High-temperature proton exchange membrane with dual proton transfer channels by incorporating phosphonic acid functionalized siloxane into poly(2,6-dimethyl-1,4-phenyleneoxide) (PPO)

Zhu, Xingyi; Shen, Chunhui; Gao, Shanjun; Jin, Huaiyang; Cheng, Xiangze; Gong, Chenliang

doi:10.1016/j.ssi.2019.04.027

Cited by 24 publications

(13 citation statements)

References 52 publications

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“…In this part, FT‐IR and 1 H‐NMR were used to analyze the chemical structure of the BPPO and AEM‐X membranes. From the Figure 1(a), the signal at 4.28 ppm (8H) which was attributed to the H atoms on CH 2 Br of BPPO proved the successful realization of bromomethylation 40 . The degree of bromination (DB) was calculated about 62% by the ratio of the integral area of 4H to 8H.…”

Section: Resultsmentioning

confidence: 93%

Quaternized poly (2,6‐dimethyl‐1,4‐phenylene oxide) crosslinked by tertiary amine and siloxane for anion exchange membranes

Ding

Zhou

Cheng

et al. 2020

J of Applied Polymer Sci

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A series of tertiary amine and siloxane crosslinked composite anion exchange membranes were prepared by incorporating 2‐(3,4‐epoxycyclohexyl) ethyltrimethoxysilane (EHTMS) and N,N,N′,N′‐Tetramethyl‐1,6‐hexanediamine (TMHDA) into N‐Methyldiethanolamine (MDEA)‐functionalized poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) backbone via sol‐gel process. The resultant membranes named as AEM‐X (X = 1, 2, 3, 4), which own a three‐dimensional (3D) cross‐linking structure, exhibit superior swelling resistance, mechanical properties, even the thermal stability is up to 220°C. Compared with AEM‐1 (contains no crosslinker), the swelling ratio of AEM‐2 obviously decreases by 10.2% at 80°C, while the OH− conductivity of AEM‐2 has a merely 1.9% decline (20.6 mS cm−1) at 80°C and can maintain 67% of its initial value in a 2 M aqueous NaOH at 80°C for 240 h. The simultaneous introduction of inorganic siloxane and organic linear crosslinker provides a new idea for the preparation of anion exchange membranes with largely improvement in dimensional stability and alkali resistance while the ionic conductivity is kept at comparatively high level.

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Section: Resultsmentioning

confidence: 93%

Quaternized poly (2,6‐dimethyl‐1,4‐phenylene oxide) crosslinked by tertiary amine and siloxane for anion exchange membranes

Ding

Zhou

Cheng

et al. 2020

J of Applied Polymer Sci

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“…The BPPO was synthesized according to the previous literature 33 . Briefly, 15 g of dried PPO powder was dissolved in 100 ml of chlorobenzene (CB) to form a homogeneous solution at 60°C in a 500 ml three‐neck round bottom flask.…”

Section: Methodsmentioning

confidence: 99%

“…The BPPO was synthesized according to the previous literature. 33 Briefly, 15 g of dried PPO powder was dissolved in 100 ml of chlorobenzene (CB) to form a homogeneous solution at 60 C in a 500 ml three-neck round bottom flask. Then, Nitrogen (N 2 ) was pumped in, and the solution was boiled at 150 C. When continuous bubbles were observed in the solution, 4 ml of liquid bromine mixed with 40 ml of CB was added via dropping.…”

Section: Bromomethylation Of Ppomentioning

confidence: 99%

Multi‐cation side‐chain‐type containing piperidinium group poly(2,6‐dimethyl‐1,4‐phenylene oxide) alkaline anion exchange membranes

Zhang

et al. 2021

J of Applied Polymer Sci

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A series of alkaline anion exchange membranes (AAEMs) based on poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) with multi‐cation side chain containing piperidinium group were fabricated via nucleophilic substitution and Menshutkin reaction. The chemical structures of the AAEMs (PPO‐AMP‐X) were determined by Fourier transform infrared and proton nuclear magnetic resonance spectra. The resultant PPO‐AMP‐X membranes with the ion exchange capacities (IECs) of 2.05–2.77 mmol g−1 displayed the hydroxide conductivities in the range of 61.04–78.92 mS cm−1 at 80°C. When tested at the same degree of functionalization levels, the PPO‐AMP‐X membranes exhibited significantly higher hydroxide conductivity and lower conductivity loss than conventional AAEMs bearing benzyltri‐methylammonium group (PPO‐TMA). The PPO‐AMP‐28 multi‐cation membrane showed a hydroxide conductivity of 70.52 mS cm−1 at 80°C, which was nearly two times higher than that of the PPO‐TMA‐28 single‐cation membrane (36.74 mS cm−1). Compared with PPO‐TMA‐28 (56.76% decrease), the hydroxide conductivity of PPO‐AMP‐28 merely decreased by 23.15% after soaked in 1 M KOH at 80°C for 500 h. Additionally, the PPO‐AMP‐X membranes displayed moderate mechanical properties and good thermal stabilities, which can meet the basic requirements for use in fuel cells. This study provides a facile method for preparing AAEMs with multi‐cation side chain containing piperidinium group.

