Skip to main content
Log in

Preparation and Characterization of Starch-Based Bioplastic Films Modified by Citric Acid-Epoxidized Soybean Oil Oligomers

  • Original Paper
  • Published:
Journal of Polymers and the Environment Aims and scope Submit manuscript

Abstract

In this work, citric acid (CA) was successfully used to improve the features of starch-based bioplastic films containing epoxidized soybean oils (ESO). Citric acid-epoxidized soybean oil oligomers (CESO) with different degrees of polymerization were synthesized by controlling the molar ratios of CA to ESO (nCOOH/epoxy = 1 ~ 4). The molecular weight and degree of polymerization of CESO decreased as more CA was incorporated. Starch-based bioplastic films with CESO were produced via solution casting and characterized by structural, thermal, tensile, water resistance, and optical properties. The hydrogen bonding interactions between starch and CESO were confirmed by Fourier transform infrared spectroscopy (FTIR). Field emission scanning electron microscopy (FESEM) micrographs suggested that CESO exhibited better compatibility with starch than ESO. Bioplastic films with CESO presented lower swelling degree and opacity as well as higher thermal property and tensile strength than the film with ESO. The composites with CESO2 (nCOOH/epoxy = 2) showed the most comprehensive properties including thermal stability, tensile strength, opacity, and water resistance than those with other CESO. Higher contents of CA in CESO (nCOOH/epoxy > 2) might cause the degradation of starch and deteriorate the properties of the films.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Scheme 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

Data Availability

The datasets generated during and/or analysed during the current study are available from the corresponding authors on reasonable request.

References

  1. Moshood TD, Nawanir G, Mahmud F, Mohamad F, Ahmad MH, Abdul Ghani A (2021) Expanding policy for biodegradable plastic products and market dynamics of bio-based plastics: challenges and opportunities. Sustainability 13(11):6170–6191

    Article  CAS  Google Scholar 

  2. Singh P, Verma R (2020) Bioplastics: a green approach toward sustainable environment. Environ Microbiol Biotechnol 1:35–53

    Article  Google Scholar 

  3. Sun S, Liu P, Ji N, Hou H, Dong H (2018) Effects of various cross-linking agents on the physicochemical properties of starch/PHA composite films produced by extrusion blowing. Food Hydrocoll 77:964–975

    Article  CAS  Google Scholar 

  4. Marinković AD, Vuksanović MM, Karić N, Đokić V, Popović M, Jančić Heinemann R, Tomić NZ (2020) The effect of natural modifiers for starch hydrophobization on performance of composite based on ethylene acrylic acid copolymer. Polymer Compos 42(3):1325–1337

    Article  Google Scholar 

  5. Lei B, Liang Y, Feng Y, He H, Yang Z (2018) Preparation and characteristics of biocomposites based on steam exploded Sisal fiber modified with amphipathic epoxidized soybean oil resin. Materials 11(9):1731–1744

    Article  PubMed  PubMed Central  Google Scholar 

  6. Zhao T, Wu Y, Li Y, Wang M, Zeng J (2017) High performance and thermal processable dicarboxylic acid cured epoxidized plant oil resins through dynamic vulcanization with poly(lactic acid). ACS Sustain Chem Eng 5(2):1938–1947

    Article  CAS  Google Scholar 

  7. Gogoi P, Boruah M, Sharma S, Dolui SK (2015) Blends of epoxidized alkyd resins based on Jatropha oil and the epoxidized oil cured with aqueous citric acid solution: a green technology approach. ACS Sustain Chem Eng 3(2):261–268

    Article  CAS  Google Scholar 

  8. Wu H, Lei Y, Lu J, Zhu R, Xiao D, Jiao C, Xia R, Zhang Z, Shen G, Liu Y, Li S, Li M (2019) Effect of citric acid induced crosslinking on the structure and properties of potato starch/chitosan composite films. Food Hydrocoll 97:105208–105218

    Article  CAS  Google Scholar 

  9. Lee S, Zhang M, Wang G, Meng W, Zhang X, Wang D, Zhou Y, Wang Z (2021) Characterization of polyvinyl alcohol/starch composite films incorporated with p-coumaric acid modified chitosan and chitosan nanoparticles: a comparative study. Carbohydr Polym 262:117930–117941

    Article  CAS  PubMed  Google Scholar 

  10. Olssona E, Menzelb C, Johanssona C, Anderssonb R, Kochb K, Järnströma L (2013) The effect of pH on hydrolysis, cross-linking and barrier properties of starch barriers containing citric acid. Carbohyd Polym 98:1505–1513

    Article  Google Scholar 

  11. Cai Z, Čadek D, Šmejkalová P, Kadeřábková A, Nová M, Kuta A (2021) The modification of properties of thermoplastic starch materials: combining potato starch with natural rubber and epoxidized natural rubber. Mater Today Commun 26:101912–101923

