Multi-fluorous-included Counter Anions-based Ionic Copolymers: Synthesis and Enhanced Hydrophobic Adsorption Films on Copper Surface for Super Protection

• Published in: Chemical research in Chinese universities 2023-10, Vol.39 (5), p.845-856
• Main Authors: Ren, Weihua, Shi, Yueting, Chen, Lingli, Yang, Song, Zhang, Shengtao, Liu, Xiaohong, Ren, Xiaolei, Li, Hongru
• Format: Article
• Language: English
• Subjects: Addition polymerization; Adsorption; Analytical Chemistry; Anions; Chemical bonds; Chemical synthesis; Chemisorption; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Copolymers; Copper; Corrosion prevention; Electrochemistry; Fourier transforms; Hydrophobicity; Infrared spectroscopy; Inorganic Chemistry; Metal surfaces; NMR; NMR spectroscopy; Nuclear magnetic resonance; Organic Chemistry; Physical Chemistry; Polymers; Sulfuric acid; Surface chemistry
• ISSN: 1005-9040; 2210-3171
• DOI: 10.1007/s40242-022-2276-6

T hree multi-fluorous-carried anions-based ionic copolymers (ICs) including (fluorosulfonyl)imide(FSI − ), (trifluoromethanesulfonyl)imide(TFSI − ) and hexafluorophosphate anions(PF 6 − ) (IC[FSI − ]; poly[1,1′-(butane-1,4-diyl)bis(3-pentyl-1 H -imidazol-3-ium) bis(fluorosulfonyl)amide](IC[TFSI − ]), poly{1,1′-(butane-1,4-diyl)bis(3-pentyl-1 H -imidazol-3-ium) bis[(trifluoromethyl)sulfonyl]-amide}(IC[PF6 − ]), poly[1,1′-(butane-1,4-diyl)bis(3-pentyl-1 H -imidazol-3-ium) bishexafluorophosphate] were synthesized with a simple ionic exchange method by using amphiphilic poly[1,1′-(butane-1,4-diyl)bis(3-pentyl-1 H -imidazol-3-ium) bisbromide] (IC[Br − ]) as the intermediate ionic polymer. The chemical srutrcures of the target ICs were characterized by nuclear magnetic resonance (NMR) spectroscopy and Fourier-transform infrared spectroscopy (FTIR). It is shown that the target ICs could be spontaneously adsorbed on copper surface in N,N -dimethflormamide(DMF), and the tight adsorption films were formed on metal surface. The contacting angles suggest that the formed adsorption layers of target ICs on copper surface were characterized with hydrophobic nature. Furthermore, the target ICs-copper chemistry bonding was confirmed by various means. The electrochemistry analysis showed that the target ICs adsorption layers could prevent from copper corrosion in H 2 SO 4 solution efficiently, and the maximal anticorrosion efficiency was over 95% at 0.100 g/L. In particular, the target ICs showed 85% or above anticorrosion efficiency for copper at a low concentration of 0.025 g/L, which was greater than the intermediate polymer IC[Br − ]. In addition, an insight of mixed chemisorption and physisorption of the target ICs on metal surface was analyzed and discussed.