可溶性耐高温含氟不对称聚酰胺的制备及其气体分离性能
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桂林理工大学

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国家自然科学基金资助项目(51963007),广西自然科学基金资助项目(2020GXNSFAA159006,2020GXNSFAA159009),桂林市科学研究与技术开发计划(2020010906)


Preparation and Gas separation of Soluble and highly heat-resistant Asymmetric Fluorinated Polyamides
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    摘要:

    通过在二胺单体(MFPAP)中引入二氟甲基和吡啶环,设计并合成了一系列新型芳香聚酰胺(PA)。采用FT-IR、热、光学、机械、气体渗透等测试进行了性能表征,结果表明:PAs有机溶解度优异,室温下溶于DMSO、DMF和NMP等高沸点有机溶剂,加热条件下能部分溶于CHCl3、THF等低沸点有机溶剂;热稳定性突出,玻璃化转变温度(Tg)均高于283 ℃,N2氛围下热失重10%的温度均在473 ℃以上;光学性能良好,其中λcut-off = 371 ~ 392 nm,λ80% = 447 ~ 504 nm;聚合物薄膜机械性能拉伸强度为46 ~ 64 MPa,杨氏模量为1.03 ~ 1.26 GPa,断裂伸长率为1.27 ~ 3.05%;PAs的链间距在0.39 ~ 0.45 nm,具有松散的链堆积和较大的自由体积;采用定容变压法测定了He、CO2、O2、N2四种纯气体的渗透性,其中PA-b表现出最好的气体分离性能,P (He) = 6.778 barrer,α (He/N2) = 33.455。

    Abstract:

    A series of novel aromatic polyamides (PAs) were designed and synthesized by introducing diamine monomer containing difluoromethyl and pyridine rings. The properties of PAs were characterized by FT-IR, thermal, optical, mechanical and gas permeation tests. The results show that PAs have excellent organic solubility, they can dissolve in high boiling organic solvents such as DMSO, DMF and NMP at room temperature, and partially dissolve in low boiling organic solvents such as CHCl3 and THF under heating conditions. PAs present outstanding thermal stability with glass transition temperature (Tg) and the degradation temperature at 10% weight loss (T10%) exceed 283 ℃ and 473 ℃ in N2 atmosphere, respectively. They possess good optical performance with cutoff wavelength range (λcut-off) and wavelength range of 80% transmittance (λ80%) at 371 ~ 392 nm and 447 ~ 504 nm, respectively. Meanwhile, the polymer films exhibit general mechanical properties. The tensile strength of the films is in the range of 46 ~ 64 MPa, the Young's modulus is in the range of 1.03 ~ 1.26 GPa, and the elongation at break is 1.27 ~ 3.05%. The d-spacing of PAs is range from 3.9 ~ 4.5 ?, indicating their loose chain stacking and relatively large fractional free volume. The permeability of He, CO2, O2 and N2 was measured by constant volume and variable pressure method. PA-b showed the best gas separation performance, P (He) = 6.778 barrer, α (He/N2) = 33.455.

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  • 收稿日期:2021-11-19
  • 最后修改日期:2022-01-14
  • 录用日期:2022-03-27
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