    Article  CAS  Google Scholar 

  12. Liu P, Li Y, Shang X, Xie F (2019) Starch-zinc complex and its reinforcement effect on starch-based materials. Carbohydr Polym 206:528–538

    Article  CAS  PubMed  Google Scholar 

  13. Sartori T, Menegalli FC (2016) Development and characterization of unripe banana starch films incorporated with solid lipid microparticles containing ascorbic acid. Food Hydrocoll 55:210–219

    Article  CAS  Google Scholar 

  14. Rafiee F, Rezaie Karder F (2020) Bio-crosslinking of chitosan with oxidized starch, its functionalization with amino acid and magnetization: as a green magnetic support for silver immobilization and its catalytic activity investigation. Int J Biol Macromol 146:1124–1132

    Article  CAS  PubMed  Google Scholar 

  15. Kadam A, Pawar M, Yemul O, Thamke V, Kodam K (2015) Biodegradable biobased epoxy resin from karanja oil. Polymer 72:82–92

    Article  CAS  Google Scholar 

  16. Dai X, Xiong Z, Na H, Zhu J (2014) How does epoxidized soybean oil improve the toughness of microcrystalline cellulose filled polylactide acid composites? Compos Sci Technol 90:9–15

    Article  CAS  Google Scholar 

  17. Mauck SC, Wang S, Ding W, Rohde BJ, Fortune CK, Yang G, Ahn S-K, Robertson ML (2016) Biorenewable tough blends of polylactide and acrylated epoxidized soybean oil compatibilized by a polylactide star polymer. Macromolecules 49(5):1605–1615

    Article  CAS  Google Scholar 

  18. Ali F (2016) Plasticizing poly(lactic acid) using epoxidized palm oil for environmental friendly packaging material. Malaysian J Anal Sci 20(5):1153–1158

    Article  Google Scholar 

  19. Belhassen R, Vilaseca F, Mutjé P, Boufi S (2014) Thermoplasticized starch modified by reactive blending with epoxidized soybean oil. Ind Crops Prod 53:261–267

    Article  CAS  Google Scholar 

  20. Yang J, Ching YC, Chuah CH, Nguyen DH, Liou N-S (2021) Synthesis and characterization of starch/fiber-based bioplastic composites modified by citric acid-epoxidized palm oil oligomer with reactive blending. Ind Crops Prod 170:113797–113808

    Article  CAS  Google Scholar 

  21. Altuna L, Herrera ML, Foresti ML (2018) Synthesis and characterization of octenyl succinic anhydride modified starches for food applications review recent literature. Food Hydrocoll 80:97–110

    Article  CAS  Google Scholar 

  22. Liu W, Qiu J, Zhu L, Fei M-E, Qiu R, Sakai E, Ito K, Song G, Tang G (2018) Tannic acid-induced crosslinking of epoxidized soybean oil for toughening poly(lactic acid) via dynamic vulcanization. Polymer 148:109–118

    Article  CAS  Google Scholar 

  23. Yang J, Dong X, Wang J, Ching YC, Liu J, l. Chunhui, Y. Baikeli, Z. li, N. Mohammed Al-Hada, S. Xu. (2022) Synthesis and properties of bioplastics from corn starch and citric acid-epoxidized soybean oil oligomers. J Mater Res Technol 20:373–380

    Article  CAS  Google Scholar 

  24. Hazarika D, Karak N (2015) Waterborne sustainable tough hyperbranched aliphatic polyester. ACS Sustain Chem Eng 3:2458–2468

    Article  CAS  Google Scholar 

  25. Orue A, Eceiza A, Arbelaiz A (2018) Preparation and characterization of poly(lactic acid) plasticized with vegetable oils and reinforced with sisal fibers. Ind Crops Prod 112:170–180

    Article  CAS  Google Scholar 

  26. Pawar M, Kadam A, Yemul O, Thamke V, Kodam K (2016) Biodegradable bioepoxy resins based on epoxidized natural oil (cottonseed & algae) cured with citric and tartaric acids through solution polymerization: a renewable approach. Ind Crops Prod 89:434–447

    Article  CAS  Google Scholar 

  27. Bonilla J, Talón E, Atarés L, Vargas M, Chiralt A (2013) Effect of the incorporation of antioxidants on physicochemical and antioxidant properties of wheat starch–chitosan films. J Food Eng 118(3):271–278

    Article  CAS  Google Scholar 

  28. Owi WT, Ong HL, Sam ST, Villagracia AR, Tsai C, Akil HM (2019) Unveiling the physicochemical properties of natural Citrus aurantifolia crosslinked tapioca starch/nanocellulose bionanocomposites. Ind Crops Prod 139:111548–111561

    Article  CAS  Google Scholar 

  29. Kahvand F, Fasihi M (2019) Plasticizing and anti-plasticizing effects of polyvinyl alcohol in blend with thermoplastic starch. Int J Biol Macromol 140:775–781

