Renewable malic acid-based plasticizers for both PVC and PLA polymers

Minsu Park; Inwoo Choi; Sangjun Lee; Seung-ju Hong; Aryeon Kim; Jihoon Shin; Ho-Cheol Kang; Young-Wun Kim

Journal of Industrial and Engineering Chemistry, Vol.88, 148-158, August, 2020

DOI10.1016/j.jiec.2020.04.007 Export Citation

Renewable malic acid-based plasticizers for both PVC and PLA polymers

Minsu Park^{1, 2}, Inwoo Choi^{1, 2}, Sangjun Lee³, Seung-ju Hong^{1, 2}, Aryeon Kim¹, Jihoon Shin^{1, 2}, Ho-Cheol Kang¹, and Young-Wun Kim^{1, 2, †}

¹Center for Environment & Sustainable Resources, Carbon Resources Institute, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Yuseong-gu, Daejeon 34114, Republic of Korea
²Department of Advanced Materials & Chemical Engineering, University of Science & Technology, 217 Gajeong-ro, Yuseong-gu, Daejeon 34113, Republic of Korea
³Yoo Sung Chem. R&T Co., Ltd., 14 Sinpyeonggongdan 1-ro, Chubu-myeon, Geumsan-gun, Chungcheongnam-do 32710, Republic of Korea

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Acetylated malic acid alkyl esters (AcMAE-Cn) with different alkyl chain lengths, as alternative plasticizers for both poly(vinyl chloride) (PVC) and poly(lactic acid) (PLA), were synthesized by the esterification of renewable malic acid with alcohols and subsequent acetylation. The molecular structure of the synthesized plasticizers was confirmed using 1H NMR and FT-IR spectroscopy. PVC or PLA blends containing 50 phr of the plasticizers were evaluated by dynamic mechanical analysis (DMA), tensile testing, and migration testing to evaluate the plasticization efficiency. The plasticized PVC films presented good plasticizing performance, as demonstrated by the results of tensile and migration testing and the Tg values (as determined by DMA). Among the plasticizers, AcMAE-C6 and AcMAE-C8 presented enhanced plasticizing performance compared with that of the commercial dioctyl adipate (DOA) and di (2-ethylhexyl) phthalate (DEHP) plasticizers. Additionally, the plasticizing properties of the plasticized PLA films depend significantly on the structure of the plasticizers. It was found that plasticizers (AcMAEC4 and AcMAE-C6) bearing short alkyl groups (n-butyl and n-hexyl, respectively) may act as excellent plasticizers. In summary, the AcMAE-C6 plasticizer showed potential as an alternative plasticizer for both PVC and PLA polymers.

Keywords:Malic acid alkyl esters;Plasticizers;Renewable resources;Poly(vinyl chloride);Poly(lactic acid)

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[2] Tickner JA, Schettler T, Guidotti T, McCally M, Rossi M, Am. J. Ind. Med., 39, 100 (2001)

[3] Waring RH, Harris RM, Mol. Cell. Endocrinol., 244, 2 (2005)

[4] Fenollar O, Sanchez-Nacher L, Garcia-Sanoguera D, Lopez J, Balart R, J. Mater. Sci., 44(14), 3702 (2009)

[5] Fontelles JB, Clarke C, OJEU, 48, 40 (2005)

[6] Public Law 110-314 - August 14, Consumer Product Safety Improvement Act of 2008, pp.3016 (2016).

[7] Erythropel HC, Dodd P, Leask RL, Maric M, Cooper DG, Chemosphere, 91, 358 (2013)

[8] Erythropel HC, Brown T, Maric M, Nicell JA, Cooper DG, Leask RL, Chemosphere, 134, 106 (2015)

[9] Erythropel HC, Shipley S, Bormann A, Nicell JA, Maric M, Leask RL, Polymer, 89, 18 (2016)

[10] Bouchareb B, Benaniba MT, J. Appl. Polym. Sci., 107, 3442 (2007)

[11] Mehta B, Kathalewar M, Sabnis A, J. Appl. Polym. Sci., 131, 40354 (2014)

[12] Greco A, Brunetti D, Renna G, Mele G, Maffezzoli A, Polym. Degrad. Stabil., 95, 2169 (2010)

[13] Liu T, Jiang P, Liu H, Li M, Dong Y, Wang R, Wang Y, Polym. Test, 61, 205 (2017)

[14] Rasal RM, Janorkar AV, Hirt DE, Prog. Polym. Sci, 35, 338 (2010)

[15] Garlotta D, J. Polym. Environ., 9, 63 (2001)

[16] Farah S, Anderson DG, Langer R, Adv. Drug Deliv. Rev., 107, 367 (2016)

[17] Nampoothiri KM, Nair NR, John RP, Bioresour. Technol., 101(22), 8493 (2010)

[18] Roberto A, Rachele C, Gennaro G, Veronica A, Stefano F, Maurizio A, Mariacristina C, Emanuela EM, Eur. Polym. J., 66, 533 (2015)

[19] Labrecque LV, Kumar RA, Dave V, Gross RA, Mccarthy SP, J. Appl. Polym. Sci., 66(8), 1507 (1997)

[20] Li Y, Shimizu H, Macromol. Biosci., 7, 921 (2007)

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[22] Wang N, Yu J, Ma X, Polym. Int., 56, 1440 (2007)

[23] Kulinski Z, Piorkowska E, Gadzinowska K, Stasiak M, Biomacromolecules, 7(7), 2128 (2006)

[24] Sungsanit K, Kao N, Bhattacharya SN, Polym. Eng. Sci., 52, 108 (2011)

[25] Bocque M, Voirin C, Lapinte V, Caillol S, Robin JJ, J. Polym. Sci. A: Polym. Chem., 54, 11 (2015)

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[28] Yu J, Sun L, Ma C, Qiao Y, Yao H, Waste Manage., 48, 300 (2016)

[29] Werpy T, Petersen G, U.S. National Renewable Energy Lab., Oak Ridge, (2004).

[30] ASTM D638-14 Standard Test Method for Tensile Properties of Plastics.

[31] ASTM D1239-98, Standard Test Method for Resistance of Plastics Films to Extraction by Chemicals.

[32] Fahnhorst GW, Hoye TR, ACS Macro Lett., 7, 143 (2018)

[33] Cao N, Yang X, Fu Y, Food Hydrocolloids, 23, 729 (2009)

[34] Landel RF, Nielsen LE, Mechanical Properties of Polymers and Composites, second ed., CRC Press, pp.6 1993.

[35] Hansen CM, A User's Handbook, second ed., CRC Press, pp.2 2007.

[36] Harte I, Birkinshaw C, Jones E, Kennedy J, DeBarra E, J. Appl. Polym. Sci., 127(3), 1997 (2013)

[37] Ljungberg N, Wesslen B, Polymer, 44(25), 7679 (2003)

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[39] Sato S, Gondo D, Wada T, Kanehashi S, Nagai K, J. Appl. Polym. Sci., 129(3), 1607 (2013)