Abstract
When cashew nutshell oil (CNSO), a well-known non-edible natural oil, is utilised as a blocking agent with diphenylmethane diisocyanate (MDI), this material displayed several advantages over commonly used petroleum-based phenolic compounds, including favourable deblocking conditions and decreased viscosity and better storage stability. When natural rubber (NR) is exposed to sunlight, ozone, UV radiation, and air, especially at high temperatures, the presence of unsaturated carbon–carbon double bonds in the backbone causes quick breakdown. In this work, the multiple bonds present in NR main chain were utilised and made saturated by the way of green emulsion polymerisation using CNSO-blocked MDI using a simple redox initiator. The polymerisation reaction was carried out at different monomer ratios to analyse the thermal stability of natural rubber. The deblocking temperature for CNSO-blocked MDI was determined using CO2 evolution and the thermo-gravimetric (TGA) methods. Gel time analysis was also conducted and found suitable for heat-curable polyurethane systems. FT-IR and NMR spectroscopic methods were used to examine structural properties. The TGA analysis of copolymer synthesised using NR and CNSO-blocked MDI at an equivalent weight ratio shows higher thermal stability. From this observation, CNSO-blocked MDI greatly improves the thermal stability of natural rubber.
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References
Avaz G, Meier WU, Casselmann H, Achten D (2012) 10.24–Polyurethanes. Polym Sci A Compr Ref 10:411–441. https://doi.org/10.1016/B978-0-444-53349-4.00275-2
Abushammala H, Mao J (2019) A review of the surface modification of cellulose and nanocellulose using aliphatic and aromatic mono- and di-isocyanates. Molecules 24(15):2782. https://doi.org/10.3390/molecules24152782
Shin SR, Liang JY, Ryu H, Song GS, Lee DS (2019) Effects of isosorbide incorporation into flexible polyurethane foams: reversible urethane linkages and antioxidant activity. Molecules 24(7):1347. https://doi.org/10.3390/molecules24071347
Sankar G, Yan N (2014) Synthesis and deblocking studies of low temperature heat-curable blocked polymeric methylene diphenyl diisocyanates. J Mol Sci Part A 52(1):47–55. https://doi.org/10.1080/10601325.2014.976748
Burelo M, Gaytán I, Loza-Tavera H, Cruz-Morales JA, Zárate-Saldaña D, Cruz-Gómez MJ, Gutiérrez S (2022) Synthesis, characterization and biodegradation studies of polyurethanes: effect of unsaturation on biodegradability. Chemosphere 23:136136. https://doi.org/10.1016/j.chemosphere.2022.136136
Adamu AA, Muhamad SN, Gan SN (2022) Polyurethane resin derived from polyol of palm olein and recycled poly(ethylene terephthalate). Pigment Resin Technol 51(1):6–12. https://doi.org/10.1108/PRT-06-2020-0056
Burelo M, Martínez A, Cruz-Morales JA, Tlenkopatchev MA, Gutierrez S (2019) Metathesis reaction from bio-based resources: synthesis of diols and macrodiols using fatty alcohols, β-citronellol and natural rubber. Polym Degrad Stabil 166:202–212. https://doi.org/10.1016/j.polymdegradstab.2019.05.021
Mohapatra S, Nando GB (2013) Chemical modification of natural rubber in the latex stage by grafting cardanol, a waste from the cashew industry and a renewable resource. Ind Eng Chem Res 52:5951–5957. https://doi.org/10.1021/ie400195v
Calo 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 9:754–759. https://doi.org/10.1039/B617180J
Mele G, Lomonaco D, Mazzetto SE (2017) Cardanol-based heterocycles: synthesis and applications. In: Cashew nut shell liquid. Springer International Publishing, pp 39–56. https://doi.org/10.1007/978-3-319-47455-7_3
Siwarote B, Sae-Oui P, Wirasate S (2017) Effects of bio-based oils on processing properties and cure characteristics of silica-filled natural rubber compounds. J Rubber Res 20:1–19. https://doi.org/10.1007/BF03449138
Preetom S, Anil KB (2017) Sustainable rubbers and rubber additives. J Appl Polym Sci 135:45701–45725. https://doi.org/10.1002/app.45701
Wongthong P, Nakason C, Pan Q, Rempel GL, Kiatkamjornwong S (2013) Modification of deproteinized natural rubber via grafting polymerization with maleic anhydride. Eur Polym J 49(12):4035–4046. https://doi.org/10.1016/j.eurpolymj.2013.09.009
Benmesli S, Riahi F (2014) Dynamic mechanical and thermal properties of a chemically modified polypropylene/natural rubber thermoplastic elastomer blend. Polym Test 36:54–61. https://doi.org/10.1016/j.polymertesting.2014.03.016
Zhong JP, Li SD, Peng Z, Yu HP (1999) Study on preparation of chlorinated natural rubber from latex and its thermal stability. J Appl Polym Sci 73:2863–2867. https://doi.org/10.1002/(SICI)1097-4628(19990929)73:14%3c2863::AID-APP9%3e3.0.CO;2-2
Gelling IR (1985) Modification of natural rubber latex with peracetic acid. Rubber Chem Technol 58(1):86–96. https://doi.org/10.5254/1.3536060
Mahittikul A, Prasassarakich P, Rempel GL (2006) Hydrogenation of natural rubber latex in the presence of OsHCl(CO)(O2)(PCy3)2. J Appl Polym Sci 100(1):640–655. https://doi.org/10.1002/app.23390
