Dziendzioł Patryk, Waśkiewicz Sylwia, Jaszcz Katarzyna
Department of Physical Chemistry and Technology of Polymers, Faculty of Chemistry, Silesian University of Technology, M. Strzody 9, 44-100 Gliwice, Poland.
Department of Development, R&D of Grupa Azoty Zakłady Azotowe Kędzierzyn S.A., Mostowa 30A Street, 47-220 Kędzierzyn-Koźle, Poland.
Materials (Basel). 2025 May 7;18(9):2155. doi: 10.3390/ma18092155.
Phthalates are compounds widely used as very effective plasticizers of PVC. Unfortunately, they are also widely known to be endocrine disruptors and are detrimental to human health and the environment. For this reason, environmentally friendly plasticizers are being intensively sought after in response to the market needs in the context of sustainable development and legislative changes regarding the use of phthalates. Our research presents an innovative approach to addressing this problem. In this paper, we propose new biobased oligoesters as non-toxic and harmless plasticizers of poly(vinyl chloride). New plasticizers were obtained by polyesterification of saturated dimerized fatty acid (DFA), adipic acid (ADA), triethylene glycol (TEG), and 2-ethylhexanol (2-EH), and were characterized by nuclear magnetic resonance, size exclusion chromatography, and viscosity analyses. The compatibility of the obtained oligoesters with PVC was determined using the method for obtaining PVC films by casting from a THF solution. Selected plasticizers were used to obtain PVC blends at 50 phr. They were then tested for plasticizer migration, hardness, thermogravimetric analysis, differential scanning calorimetry, and mechanical strength. Their properties were compared with the commercially available monomeric plasticizers di(2-ethylhexyl) terephthalate and di(2-ethylhexyl) adipate. The conducted study shows that the oligoesters obtained at a molar ratio of ADA to DFA of 9:1 and using an excess of 2-EH exhibit very good compatibility and plasticizing ability. The use of higher amounts of DFA worsens the compatibility of the oligoesters with PVC. However, a 4:1 ADA-to-DFA molar ratio produced results that still allow for the use of these compounds as plasticizers at lower concentrations or in combination with other plasticizers.
邻苯二甲酸盐是广泛用作聚氯乙烯（PVC）非常有效的增塑剂的化合物。不幸的是，它们也广为人知是内分泌干扰物，对人类健康和环境有害。因此，在可持续发展背景下以及关于邻苯二甲酸盐使用的立法变化的市场需求下，人们正在积极寻求环保型增塑剂。我们的研究提出了一种创新方法来解决这个问题。在本文中，我们提出了新型生物基低聚酯作为聚氯乙烯的无毒无害增塑剂。通过饱和二聚脂肪酸（DFA）、己二酸（ADA）、三甘醇（TEG）和2-乙基己醇（2-EH）的聚酯化反应获得了新型增塑剂，并通过核磁共振、尺寸排阻色谱和粘度分析对其进行了表征。使用从四氢呋喃溶液浇铸获得PVC薄膜的方法确定了所得低聚酯与PVC的相容性。选择的增塑剂用于制备50份/100份树脂（phr）的PVC共混物。然后对它们进行增塑剂迁移、硬度、热重分析、差示扫描量热法和机械强度测试。将它们的性能与市售的单体增塑剂对苯二甲酸二（2-乙基己基）酯和己二酸二（2-乙基己基）酯进行了比较。进行的研究表明，ADA与DFA摩尔比为9:1并使用过量2-EH获得的低聚酯表现出非常好的相容性和增塑能力。使用更高量的DFA会降低低聚酯与PVC的相容性。然而，ADA与DFA摩尔比为4:1时产生的结果仍然允许在较低浓度下或将这些化合物与其他增塑剂组合用作增塑剂。
