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Preparation, Characterization, and Antioxidant Activity of β-Carotene Impregnated Polyurethane Based on Epoxidized Soybean Oil and Malic Acid

  • Pathikrit Saha
  • Beom Soo KimEmail author
Original paper
  • 17 Downloads

Abstract

A new polyol was synthesized based on epoxidized soybean oil (ESO) and malic acid (MA) for the formulation of a bio-based polyurethane. The synthesized polyol was characterized by Fourier transform-infrared spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry. Polyurethanes were formed by reacting the synthesized ESO-MA polyol with 1,6-hexamethylene diisocyanate at different isocyanate/hydroxyl ratios. The tensile and thermal properties of the prepared polyurethanes were analyzed by differential scanning calorimetry, thermogravimetric analysis, and universal testing machine. The polyurethanes exhibited a tensile strength of 1.34–5.56 MPa, an elongation at break of 20–41%, and a glass transition temperature of − 2.7 to 0.6 °C. In addition, β-carotene, a natural antioxidant, was impregnated on the polyurethane surface and its effect on the tensile and thermal properties of polyurethane was investigated. An increase in tensile strength and a reduction in elongation at break were observed in these β-carotene impregnated polyurethane films. They also showed up to 61% radical scavenging activity against 2,2-diphenyl-1-picryhydrazyl radical in methanol. Moreover, these films retained radical scavenging activity for more than 50 days.

Keywords

Soybean oil Malic acid Bio-based polyurethane β-Carotene Antioxidant activity 

Notes

Acknowledgments

This research was supported by the National Research Foundation of Korea (NRF-2017R1A2B4002371 and 2019R1I1A3A02058523).

