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Economical preparation of fluorine-containing thermoplastic elastomer with good phase miscibility and elasticity based on dynamic vulcanization
Polymer International ( IF 2.9 ) Pub Date : 2023-04-24 , DOI: 10.1002/pi.6534 Yongsheng Zhao 1, 2 , Youhao Xiong 1 , Haonan Yan 1 , Hongzhe Bi 1 , Jianbin Qin 1 , Xuetao Shi 1 , Guangcheng Zhang 1
Polymer International ( IF 2.9 ) Pub Date : 2023-04-24 , DOI: 10.1002/pi.6534 Yongsheng Zhao 1, 2 , Youhao Xiong 1 , Haonan Yan 1 , Hongzhe Bi 1 , Jianbin Qin 1 , Xuetao Shi 1 , Guangcheng Zhang 1
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Thermoplastic elastomers are a green and sustainable category of high performance polymers and show the great advantage of easy processability relative to conventional rubbers. In this work, a fluorine-containing thermoplastic elastomer was prepared through dynamic crosslinking of poly(vinylidene fluoride)/poly(ethylene−methyl acrylate−glycidyl methacrylate) (PVDF/EGMA) blends with the aid of amino-terminated crosslinker (KH602). The reaction kinetics of EGMA with KH602 were evaluated by the DSC Kissinger method with an activation energy (Ea) of 103.04 kJ mol−1. The increased ‘S-type’ torque curve during dynamic crosslinking indicates the occurrence of chemical crosslinking while Fourier transform infrared spectra further demonstrate the dehydrofluorination of PVDF and the reaction between the amino group of KH602 and the epoxy group in EGMA. The prepared PVDF/EGMA (30/70) thermoplastic vulcanizate shows good reprocessability, mechanical robustness and elasticity. With increasing content of crosslinker, the stress at 300% increases from 2.3 MPa to 3.5 MPa while elongation at break decreases from 1150% to 380%. The PVDF/EGMA blend has a typical ‘sea-island’ morphology with ca 7 μm dispersed phase while PVDF/EGMA thermoplastic vulcanizates have gradually elongated disperse phases due to improved interfacial miscibility as evidenced by quantitative nanomechanical mapping AFM modulus analysis. Therefore, dynamic vulcanization is an effective and economical approach to integrate thermoplasticity and rubber elasticity into plastic/rubber pairs with good phase miscibility. © 2023 Society of Industrial Chemistry.
中文翻译：
基于动态硫化经济制备具有良好相混溶性和弹性的含氟热塑性弹性体
热塑性弹性体是一类绿色、可持续的高性能聚合物，相对于传统橡胶表现出易于加工的巨大优势。在这项工作中，通过聚偏二氟乙烯/聚（乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯）（PVDF/EGMA）共混物在氨基封端交联剂（KH602）的帮助下动态交联制备了含氟热塑性弹性体。通过DSC Kissinger方法评估了EGMA与KH602的反应动力学，活化能( E a )为103.04 kJ mol -1。动态交联过程中增加的“S型”扭矩曲线表明化学交联的发生，而傅里叶变换红外光谱进一步证明了PVDF的脱氟化氢以及KH602的氨基与EGMA中的环氧基之间的反应。制备的PVDF/EGMA（30/70）热塑性硫化橡胶具有良好的可再加工性、机械强度和弹性。随着交联剂含量的增加，300%应力从2.3 MPa增加到3.5 MPa，而断裂伸长率从1150%降低到380%。PVDF/EGMA 共混物具有典型的“海岛”形态，分散相约为7 μm，而 PVDF/EGMA 热塑性硫化橡胶由于界面混溶性的改善而具有逐渐拉长的分散相，定量纳米力学映射 AFM 模量分析证明了这一点。因此，动态硫化是将热塑性和橡胶弹性整合到具有良好相混溶性的塑料/橡胶对中的有效且经济的方法。© 2023 工业化学学会。
更新日期：2023-04-24
中文翻译：
基于动态硫化经济制备具有良好相混溶性和弹性的含氟热塑性弹性体
热塑性弹性体是一类绿色、可持续的高性能聚合物，相对于传统橡胶表现出易于加工的巨大优势。在这项工作中，通过聚偏二氟乙烯/聚（乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯）（PVDF/EGMA）共混物在氨基封端交联剂（KH602）的帮助下动态交联制备了含氟热塑性弹性体。通过DSC Kissinger方法评估了EGMA与KH602的反应动力学，活化能( E a )为103.04 kJ mol -1。动态交联过程中增加的“S型”扭矩曲线表明化学交联的发生，而傅里叶变换红外光谱进一步证明了PVDF的脱氟化氢以及KH602的氨基与EGMA中的环氧基之间的反应。制备的PVDF/EGMA（30/70）热塑性硫化橡胶具有良好的可再加工性、机械强度和弹性。随着交联剂含量的增加，300%应力从2.3 MPa增加到3.5 MPa，而断裂伸长率从1150%降低到380%。PVDF/EGMA 共混物具有典型的“海岛”形态，分散相约为7 μm，而 PVDF/EGMA 热塑性硫化橡胶由于界面混溶性的改善而具有逐渐拉长的分散相，定量纳米力学映射 AFM 模量分析证明了这一点。因此，动态硫化是将热塑性和橡胶弹性整合到具有良好相混溶性的塑料/橡胶对中的有效且经济的方法。© 2023 工业化学学会。
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