全氟磺酸复合膜加工性能研究
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摘要
本文针对其转型前全氟磺酰树脂的各种性能参数进行了深入的研究,根据其特有的加工流动性能,采用符合该树脂的熔融挤出流延成膜工艺,复合制备全氟磺酸离子交换薄膜。
本实验选取了几种不同离子交换容量(IEC值)的氟型全氟磺酸离子交换树脂(PFSR),分别利用热失重分析(TGA)、熔体流动速率仪(MFI)、毛细管流变仪、哈克扭矩流变仪、X射线衍射(XRD)和红外透射光谱(IR)对不同树脂的熔融加工稳定性、熔体流变性能及挤出树脂的结晶性能进行了全面的分析研究。实验表明,树脂在380℃以下静态稳定性都很好,但当温度升高后随IEC值的升高而下降。低剪切速率下PFSR熔融温度随IEC的升高而明显降低。通过流变学测试得出PFSR树脂为剪切变稀型非牛顿流体,其表观粘度对加工剪切速率敏感。PFSR树脂在高剪切速率下的动态热稳定性能明显下降,当达到240℃以上树脂中会出现微小气泡,其加工和动态热稳定温度随IEC值的降低而增加。通过XRD测试得出PFSR树脂为一种低结晶型聚合物,其结晶能力主要受其IEC值影响,并随其增加而下降。
强碱条件下水解生成离子交换基团(—SO_3Na),成为全氟磺酸离子交换树脂。对转型前后树脂各项性能指标进行对比测试,其红外透射光谱(IR)发生了很大改变,热稳定性、结晶性能和熔融加工性能大幅下降,但是力学强度明显增加。
在实验中改善全氟磺酸离子交换膜的制备工艺,采用熔融流延挤出方法来制备不同IEC值的全氟磺酸离子交换薄膜,并对加工设备、模具选择。
In this paper,we carefully researched on all kinds of performance of Perfluorosulfonated ion-exchanged resins(PFSR) before it was hydrolyzed. we used the melt casting technology to become membrane,to which fabricate the composite membrane accrondant to PFSR's characteristics.This process technology is based on PFSR's special rheology performance.
Many kinds of perfluorosulfonyl fluoride resins with different IEC values were chosen to be candidates for preparing the perfluorosulfonate fluoride ion-exchange membrane(PFSIEM).Thermal stability,rheology of the PFSR and crystallinity of the PFSR were studied by means of TGA,MFI,capillarity rheometer,Hakke torque and XRD.Laboratory tests show that the static thermal stability of PFSRs are perfect under 380℃,but they decrease with rise of IEC values when persistent overheating.At a low rate of shear,melting temperature of PFSRs decreases with increases of IEC.Throught the rheology testing shows that PFSRs are shear thinned fluid and their appearent viscosity are sensitive to shear rate.Dynamic thermal stability of PFSRs are degrade distinctly under high shear rate,and tiny bubbles will appear when arrive at 240℃.their dynamic thermal stability increase with decrease of IEC values. XRD tests shows that PFSR is a kind of low crystalline polymer and the degree of crystallization is mainly influenced by IEC values and decrease with its increase.
In alkaline condition,PFSR hydrolyse to become perfluorosulfunic acid resin and to generate ion-exchange group(-SO_3Na).Compared the tests of all kinds of hydrolytic resin's performance with un-hydrolytic,they shows that IR spectrum has made a great changes and its thermal stability,crystallinity,melt extrusion performance degrade greatly.But its tensile strenght grow obviously.
The process technic was improved in the experiments.PEFSIEMs were fabricated by melt extrusion casting techonlogy on PFSR resins with different IEC values.Throught careful research of resin's feature,the processing equipment,the choice of flow casting mold and the processing technology of membranes were studied.
本实验选取了几种不同离子交换容量(IEC值)的氟型全氟磺酸离子交换树脂(PFSR),分别利用热失重分析(TGA)、熔体流动速率仪(MFI)、毛细管流变仪、哈克扭矩流变仪、X射线衍射(XRD)和红外透射光谱(IR)对不同树脂的熔融加工稳定性、熔体流变性能及挤出树脂的结晶性能进行了全面的分析研究。实验表明,树脂在380℃以下静态稳定性都很好,但当温度升高后随IEC值的升高而下降。低剪切速率下PFSR熔融温度随IEC的升高而明显降低。通过流变学测试得出PFSR树脂为剪切变稀型非牛顿流体,其表观粘度对加工剪切速率敏感。PFSR树脂在高剪切速率下的动态热稳定性能明显下降,当达到240℃以上树脂中会出现微小气泡,其加工和动态热稳定温度随IEC值的降低而增加。通过XRD测试得出PFSR树脂为一种低结晶型聚合物,其结晶能力主要受其IEC值影响,并随其增加而下降。
强碱条件下水解生成离子交换基团(—SO_3Na),成为全氟磺酸离子交换树脂。对转型前后树脂各项性能指标进行对比测试,其红外透射光谱(IR)发生了很大改变,热稳定性、结晶性能和熔融加工性能大幅下降,但是力学强度明显增加。
在实验中改善全氟磺酸离子交换膜的制备工艺,采用熔融流延挤出方法来制备不同IEC值的全氟磺酸离子交换薄膜,并对加工设备、模具选择。
In this paper,we carefully researched on all kinds of performance of Perfluorosulfonated ion-exchanged resins(PFSR) before it was hydrolyzed. we used the melt casting technology to become membrane,to which fabricate the composite membrane accrondant to PFSR's characteristics.This process technology is based on PFSR's special rheology performance.
Many kinds of perfluorosulfonyl fluoride resins with different IEC values were chosen to be candidates for preparing the perfluorosulfonate fluoride ion-exchange membrane(PFSIEM).Thermal stability,rheology of the PFSR and crystallinity of the PFSR were studied by means of TGA,MFI,capillarity rheometer,Hakke torque and XRD.Laboratory tests show that the static thermal stability of PFSRs are perfect under 380℃,but they decrease with rise of IEC values when persistent overheating.At a low rate of shear,melting temperature of PFSRs decreases with increases of IEC.Throught the rheology testing shows that PFSRs are shear thinned fluid and their appearent viscosity are sensitive to shear rate.Dynamic thermal stability of PFSRs are degrade distinctly under high shear rate,and tiny bubbles will appear when arrive at 240℃.their dynamic thermal stability increase with decrease of IEC values. XRD tests shows that PFSR is a kind of low crystalline polymer and the degree of crystallization is mainly influenced by IEC values and decrease with its increase.
In alkaline condition,PFSR hydrolyse to become perfluorosulfunic acid resin and to generate ion-exchange group(-SO_3Na).Compared the tests of all kinds of hydrolytic resin's performance with un-hydrolytic,they shows that IR spectrum has made a great changes and its thermal stability,crystallinity,melt extrusion performance degrade greatly.But its tensile strenght grow obviously.
The process technic was improved in the experiments.PEFSIEMs were fabricated by melt extrusion casting techonlogy on PFSR resins with different IEC values.Throught careful research of resin's feature,the processing equipment,the choice of flow casting mold and the processing technology of membranes were studied.
引文
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