References

  1. 1.
    Akindoyo JO, Beg MDH, Ghazali S, Islam MR, Jeyaratnam N, Yuvaraj AR (2016) Polyurethane types, synthesis and applications—a review. RSC Adv 6:114453–114482CrossRefGoogle Scholar
  2. 2.
    Hu S, Wan C, Li Y (2012) Production and characterization of biopolyols and polyurethanefoams from crude glycerol based liquefaction of soybean straw. Bioresour Technol 103:227–233CrossRefGoogle Scholar
  3. 3.
    Kong X, Yue J, Narine SS (2007) Physical properties of canola oil based polyurethane networks. Biomacromolecules 8:3584–3589CrossRefGoogle Scholar
  4. 4.
    Petrović ZS, Yang L, Zlatanic A, Zhang W, Javni I (2007) Network structure and properties of polyurethanes from soybean oil. J Appl Polym Sci 105:2717–2727CrossRefGoogle Scholar
  5. 5.
    Zhang C, Li Y, Chen R, Kessler MR (2014) Polyurethanes from solvent-free vegetable oil-based polyols. ACS Sustain Chem Eng 2:2465–2476CrossRefGoogle Scholar
  6. 6.
    Pfister DP, Xia Y, Larock RC (2011) Recent advances in vegetable oil-based polyurethanes. Chemsuschem 4:703–717CrossRefGoogle Scholar
  7. 7.
    Pechar TW, Sohn S, Wilkes GL, Ghosh S, Frazier CE, Fornof A, Long TE (2006) Characterization and comparison of polyurethane networks prepared using soybean-based polyols with varying hydroxyl content and their blends with petroleum-based polyols. J Appl Polym Sci 101:1432–1443CrossRefGoogle Scholar
  8. 8.
    Feng Y, Liang H, Ziming Y, Teng Y, Ying L, Puwang L, Yang Z, Zhang C (2017) A solvent-free and scalable method to prepare soybean-oil-based polyols by thiol–ene photo-click reaction and biobased polyurethanes therefrom. ACS Sustain Chem Eng 5:7365–7373CrossRefGoogle Scholar
  9. 9.
    Tu Y-C, Kiatsimkul P, Suppes G, Hsieh FH (2007) Physical properties of water-blown rigid polyurethane foams from vegetable oil-based polyols. J Appl Polym Sci 105:453–459CrossRefGoogle Scholar
  10. 10.
    Ji D, Fang Z, He W, Zhang K, Luo Z, Wang T, Guo K (2015) Synthesis of soy-polyols using a continuous microflow system and preparation of soy-based polyurethane rigid foams. ACS Sustain Chem Eng 3:1197–1204CrossRefGoogle Scholar
  11. 11.
    Sienkiewicz AM, Czub P (2016) The unique activity of catalyst in the epoxidation of soybean oil and following reaction of epoxidized product with bisphenol A. Ind Crops Prod 83:755–773CrossRefGoogle Scholar
  12. 12.
    Desroches M, Caillol S, Lapinte V, Auvergne R, Boutevin B (2011) Synthesis of biobased polyols by thiol–ene coupling from vegetable oils. Macromolecules 44:2489–2500CrossRefGoogle Scholar
  13. 13.
    Caillol S, Desroches M, Boutevin G, Loubat C, Auvergne R, Boutevin B (2012) Synthesis of new polyester polyols from epoxidized vegetable oils and biobased acids. Eur J Lipid Sci Technol 114:1447–1459CrossRefGoogle Scholar
  14. 14.
    Datta J, Głowińska E (2014) Effect of hydroxylated soybean oil and bio-based propanediol on the structure and thermal properties of synthesized bio-polyurethanes. Ind Crops Prod 61:84–91CrossRefGoogle Scholar
  15. 15.
    Dai H, Yang L, Lin B, Wang C, Shi G (2009) Synthesis and characterization of the different soy-based polyols by ring opening of epoxidized soybean oil with methanol, 1,2-ethanediol and 1,2-propanediol. J Am Oil Chem Soc 86:261–267CrossRefGoogle Scholar
  16. 16.
    Narine SS, Kong X, Bouzidi L, Sporns P (2007) Physical properties of polyurethanes produced from polyols from seed oils: I. Elastomers. J Am Oil Chem Soc 84:55–63CrossRefGoogle Scholar
  17. 17.
    Lu Y, Larock RC (2008) Soybean-oil-based waterborne polyurethane dispersions: effects of polyol functionality and hard segment content on properties. Biomacromolecules 9:3332–3340CrossRefGoogle Scholar
  18. 18.
    Lubguban AA, Tu Y-C, Lozada ZR, Hsieh F-H, Suppes GJ (2009) Noncatalytic polymerization of ethylene glycol and epoxy molecules for rigid polyurethane foam applications. J Appl Polym Sci 112:2185–2194CrossRefGoogle Scholar