Huang NJ, Sundberg DC (1995) Fundamental studies of grafting reactions in free radical copolymerization I: a detailed kinetic model for solution polymerization. J Polym Sci Part A Polym Chem 33(15):2533–2549. https://doi.org/10.1002/pola.1995.080331502
Kim S, Adkins J, Biswas A (2017) Reinforcement of latex rubber by the incorporation of amphiphilic particles. J Rubber Res 20:87–100. https://doi.org/10.1007/BF03449144
Okieimen FE, Urhoghide IN (2002) Graft copolymerization of acrylonitrile and methyl methacrylate monomer mixtures on crumb natural rubber. J Appl Polym Sci 84(10):1872–1877. https://doi.org/10.1002/app.10474
Arayapranee W, Prasassarakich P, Rempel GL (2002) Synthesis of graft copolymers from natural rubber using cumene hydroperoxide redox initiator. J Appl Polym Sci 83(14):2993–3001. https://doi.org/10.1002/app.2328
Songsing K, Vatanatham T, Hansupalak N (2013) Kinetics and mechanism of grafting styrene onto natural rubber in emulsion polymerization using cumene hydroperoxide–tetraethylenepentamine as redox initiator. Eur Polym J 49(5):1007–1016. https://doi.org/10.1016/j.eurpolymj.2013.01.027
Kawahara S, Kawazura T, Sawada T, Isono Y (2003) Preparation and characterization of natural rubber dispersed in nano-matrix. Polymer 44(16):4527–4531. https://doi.org/10.1016/S0032-3861(03)00415-4
Zhang Y, Dubé MA (2017) Polymer reaction engineering of dispersed systems. J Adv Polym Sci. https://doi.org/10.1007/12_2017_8
Karthi R, Vennila S, Sankar G (2022) Synthesis and deblocking investigations of phenol blocked aliphatic isocyanates and their application in the development of epoxy-polyurethane films. Asian J Chem 34(2):361–370. https://doi.org/10.14233/ajchem.2022.23574
Kochthongrasamee T, Prasassarakich P, Kiatkamjornwong S (2006) Effects of redox initiator on graft copolymerization of methyl methacrylate onto natural rubber. J Appl Polym Sci 101(4):2587–2601. https://doi.org/10.1002/app.23997
Irina D, Peter JCH, Li D, Rebecca P, Marcus R, Regina P (2016) Alternative monomers based on lignocellulose and their use for polymer production. Chem Rev 116(3):1540–1599. https://doi.org/10.1021/acs.chemrev.5b00354
Balgude D, Konge K, Sabnis A (2013) Synthesis and characterization of sol-gel derived CNSL based hybrid anti-corrosive coatings. J Sol-Gel Sci Technol 69:155–165. https://doi.org/10.1007/s10971-013-3198-z
Hu Y, Shang Q, Bo C, Jia P, Feng G, Zhang F, Liu C, Zhou Y (2019) Synthesis and properties of UV-curable polyfunctional polyurethane acrylate resins from cardanol. ACS Omega 4(7):12505–12511. https://doi.org/10.1021/acsomega.9b01174
Samantarai S, Mahata D, Nag A, Nando GB, Das NC (2017) Functionalization of acrylonitrile butadiene rubber with meta-pentadecenyl phenol, a multifunctional additive and a renewable resource. Rubber Chem Technol 90(4):683–698. https://doi.org/10.5254/rct.17.83728
Intapun J, Rungruang T, Suchat S, Cherdchim B, Hiziroglu S (2021) The characteristics of natural rubber composites with Klason lignin as a green reinforcing filler: thermal stability, mechanical and dynamical properties. Polymers 13(7):1109. https://doi.org/10.3390/polym13071109
Lomonaco D, Maia FJN, Mazzetto SE (2012) Thermal evaluation of cashew nutshell liquid as new bioadditives for poly(methyl methacrylate). J Therm Anal Calorim 111(1):619–626. https://doi.org/10.1007/s10973-012-2383-6
Valencia-Bermudez S, Hernández-López S, Gutiérrez-Nava M, Rojas-García JM, Lugo-Uribe LE (2020) Chain-end functional di-sorbitan oleate monomer obtained from renewable resources as precursors for bio-based polyurethanes. J Polym Environ 28:1406–1419. https://doi.org/10.1007/s10924-020-01692-0
Nguyen TN, Duy HN, Anh DT, Thi TN, Nguyen TH, Van NN, Quang TT, Huy TN, Thi TT (2020) Improvement of thermal and mechanical properties of vietnam deproteinized natural rubber via graft copolymerization with methyl methacrylate. Int J Polym Sci 11:9037827. https://doi.org/10.1155/2020/9037827
Nam NH, Anh KD, Truc LGT, Ha TA, Ha VTT (2020) Pyrolysis of cashew nut shell: a parametric study. Vietnam J Chem 58:506–511. https://doi.org/10.1002/vjch.202000015
Acknowledgements
Author Sankar Govindarajan is grateful for the funding of the project under RUSA 2.0 (C3/RI and QI/PF5-Appoint/Theme-2/Group-3/2021/175 dated 14 June 2021). One of the authors (Elavazhagan Gunasekaran) thanks UGC-CSIR, New Delhi, India, for the financial assistance in the form of Junior Research Fellowship (JRF).
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RUSA 2.0 (C3/RI and QI/PF5-Appoint/Theme-2/Group-3/2021/175 dated 14 June 2021), Author Sankar Govindarajan.
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Formal analysis, investigation, data curation, methodology, EG and VS; conceptualisation, investigation, methodology, SV; resources, supervision, writing—original draft, SG.
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Gunasekaran, E., Srinivasan, V., Vasam, S. et al. Sustainable cashew nutshell oil-blocked diphenylmethane diisocyanates in co-polymerisation with natural rubber. J Rubber Res 26, 279–289 (2023). https://doi.org/10.1007/s42464-023-00207-5
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DOI: https://doi.org/10.1007/s42464-023-00207-5