    Article  CAS  PubMed  Google Scholar 

  30. Ren L, Yan X, Zhou J, Tong J, Su X (2017) Influence of chitosan concentration on mechanical and barrier properties of corn starch/chitosan films. Int J Biol Macromol 105(Pt 3):1636–1643

    Article  CAS  PubMed  Google Scholar 

  31. Liu H, Adhikari R, Guo Q, Adhikari B (2013) Preparation and characterization of glycerol plasticized (high-amylose) starch-chitosan films. J Food Eng 116(2):588–597

    Article  CAS  Google Scholar 

  32. Teaca CA, Bodirlau R, Spiridon I (2013) Effect of cellulose reinforcement on the properties of organic acid modified starch microparticles/plasticized starch bio-composite films. Carbohydr Polym 93(1):307–315

    Article  CAS  PubMed  Google Scholar 

  33. Wang R, Liu P, Cui B, Kang X, Yu B (2019) Effects of different treatment methods on properties of potato starch-lauric acid complex and potato starch-based films. Int J Biol Macromol 124:34–40

    Article  CAS  PubMed  Google Scholar 

  34. Suriyatem R, Auras RA, Rachtanapun P (2018) Improvement of mechanical properties and thermal stability of biodegradable rice starch–based films blended with carboxymethyl chitosan. Ind Crops Prod 122:37–48

    Article  CAS  Google Scholar 

  35. Mendes JF, Paschoalin RT, Carmona VB, Sena Neto AR, Marques ACP, Marconcini JM, Mattoso LHC, Medeiros ES, Oliveira JE (2016) Biodegradable polymer blends based on corn starch and thermoplastic chitosan processed by extrusion. Carbohydr Polym 137:452–458

    Article  CAS  PubMed  Google Scholar 

  36. Liu W, Qiu J, Chen T, Fei M, Qiu R, Sakai E (2019) Regulating tannic acid-crosslinked epoxidized soybean oil oligomers for strengthening and toughening bamboo fibers-reinforced poly(lactic acid) biocomposites. Compos Sci Technol 181:107709–107718

    Article  CAS  Google Scholar 

  37. Muscat D, Adhikari B, Adhikari R, Chaudhary DS (2012) Comparative study of film forming behaviour of low and high amylose starches using glycerol and xylitol as plasticizers. J Food Eng 109(2):189–201

    Article  CAS  Google Scholar 

  38. Thakur R, Pristijono P, Golding JB, Stathopoulos CE, Scarlett CJ, Bowyer M, Singh SP, Vuong QV (2017) Amylose-lipid complex as a measure of variations in physical, mechanical and barrier attributes of rice starch-ι-carrageenan biodegradable edible film. Food Packag Shelf Life 14:108–115

    Article  Google Scholar 

  39. Kim JY, Huber KC (2013) Corn starch granules with enhanced load-carrying capacity via citric acid treatment. Carbohydr Polym 91(1):39–47

    Article  CAS  PubMed  Google Scholar 

  40. Yang J, Ching YC, Sabariah J, Chuah CH, Nguyen DH, Lin PC (2022) Comparative study on the properties of starch-based bioplastics incorporated with palm oil and epoxidized palm oil. Polym Polym Compos 30:1–11

    Google Scholar 

  41. Yang J, Ching YC, Chuah CH (2021) Nai-Shang L, Preparation and characterization of starch/empty fruit bunch-based bioplastic composites reinforced with epoxidized oils. Polym 13:94

    Article  CAS  Google Scholar 

Download references

Funding

This work has been funded by the Talent Introduction Project of Dezhou University (No. 2022xjrc102) and University Malaya research grant (ST078-2022, PV13-2019 and PR006-2019A).

Author information

Authors and Affiliations

Authors

Contributions

Jianlei Yang wrote the conducted experiments and analysis and wrote the main manuscript text. Yern Chee Ching provided supervision, funding, conceptualization, reviewed and Edited. Shicai Xu provided supervision and result validation Kuan Yong Ching, Xiuzhen Ran, Naif Mohammed Al-Hada, and Xiao Sui provided conceptualization and formal analysis Xiao Sui, YunWei Wei, Jiafeng Yu, Jihua Wang and Jiehua Zhou provided conceptualization, Methodology, Writing - Review and Editing

Corresponding authors

Correspondence to Yern Chee Ching or Shicai Xu.

Ethics declarations

Conflict of interest

The authors have no relevant financial or non-financial interests to disclose.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 98 KB)

Supplementary file2 (DOCX 231 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yang, J., Ching, Y.C., Ching, K.Y. et al. Preparation and Characterization of Starch-Based Bioplastic Films Modified by Citric Acid-Epoxidized Soybean Oil Oligomers. J Polym Environ 31, 954–964 (2023). https://doi.org/10.1007/s10924-022-02661-5

Download citation

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10924-022-02661-5

Keywords

Navigation