  19. 19.
    Dahlke B, Helbert S, Paetow M, Zech W-H (1995) Polyhydroxy fatty acids and their derivatives from plant oils. J Am Oil Chem Soc 72:349–353CrossRefGoogle Scholar
  20. 20.
    Li Z, Zhang R, Moon K-S, Liu Y, Hansen K, Le T, Wong CP (2013) Highly conductive, flexible, polyurethane-based adhesives for flexible and printed electronics. Adv Funct Mater 23:1459–1465CrossRefGoogle Scholar
  21. 21.
    Li Y, Sun XS (2014) Di-hydroxylated soybean oil polyols with varied hydroxyl values and their influence on UV-curable pressure-sensitive adhesives. J Am Oil Chem Soc 91:1425–1432CrossRefGoogle Scholar
  22. 22.
    Guo A, Cho Y, Petrović ZS (2000) Structure and properties of halogenated and nonhalogenated soy-based polyols. J Polym Sci Pol Chem 38:3900–3910CrossRefGoogle Scholar
  23. 23.
    Pelletier H, Belgacem N, Gandini A (2006) Acrylated vegetable oils as photocrosslinkable materials. J Appl Polym Sci 99:3218–3221CrossRefGoogle Scholar
  24. 24.
    Doll KM, Sharma BK, Erhan SZ (2007) Synthesis of branched methyl hydroxy stearates including an ester from bio-based levulinic acid. Ind Eng Chem Res 46:3513–3519CrossRefGoogle Scholar
  25. 25.
    Datta J, Kosiorek P, Włoch M (2017) Synthesis, structure and properties of poly(ether-urethane)s synthesized using a tri-functional oxypropylated glycerol as a polyol. J Therm Anal Calorim 128:155–167CrossRefGoogle Scholar
  26. 26.
    Miao S, Zhang S, Su Z, Wang P (2013) Synthesis of bio-based polyurethanes from epoxidized soybean oil and isopropanolamine. J Appl Polym Sci 127:1929–1936CrossRefGoogle Scholar
  27. 27.
    Miao S, Zhang S, Su Z, Wang P (2010) A novel vegetable oil–lactate hybrid monomer for synthesis of high-T g polyurethanes. J Polym Sci Pol Chem 48:243–250CrossRefGoogle Scholar
  28. 28.
    Li Y, Sun XS (2015) Polyols from epoxidized soybean oil and alpha hydroxyl acids and their adhesion properties from UV polymerization. Int J Adhes Adhes 63:1–8CrossRefGoogle Scholar
  29. 29.
    Keykhosravi K, Javan JA, Parsaiemehr M (2016) Effect of malic acid on bioactive components and antioxidant properties of sliced button mushroom (Agaricus bisporus) during storage. Iran J Vet Med 9:287–294Google Scholar
  30. 30.
    Assis RQ, Pagno CH, Costa TMH, Flores SH, Rios AO (2018) Synthesis of biodegradable films based on cassava starch containing free and nanoencapsulated β-carotene. Packag Technol Sci 31:157–166CrossRefGoogle Scholar
  31. 31.
    Martins JT, Cerqueira MA, Vicente AA (2012) Influence of α-tocopherol on physicochemical properties of chitosan-based films. Food Hydrocolloid 27:220–227CrossRefGoogle Scholar
  32. 32.
    Kim S, Baek S-K, Go E, Song KB (2018) Application of adzuki bean starch in antioxidant films containing cocoa nibs extract. Polymers 10:1210CrossRefGoogle Scholar
  33. 33.
    Norajit K, Kim KM, Ryu GH (2010) Comparative studies on the characterization and antioxidant properties of biodegradable alginate films containing ginseng extract. J Food Eng 98:377–384CrossRefGoogle Scholar
  34. 34.
    Pagno CH, Faris YB, Costa TMH, Rios AO, Flores SH (2016) Synthesis of biodegradable films with antioxidant properties based on cassava starch containing bixin nanocapsules. J Food Sci Technol 53:3197–3205CrossRefGoogle Scholar
  35. 35.
    Noronha CM, Carvalho SM, Lino RC, Barreto PLM (2014) Characterization of antioxidant methylcellulose film incorporated with α-tocopherol nanocapsules. Food Chem 159:529–535CrossRefGoogle Scholar
  36. 36.
    Zaccari F, Cabrera MC, Ramos A, Saadoun A (2015) In vitro bioaccessibility of β-carotene, Ca, Mg and Zn in landrace carrots (Daucus carota, L.). Food Chem 166:365–371CrossRefGoogle Scholar
  37. 37.
    Dinda S, Patwardhan AV, Goud VV, Pradhan NC (2008) Epoxidation of cottonseed oil by aqueous hydrogen peroxide catalysed by liquid inorganic acids. Bioresour Technol 99:3737–3744CrossRefGoogle Scholar
