Li Zhiyong, Chu Yongjing, Huang Qing, Jin Xiaopei, Qiu Zhicheng, Jin Jian
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China.
State Key Laboratory of Biobased Fiber Manufacturing Technology, China Textile Academy Co., Ltd., Beijing 100025, China.
Polymers (Basel). 2024 Apr 22;16(8):1177. doi: 10.3390/polym16081177.
The polar sulfonate groups in cationic dyeable polyester (CDP) lead to complex crystallization behavior, affecting CDP production's stability. In this study, cationic dyeable polyesters (CDP) with different sulfonate group contents were prepared via one-step feeding of sodium isophthalic acid-5-sulfonate (SIPA), terephthalic acid (PTA), and ethylene glycol (EG). The non-isothermal crystallization behavior of these copolyesters was analyzed by differential scanning calorimetry (DSC). Results show that the crystallization temperature of the sample shifts to lower values with the increase in SIPA content. The relaxation behavior of the molecular chain is enhanced due to the ionic aggregation effect of sulfonate groups in CDP. Therefore, at low cooling rates (2.5 °C/min and 5 °C/min), some molecular chain segments in CDP are still too late to orderly stack into the lattice, forming metastable crystals, and melting double peaks appear on the melting curve after crystallization. When the cooling rate increases (10-20 °C/min), the limited region of sulfonate aggregation in CDP increases, resulting in more random chain segments, and a cold crystallization peak appears on the melting curve after crystallization. The non-isothermal crystallization behavior of all samples was fitted and analyzed by the Jeziorny equation, Ozawa equation, and Mo equation. The results indicate that the nucleation density and nucleation growth rate of CDP decrease with the increase in SIPA content. Meanwhile, analysis of the Kissinger equation reveals that the activation energy of non-isothermal crystallization decreases gradually with the increase in SIPA content, and the addition of SIPA makes CDP crystallization more difficult.
阳离子可染聚酯(CDP)中的极性磺酸基团导致复杂的结晶行为,影响CDP生产的稳定性。本研究通过一步法加入间苯二甲酸-5-磺酸钠(SIPA)、对苯二甲酸(PTA)和乙二醇(EG)制备了具有不同磺酸基团含量的阳离子可染聚酯(CDP)。采用差示扫描量热法(DSC)分析了这些共聚酯的非等温结晶行为。结果表明,随着SIPA含量的增加,样品的结晶温度向低温方向移动。由于CDP中磺酸基团的离子聚集效应,分子链的松弛行为增强。因此,在低冷却速率(2.5℃/min和5℃/min)下,CDP中的一些分子链段仍来不及有序堆叠到晶格中,形成亚稳晶体,结晶后熔融曲线上出现熔融双峰。当冷却速率增加(10 - 20℃/min)时,CDP中磺酸基团聚集的受限区域增大,导致链段更加无序,结晶后熔融曲线上出现冷结晶峰。采用Jeziorny方程、Ozawa方程和Mo方程对所有样品的非等温结晶行为进行拟合和分析。结果表明,CDP的成核密度和成核生长速率随SIPA含量的增加而降低。同时,对Kissinger方程的分析表明,非等温结晶的活化能随SIPA含量的增加而逐渐降低,SIPA的加入使CDP结晶更加困难。