화학공학소재연구정보센터
Journal of Industrial and Engineering Chemistry, Vol.110, 248-261, June, 2022
Eco-friendlier and sustainable natural-based additives for poly(vinyl chloride)-based composites
E-mail:,
This work presents novel natural-based and solvent-free additives for poly(vinyl chloride) (PVC), namely calcium soaps, obtained for the first time from naturally occurring epoxidized soybean and linseed oils (ESO/ELO); and biogenic calcium carbonate, obtained from chicken eggshells (EG) after different acid and/or thermal pre-treatments. Results show that these additives were able to: i) reduce the concentration of volatile organic compounds released from PVC films, including alcohols, aldehydes, esters and phthalates (97,95,90 and 84% chromatographic peak area reduction, respectively), originating safer materials; ii) improve the long-term thermal stability of PVC-based materials, while maintaining their mechanical performance and when compared to control samples formulated with a high-performance commonly employed solvent-based thermal stabilizer. Films formulated with ESO-based calcium soaps and with EG powders treated with acid and thermal treatment (200 ℃) presented the best performance in terms of heat aging and long-term thermal stability. The former also slightly improved the thermomechanical properties of the films indicating that these additives are also working as secondary plasticizers for PVC. This work gives an important contribution towards the safety and sustainability of highperformance PVC-based materials, by allowing the substitution of commercially available thermal stabilizers by new eco-friendlier and safer alternatives obtained from renewable sources.
  1. Howick C, Green Chem., 9, 243 (2007)
  2. EPA, Environmental Protection Agency, Indoor Air Quality, Volatile Organic Coumpounds’ Impat on Indoor Air Quality.
  3. Zulauf N, Dröge J, Klingelhöfer D, Braun M, Oremek GM, Groneberg DA, Int. J. Environ. Res. Public Health, 16, 2441 (2019)
  4. Yang S, Yang X, Licina D, Build. Environ., 170, 106599 (2020)
  5. Fedoruk MJ, Kerger BD, J. Expo. Sci. Env. Epid., 13, 31 (2003)
  6. Geiss O, Tirendi S, Barrero-Moreno J, Kotzias D, Environ. Int., 35, 1188 (2009)
  7. Heudorf U, Mersch-Sundermann V, Angerer J, J. Environ. Health, 210, 623 (2007)
  8. Chien YC, Sci. Total Environ., 382, 228 (2007)
  9. You KW, Ge YS, Ning ZW, J. Environ. Sci., 19, 1208 (2007)
  10. Yoshida T, Matsunaga I, Environ. Int., 32, 58 (2006)
  11. Fu ZM, Yang ZH, Rong Y, Deng L, Wu J, J. Vinyl Addit. Techn., 27, 367 (2021)
  12. Han W, Zhang M, Kong Y, Li D, Liu L, Tang S, Ding J, Liu S, Polym. Degrad. Stabil., 175, 109129 (2020)
  13. Wu J, Tang Z, Liu X, Lin W, Feng M, Lin X, Gu Y, Li Y, Yi G, Polym. Degrad. Stabil., 181, 109343 (2020)
  14. Greco A, Ferrari F, Maffezzoli A, J. Clean Prod., 164, 757 (2017)
  15. Li M, Xia J, Ding H, Ding C, Wang M, Li S, Polym. Degrad. Stabil., 139, 117 (2017)
  16. Li M, Zhang J, Xin J, Huang K, Li S, Wang M, Xia J, J. Appl. Polym. Sci., 135, 45940 (2018)
  17. Li M, Zhang J, Xin J, Huang K, Li S, Wang M, Xia J, J. Appl. Polym. Sci., 134, 44679 (2017)
  18. Li M, Jiang J, Zhang J, Yang X, Zhang Y, Li S, Song J, Huang K, Xia J, Polym. Degrad. Stabil., 109, 129 (2014)
  19. Zhang Z, Jiang P, Liu D, Feng S, Zhang P, Wang Y, Fu J, Agus H, J. Mater. Sci., 56, 10155 (2021)
  20. Cai DL, Yue X, Hao B, Ma PC, J. Clean Prod., 274, 122781 (2020)
  21. Ma Y, Song F, Kong Q, Li Q, Jia P, Zhou Y, J. Polym. Environ., 28, 2101 (2020)
  22. Tan J, Zhang S, Lu T, Li R, Zhong T, Zhu X, J. Clean Prod., 229, 1274 (2019)
