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Thermally rearranged copolymer membranes containing Cardo fluorene-containing structures for enhanced gas separation performance
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DOI：10.1016/j.polymer.2025.129514.png)
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Abstract
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In this work, two fluorenyl-containing diamine monomers, 9,9-bis[3-methyl-4-(4-amino-3-hydroxyphenoxy) phenyl]fluorene (BMAHPF) and 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHF), were synthesized. Then, the poly(amic acid) solutions were synthesized via copolymerization of BMAHPF and BAHF at varying molar ratios with 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). After thermal imidization and further rearrangement, the copolyimide (CPI) and copolymerized thermally rearranged (CTR) membranes were prepared, respectively. The test results showed that as the BMAHPF/BAHF molar ratio varied from 9:1 to 5:5, the tensile strength of the CPI membranes decreased from 113.7 MPa to 73.7 MPa, while the glass transition temperature increased from 345 degrees C to 380 degrees C. After thermal rearrangement, the mechanical properties of the membrane samples declined, but their gas permeabilities increased significantly. Additionally, with an increase in the molar ratio of rigid BAHF, the permeabilities of the four gases through the CTR(BMAHPF-BAHF) membranes showed a marked upward trend. The CO2, H2, O2, and N2 permeabilities of the CTR(BMAHPF-BAHF)-5:5 reached 889.67, 927.01, 189.95, and 40.90 Barrer, respectively. Meanwhile, the CTR(BMAHPF-BAHF)-8:2 exhibited optimal O2/N2 separation performance, and the CTR(BMAHPF-BAHF)-9:1 achieved the best CO2/N2 separation performance, both exceeding the 2008 Robeson Upper Bound. Consequently, the fluorenyl-containing CTR(BMAHPF-BAHF) membranes demonstrated attractive gas separation performance and excellent anti-aging properties, making them promising candidates for practical gas separation applications.
Keywords:
Thermally rearranged copolymers
Fluorenyl structures
Gas separation
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