Chen Chin-Wen, Ranganathan Palraj, Mutharani Bhuvanenthiran, Shiu Jia-Wei, Rwei Syang-Peng, Chang Yen-Hsiang, Chiu Fang-Chyou
Department of Molecular Science and Engineering, Institute of Organic and Polymeric Materials, Research and Development Center of Smart Textile Technology, National Taipei University of Technology, Taipei 10608, Taiwan.
Department of Chemical and Materials Engineering, Chang Gung University, Taoyuan 333, Taiwan.
Polymers (Basel). 2024 Jan 4;16(1):159. doi: 10.3390/polym16010159.
The search for alternatives to petroleum-based thermoplastic polyamide elastomers (TPAEs) has recently drawn great interest. In this study, a bio-massed TPAE, PA12,36, was synthesized using 1,12-dodecanediamine (DDA) and fatty dimer acid (FDA, Pripol1009) precursors via catalyst and solvent-free melt polycondensation. The molecular structure and molecular weight of the PA12,36 were characterized by H NMR, FTIR, and GPC. PA12,36 displayed a low melting temperature of 85.8 °C, an initial degradation temperature of 425 °C, and a glass-transition temperature of 30.4 °C, whereas it sustained satisfactory tensile strength (10.0 MPa) and superior strain at break (1378%). Furthermore, PA12,36 was foamed by supercritical CO, and the cell size, cell density, and porosity were determined. The entangled long-chained FDA component generated a physically crosslinked network, which promoted the melt viscosity of PA12,36 against elongations of foam cell growth and increased foamability significantly. As a result, uniform structured cellular foams with a cell diameter of 15-24 µm and high cell density (10 cells/cm-10 cells/cm) were successfully achieved. The foaming window was widened from 76 to 81 °C, and the expansion ratio was increased from 4.8 to 9.6. Additionally, PA12,36 foam with a physically crosslinked structure presented a better creep shape recovery percentage (92-97.9%) and sturdier dimensional stability. This bio-based PA12,36 foam is a promising candidate to replace petroleum-based thermoplastic elastomer foams for engineering applications, particularly shoe soles.
最近,寻找石油基热塑性聚酰胺弹性体(TPAE)的替代品引起了人们极大的兴趣。在本研究中,通过无催化剂和无溶剂的熔融缩聚反应,使用1,12-十二烷二胺(DDA)和脂肪二聚酸(FDA,Pripol1009)前体合成了一种生物质TPAE,即PA12,36。通过核磁共振氢谱(1H NMR)、傅里叶变换红外光谱(FTIR)和凝胶渗透色谱(GPC)对PA12,36的分子结构和分子量进行了表征。PA12,36的熔点低至85.8℃,初始降解温度为425℃,玻璃化转变温度为30.4℃,同时具有令人满意的拉伸强度(10.0MPa)和优异的断裂伸长率(1378%)。此外,采用超临界CO2对PA12,36进行发泡,并测定了泡孔尺寸、泡孔密度和孔隙率。缠结的长链FDA组分形成了物理交联网络,这提高了PA12,36在泡孔生长伸长时的熔体粘度,并显著提高了发泡性。结果,成功制备出泡孔直径为15-24μm且泡孔密度高(108-109个细胞/cm3)的结构均匀的泡沫材料。发泡窗口从76℃拓宽到81℃,膨胀比从4.8提高到9.6。此外,具有物理交联结构的PA12,36泡沫材料具有更好的蠕变形状恢复率(92-97.9%)和更稳定的尺寸稳定性。这种生物基PA12,36泡沫材料有望替代石油基热塑性弹性体泡沫材料,用于工程应用,特别是鞋底。