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含氟三苯二胺結構強化聚酰亞胺氣體滲透性
作者:王漢利1 2 阮雪華1 代巖1 賀高紅1* 單體美2 王磊1 2 孟祥青2 許國鋒2 
單位:1.大連理工大學 精細化工國家重點實驗室 膜科學與技術研發中心 石油與化學工程學院 遼寧省石化行業高效節能分離技術工程實驗室 盤錦 124221  2.山東華夏神舟新材料有限公司 山東東岳集團含氟功能膜國家重點實驗室 淄博 255000 
關鍵詞:結構設計 含氟聚酰亞胺 氣體滲透性 分子模擬 
分類號:TQ028.3
出版年,卷(期):頁碼:2018,38(6):34-40
摘要:

 在玻璃態聚合物中引入立體側基,能夠降低主鏈堆疊、增加自由體積,提高聚合物的氣體滲透性。本文提出利用立體結構的六氟三苯二胺(BABTFMM),同六氟二酐(6FDA)進行縮聚制備具有高氣體滲透性的含氟聚酰亞胺,采用巨正則蒙特卡羅(GCMC)和分子動力學(MD)方法預測了其氣體滲透分離性能。分子模擬結果表明,二胺單體中的六氟二甲苯側基,通過空間位阻和主鏈構型限制,增加了含氟聚酰亞胺的主鏈間距,降低了堆積密度、增加了自由體積,可以提高含氟聚酰亞胺的氣體滲透性。制備了6FDA-BABTFMM和6FDA-ODA兩種含氟聚酰亞胺的均質膜進行氣體滲透性能測試。結果表明,氣體滲透性能測試結果同分子模擬結果一致,6FDA-BABTFMM較6FDA-ODA型聚酰亞胺的滲透性大幅增加,O2、N2、CH4和CO2滲透速率分別為75.2、20.5、17.2、311.3 Barrer。

 The incorporation of stereo side groups in the glassy polymer is an effective method to reduce the accumulation of the main chain, increase the free volume, and increase the gas permeability of the polymer. In this paper, the hexafluorotriphenylenediamine(BABTFMM) with tri-dimensional structure was polycondensed with hexafluoro dianhydride (6FDA) to prepare polyimides with high gas permeabilities, and using Grand Canonical Monte Carlo and molecular dynamics methods to predict its gas permeation separation performance. Homogeneous membranes were prepared for experimental test. The results of molecular simulations show that the hexafluoroxylene side groups in the diamine monomer is useful to increase the main chain spacing of the polyimide, reduce the packing density, and increase the free volume by the effect of steric hindrance and main chain configuration restriction, as a result, the gas permeability of 6FDA-BABTFMM polyimides is improved. Homogenous films of 6FDA-BABTFMM and 6FDA-ODA fluorine-containing polyimide were prepared for gas permeability test. The gas permeation performance test results are consistent with those of the molecular simulation. The permeability of 6FDA-BABTFMM is significantly higher than that of 6FDA-ODA polyimide, and the permeation rates of oxygen, nitrogen, methane, and carbon dioxide are 75.2, 20.5, 17.2, 311.3 bar, respectively.

基金項目:
國家自然科學基金青年基金(21606035, 21706023);中國博士后科學基金資助項目(2018M631167)
作者簡介:
第一作者簡介:王漢利(1974-),男,山東濱州博興人,博士研究生,高級工程師,主要研究方向為含氟膜材料制備及氣體膜分離,Email:[email protected];  通訊作者,Email:[email protected]
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