  38. 38.
    Hojabri L, Kong X, Narine SS (2009) Fatty acid-derived diisocyanate and biobased polyurethane produced from vegetable oil: synthesis, polymerization, and characterization. Biomacromolecules 10:884–891CrossRefGoogle Scholar
  39. 39.
    Tran TK, Kumar P, Kim H-R, Hou CT, Kim BS (2018) Microbial conversion of vegetable oil to hydroxy fatty acid and its application to bio-based polyurethane synthesis. Polymers 10:927CrossRefGoogle Scholar
  40. 40.
    Li J, Zhu M (2017) Structural characterization of a vegetable oil-based polyol through liquid chromatography multistage mass spectrometry. J Polym Sci Pol Chem 55:255–262CrossRefGoogle Scholar
  41. 41.
    Baheiraei N, Yeganesh H, Ai J, Gharibi R, Azami M, Faghihi F (2014) Synthesis, characterization and antioxidant activity of a novel electroactive and biodegradable polyurethane for cardiac tissue engineering application. Mater Sci Eng C 44:24–37CrossRefGoogle Scholar
  42. 42.
    Singh BB, Shakil NA, Kumar J, Walia S, Kar A (2015) Development of slow release formulations of β-carotene employing amphiphilic polymers and their release kinetics study in water and different pH conditions. J Food Sci Technol 52:8068–8076CrossRefGoogle Scholar
  43. 43.
    Semsarzadeh MA, Navarchian AH (2003) Effects of NCO/OH ratio and catalyst concentration on structure, thermal stability, and crosslink density of poly(urethane-isocyanurate). J Appl Polym Sci 90:963–972CrossRefGoogle Scholar
  44. 44.
    Semnani D, Nasari M, Fakhrali A (2018) PCL nanofibers loaded with beta-carotene: a novel treatment for eczema. Polym Bull 75:2015–2026CrossRefGoogle Scholar
  45. 45.
    Crick CR, Noimark S, Peveler WJ, Bear JC, Ivanov AP, Edel JB, Parkin IP (2015) Advanced analysis of nanoparticle composites—a means toward increasing the efficiency of functional materials. RSC Adv 5(66):53789–53795CrossRefGoogle Scholar
  46. 46.
    Perni S, Piccirillo C, Pratten J, Prokovich P, Chrzanowski W, Parkin IP, Wilson M (2009) The antimicrobial properties of light-activated polymers containing methylene blue and gold nanoparticles. Biomaterials 30:89–93CrossRefGoogle Scholar
  47. 47.
    Piñeros-Hernandez D, Medina-Jaramilo C, Lopez-Cordoa A, Goyanes S (2017) Edible cassava starch films carrying rosemary antioxidant extracts for potential use as active food packaging. Food Hydrocolloid 63:488–495CrossRefGoogle Scholar
  48. 48.
    Gogoi S, Karak N (2014) Biobased biodegradable waterborne hyperbranched polyurethane as an ecofriendly sustainable material. ACS Sustain Chem Eng 2:2730–2738CrossRefGoogle Scholar
  49. 49.
    López-Rubio A, Lagaron JM (2010) Improvement of UV stability and mechanical properties of biopolyesters through the addition of β-carotene. Polym Degrad Stabil 95:2162–2168CrossRefGoogle Scholar
  50. 50.
    Lotfy S, Fawzy YHA (2014) Characterization and enhancement of the electrical performance of radiation modified poly (vinyl) alcohol/gelatin copolymer films doped with carotene. J Radiat Res Appl Sci 7:338–345CrossRefGoogle Scholar
  51. 51.
    Mueller L, Boehm V (2011) Antioxidant activity of β-carotene compounds in different in vitro assays. Molecules 16:1055–1069CrossRefGoogle Scholar
  52. 52.
    Quirós-Sauceda AE, Ayala-Zavala JF, Olivas GI, Gonzalez-Aguilar GA (2014) Edible coatings as encapsulating matrices for bioactive compounds: a review. J Food Sci Technol 51:1674–1685CrossRefGoogle Scholar
  53. 53.
    Barba AIO, Hurtado MC, Mata MCS, Ruiz VF, Tejada MLS (2006) Application of a UV–vis detection-HPLC method for a rapid determination of lycopene and β-carotene in vegetables. Food Chem 95:328–336CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemical EngineeringChungbuk National UniversityCheongjuRepublic of Korea

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