Phthalide-containing poly(ether-imide)s based thermal rearrangement membranes for gas separation application

• Published in: RSC advances Vol. 12; no. 2; pp. 728 - 742
• Main Authors: He, Lei, Lu, Yunhua, Xiao, Guoyong, Hou, Mengjie, Chi, Haijun, Wang, Tonghua
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 22.12.2021; The Royal Society of Chemistry
• Subjects: Carbon dioxide; Chemical reduction; Chemistry; Crosslinking; Cyclobutane; Diamines; Dianhydrides; Gas separation; Heat treatment; Mechanical properties; Membranes; Methane; Nitrophenol; Phenolphthalein; Polyetherimides; Selectivity; Substitution reactions
• ISSN: 2046-2069; 2046-2069
• DOI: 10.1039/d1ra07013d

The diamine monomer 3,3-bis[4-(3-hydroxy-4-amino-phenoxy)phenyl]phthalide (BHAPPP) was firstly synthesized by the nucleophilic substitution of 5-fluoro-2-nitrophenol and phenolphthalein, followed by a reduction reaction. A series of phthalide-containing poly(ether imide)s (PEI) were then prepared through the polycondensation of BHAPPP with six kinds of dianhydrides, including 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4-benzophenone tetracarboxylic dianhydride (BTDA), 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA), 4,4′-oxydiphthalic dianhydride (ODPA), 1,2,3,4-cyclobutane tetracarboxylic dianhydride (CBDA) and pyromellitic dianhydride (PMDA), as well as thermal imidization. After further thermal treatment, the corresponding thermal rearrangement (TR) membranes were obtained. Due to the existence of the phthalide lactone ring, the PEIs probably underwent TR and crosslinking simultaneously. With the increase of thermal treatment temperature, the mechanical properties of the TR membranes dramatically decreased, but the gas separation properties obviously increased. When the PEIs were treated at 450 °C for 1 h, the CO 2 , H 2 , O 2 , N 2 and CH 4 permeability of TR(BHAPPP-6FDA) reached 258.5, 190.5, 38.35, 4.25 and 2.15 Barrers, respectively. Meanwhile, the CO 2 /CH 4 selectivity of 120.2 sharply exceeded the 2008 Robeson limit, and O 2 /N 2 selectivity was 9.02, close to the 2015 upper limit. Therefore, the TR membranes derived from phthalide-containing PEIs exhibit superior gas separation performance, andare expected to be applied in the field of gas separation. The 3,3-bis[4-(3-hydroxy-4-amino-phenoxy)phenyl]phthalide was firstly synthesized and polymerized to prepare six kinds of phthalide-containing poly(ether imide)s. After further thermal rearrangement, the corresponding membranes exhibited excellent gas separation performance.