  23. Marceneiro S, Alves R, Dias AMA, Lobo I, Dias I, de Pinho E, Rasteiro MG, de Sousa HC, Ind. Eng. Chem. Res., 57, 1454 (2018)
  24. Arrieta MP, Sampera MD, Jiménez-López M, Aldas M, López J, Ind. Crop. Prod., 99, 196 (2017)
  25. Kandula S, Stolp L, Grass M, Woldt B, Kodali D, J. Vinyl Addit. Technol., 23, 93 (2017)
  26. Jia PY, Zhang M, Hu L, Zhou Y, Korean J. Chem. Eng., 33, 1080 (2016)
  27. Greco A, Ferrari F, Maffezzoli A, Polym. Degrad. Stabil., 134, 220 (2016)
  28. Benaniba MT, Massardier-Nageotte V, J. Appl. Polym. Sci., 118, 3499 (2010)
  29. Jia PY, Xia H, Tang K, Zhou Y, Polymer, 10, 1303 (2018)
  30. Gönen M, Egbuchunam TO, Balköse D, Inal F, Ülkü S, J. Vinyl Addit. Technol., 21, 235 (2015)
  31. Balköse D, Egbuchunam TO, Okieimen FE, J. Therm. Anal. Calorim., 101, 795 (2010)
  32. Karmalm P, Hjertberg T, Jansson A, Dahl R, Ankner K, Polym. Degrad. Stabil., 94, 1986 (2009)
  33. Egbuchuman TO, Balköse D, Okieimen FE, Polym. Degrad. Stabil., 92, 1572 (2007)
  34. Mohammed FS, Conley M, Saunders SR, Switzer J, Jha R, Cogen JM, Chaudhary BI, Pollet P, Eckert CA, Liotta CL, J. Appl. Polym. Sci., 132, 41736 (2015)
  35. González-Ortiz LJ, Arellano M, Jasso CF, Mendizábal E, Sánchez-Peña MJ, Polym. Degrad. Stabil., 90, 154 (2005)
  36. Hosney H, Nadiem B, Ashour I, Mustafa I, El-Shibiny A, J. Appl. Polym. Sci., 135, 46270 (2018)
  37. Chaudhary BI, Nguyen BD, Smith P, Sunday N, Luong M, Zamanskiy A, Polym. Eng. Sci., 55, 643 (2015)
  38. Sun B, Chaudhary BI, Shen CY, Mao D, Yuan DM, Dai GC, Li B, Cogen JM, Polym. Eng. Sci., 53, 1645 (2013)
  39. Fenollar O, García-Sanoguera D, Sánchez-Nácher L, López J, Balart R, J. Appl. Polym. Sci., 124, 2550 (2012)
  40. Wypych G, PVC Degradation and Stabilization, 4th Edition., ChemTec Publishing, Toronto, Canada, 2020.
  41. He W, Zhu G, Gao Y, Wu H, Fang Z, Guo K, Chem. Eng. J., 380, 122532 (2020)
  42. Ye Q, Ma X, Li B, Jin Z, Xu Y, Fang C, Zhou X, Ge Y, Ye F, Polymer, 11, 531 (2019)
  43. Kumar S, Ind. Eng. Chem. Res., 58, 11659 (2019)
  44. Fu Q, Long Y, Gao Y, Ling Y, Qian H, Wang F, Zhu X, RSC Adv., 9, 10049 (2019)
  45. Meier MAR, Metzger JO, Schubert US, Chem. Soc. Rev., 36, 1788 (2007)
  46. Grossman RF, Handbook of Vinyl Formulation; John Wiley & Sons Inc, United States of America, New Jersey, 2008.
  47. Suna RD, Iriea H, Nishikawa T, Nakajima A, Watanabe T, Hashimoto K, Polym. Degrad. Stabil., 79, 253 (2003)
  48. Cohen A, Calcium Carbonate: Occurrence, Characterization and Applications; Nova Science Publishers, United States of America, 2015.
  49. Tegethoff FW, Calcium Carbonate - From the Cretaceous Period into the 21st Century, Birkhäuser Verlag Basel, Switzerland, 2012.
  50. Vandeginste V, Sustain. Mater. Technol., 29, e00317 (2021)
  51. Tiimob BJ, Jeelani S, Rangari VK, J. Appl. Polym. Sci., 133, 43124 (2016)
  52. Cree D, Rutter A, ACS Sustain. Chem. Eng., 3, 941 (2015)
  53. Artok OA, Schiller M, Everard M, J. Vinyl. Addit. Techn., 23, 125 (2017)
  54. Murungan S, Munusamy Y, Ismail H, Plast. Rubber Compos., 46, 42 (2017)
  55. Sharmeeni M, Munusamy Y, Ismail H, J. Vinyl Addit. Technol., 23, 298 (2017)
  56. Pereira RFP, Valente AJM, Fernandes M, Burrows HD, Phys. Chem. Chem. Phys., 14, 7517 (2012)
  57. Filopoulou A, Vlachou S, Boyatzis SC, Molecules, 26, 6005 (2021)
  58. Melchor JJ, Fortes ICP, J. Anal. Appl. Pyrolysis, 135, 101 (2018)
  59. Owuamanam S, Cree D, J. Compos. Sci., 4, 70 (2020)
  60. Abdesselam Y, Agassant JF, Castellani R, Valette R, Demay Y, Gourdin D, Peres R, Polym. Eng. Sci., 57, 982 (2017)
  61. Yu J, Sun L, Ma C, Qiao Y, Yao H, Waste Manage., 48, 300 (2016)
  62. Bueno-Ferrer C, Garrigós MC, Jimenez A, Polym. Degrad. Stabil., 95, 2207 (2011)