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“…The wide band in a region of 3500-3000 cm −1 characterizes the formation of multiple hydrogen bonds in the copolymer. It is known [24,37,38] that nitrogen-containing heterocycles are capable of forming hydrogen-bound networks. To provide fast transport, imidazole membranes are generally doped by an excess of sulfuric or phosphonic acids [38] which provide ion transport by the Grotthuss mechanism.…”

Section: (1)mentioning

confidence: 99%

“…It is known [24,37,38] that nitrogen-containing heterocycles are capable of forming hydrogen-bound networks. To provide fast transport, imidazole membranes are generally doped by an excess of sulfuric or phosphonic acids [38] which provide ion transport by the Grotthuss mechanism. In our case, the role of the acid dopant is played by the sulfo groups of SS, and proton transport occurs by the formed intermolecular hydrogen bonds.…”

Section: (1)mentioning

confidence: 99%

Sodium p-Styrene Sulfonate–1-Vinylimidazole Copolymers for Acid–Base Proton-Exchange Membranes

Лебедева

Pozhidaev

Малахова

et al. 2020

Membr. Membr. Technol.

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Binary copolymers possessing thermal stability up to 290°C and suitable for the formation of ionexchange membranes have been obtained by free radical copolymerization of sodium p-styrene sulfonate and 1-vinylimidazole with subsequent conversion to the H-form. The composition and structure of the copolymers are confirmed by elemental analysis and IR and NMR spectroscopy. Multicomponent membranes based on the copolymers of sodium p-styrene sulfonate and 1-vinylimidazole have been obtained using poly(vinyl alcohol) crosslinked by oxalic acid as a film-forming agent. It is shown by scanning electron microscopy that the surface and cut of the membranes have a uniform structure. The specific electric conductivity of the membranes with different concentrations of styrene sulfonic acid (20 to 80 mol % in the copolymer) increases with an increase in the fraction of styrene sulfonic acid and is 29.5 to 52.0 mS cm −1 at 80°C. The activation energy of proton transport of the membranes is 12.5 to 15.5 kJ mol −1. The water uptake of the membranes decreases with the increase in the concentration of the basic (imidazole) component in them, which may be associated with the increase in the density of ionic crosslinking due to the acid-base interaction of the sulfo groups and pyridine nitrogen atoms of the imidazole cycle. The formation of acid-base pairs results in the formation of continuous proton transport channels in addition to the sulfonic acid channels, which is confirmed by the high values of specific electric conductivity even in the case of a decrease in the concentration of sulfostyrene in the composition of the membrane. Increasing the concentration of 1-vinylimidazole in the composition of the copolymer from 20 to 80 mol % leads to an increase in the relative elongation at break from 3 to 6%, an increase in the tensile strength at break from 4 to 7 MPa, a decrease in the Young modulus of the membranes from 127 to 102 MPa, and a decrease in the water uptake from 45 to 15.

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High-temperature proton exchange membrane with dual proton transfer channels by incorporating phosphonic acid functionalized siloxane into poly(2,6-dimethyl-1,4-phenyleneoxide) (PPO)

Cited by 24 publications

References 52 publications

Quaternized poly (2,6‐dimethyl‐1,4‐phenylene oxide) crosslinked by tertiary amine and siloxane for anion exchange membranes

Quaternized poly (2,6‐dimethyl‐1,4‐phenylene oxide) crosslinked by tertiary amine and siloxane for anion exchange membranes

Multi‐cation side‐chain‐type containing piperidinium group poly(2,6‐dimethyl‐1,4‐phenylene oxide) alkaline anion exchange membranes

Sodium p-Styrene Sulfonate–1-Vinylimidazole Copolymers for Acid–Base Proton-Exchange Membranes

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