polybenzoxazines as an efficient coatings to protect mild steel surfaces from corrosion. High Perform Polym 34:593–603. https://doi.org/10.1177/09540083221085163

    Article  CAS  Google Scholar 

  46. Soliman AMM, Aly KI, Mohamed MG et al (2023) Synthesis, characterization and protective efficiency of novel polybenzoxazine precursor as an anticorrosive coating for mild steel. Sci Rep 13:5581. https://doi.org/10.1038/s41598-023-30364-x

    Article  CAS  Google Scholar 

  47. Aly KI, Mahdy A, Hegazy MA et al (2020) Corrosion resistance of mild steel coated with phthalimide-functionalized polybenzoxazines. Coatings 10:1–1114. https://doi.org/10.3390/coatings10111114

    Article  CAS  Google Scholar 

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Acknowledgements

Authors would like to express their sincere thanks to the PSG Management, Secretary and Principal of the PSG Institute of Technology and Applied Research, Coimbatore, 641062, India. Also, the authors would also like to express their sincere appreciation to DRDL-CARS, India (Dr. A. Hariharan/2023) for the financial support.

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Authors and Affiliations

  1. Polymer Engineering Laboratory, PSG Institute of Technology and Applied Research, Neelambur, Coimbatore , 641 062, India

    K Mohamed Mydeen, Hariharan Arumugam, Balaji Krishnasamy & Alagar Muthukaruppan

  2. Polymer Composites Lab, Department of Chemistry, School of Applied Sciences and Humanities, Vignan’s Foundation for Science, Technology and Research, Vadlamudi, Guntur, 522 213, India

    Devaraju Subramani

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Contributions

MMK was involved in synthesis, methodology, investigation, writing—original draft. AH was involved in conceptualization, methodology, investigation, validation, writing—original draft, review & editing, resources, supervision. KB contributed to methodology, review & editing, project administration. DS was involved in characterization, validation. Muthukaruppan Alagar helped in resources, validation, supervision.

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Correspondence to Hariharan Arumugam, Balaji Krishnasamy or Alagar Muthukaruppan.

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Mohamed Mydeen, K., Arumugam, H., Krishnasamy, B. et al. Nonylphenol-based polybenzoxazine composites: hydrophobic coating, ultra-low-k and anticorrosion applications. J Mater Sci 58, 10340–10358 (2023). https://doi.org/10.1007/s10853-023-08671-5

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