生物基半芳香聚酰胺PXD10的非等温结晶动力学  

Non-isothermal crystallization kinetics of bio-based semi-aromatic polyamide PXD10

作　　者：孙宇露 杨韶辉 李修函 SUN Yulu;YANG Shaohui;LI Xiuhan(Shanghai Gengcai New Material Co.,Ltd.,Shanghai 201100,China;Anshan Hifichem Co.,Ltd.,Anshan 114225,China)

机构地区：[1]上海庚彩新材料科技有限公司,上海201100 [2]鞍山七彩化学股份有限公司,辽宁鞍山114225

出　　处：《工程塑料应用》2025年第2期147-152,共6页Engineering Plastics Application

摘　　要：以对苯二甲胺和生物基癸二酸为原料,采用一步缩聚法合成了生物基半芳香族聚酰胺—聚癸二酰对苯二甲胺(PXD10)。利用差示扫描量热仪测试PXD10的非等温结晶过程,分别采用Jeziorny方法和莫志深方法(Mo方法)对PXD10进行非等温结晶动力学分析,运用Kissinger方程进一步计算得出PXD10的非等温结晶活化能。采用偏光显微镜(POM)观察PXD10晶体形貌。结果表明,在非等温结晶过程中,PXD10的结晶温度会随着降温速率的提升而向较低的温度方向偏移,结晶时间缩短。采用Jeziorny方法能够准确地描述PXD10的主要结晶阶段的非等温结晶行为,Avrami指数n在3.03~3.86范围内,且均不是整数,表明PXD10晶体成核和生长方式并不单一,可能同时存在异相成核和均相成核,晶体生长方式可能是三维和二维生长共存。Mo方法适用于PXD10的整个非等温结晶过程的分析,通过Mo方法得到的a值在1.15~1.22范围内基本保持稳定,降温速率的函数F(T)值在8.48~15.58范围内,并随着相对结晶度的增加而增大,表明降温速率增加能加速PXD10结晶过程,获得更高的结晶度。用Kissinger方程计算得到PXD10的非等温结晶活化能ΔE为-244.76 kJ/mol。POM观测表明,不同降温速率下,PXD10晶体形态变化较大,随着降温速率的增大,PXD10的晶体成核密度变大,晶体尺寸减小。The bio-based semi-aromatic polyamide—poly(p-xylylene sebacamide)(PXD10)was synthesized using sebacic acid and p-xylylenediamine as raw materials through a one-step condensation process.The non-isothermal crystallization behavior of PXD10 was investigated using differential scanning calorimetry.Its non-isothermal crystallization kinetics were analyzed using the Jeziorny method and Mo method,and the non-isothermal crystallization activation energy of PXD10 was calculated using the Kissinger equation.The PXD10 crystal morphology was observed by means of a polarized microscope(POM).It was found that the crystallization temperature of PXD10 decreased and the crystallization time shortened with the increase in cooling rate.The Jeziorny method was employed to accurately describe the non-isothermal crystallization behavior during the most crystallization stage of PXD10.The Avrami index n range from 3.03 to 3.86,with none of them being integers,indicating that the nucleation mode is not uniform and that both heterogeneous and homogeneous nucleation might coexist.Additionally,the crystal growth might occur in both three-dimensional and two-dimensional growth ways.The Mo method is suitable for analyzing the entire non-isothermal crystallization process of polyamide PXD10.The a values obtained through the Mo method remaine stable within the range of 1.15 to 1.22,while F(T)values range from 8.48 to 15.58 and increase with the relative crystallinity,indicating that the increased cooling rate can accelerate PXD10 crystallization process and obtain higher crystallinity.The crystallization activation energyΔE of PXD10 was calculated using the Kissinger equation to be-244.76 kJ/mol.The POM observation show that the crystal morphology of PXD10 change greatly under different cooling rates,and the crystal nucleation density of PXD10 increase and the crystal size decrease with the increase of cooling rate.

关 键 词：对苯二甲胺 癸二酸 生物基 聚酰胺 差示扫描量热 结晶动力学 结晶活化能 

分 类 号：TQ323.6[化学工程—合成树脂塑料工业]