Phosphonium-based Crosslinked Poly(aryl ether ketone) Anion Exchange Membranes with 1,4-Bis(diphenylphosphino)butane as the Crosslinker†

doi:10.7503/cjcu20170240

Abstract

Abstract:

Two phosphines, rigid triphenylphosphine(TPP) and flexible tributylphosphine(TBP), were chosen to functionalize tetramethylbiphenyl-contained poly(aryl ether ketone)(PAEK), respectively, to prepare anion exchange membranes(AEMs). 1,4-bis(diphenylphosphino)butane was used as the crosslinker to crosslink PAEK, and the crosslinker was quaternized simultaneously. Thus the amount of functional groups of the crosslinked membranes was as the same as those of the uncrosslinked phosphonium-based PAEK membranes. Moreover, the mechanical properties of the crosslinked membranes were more effectively enhanced. The dimensional stability, conductivity, mechanical property and alkali resistance stability of the AEMs were investigated. As the crosslinking degree increased from 0 to 20%, the tensile stress of TPP and TBP modified AEMs increased from 27 MPa to 45 MPa, and from 18 MPa to 30 MPa, respectively. After exposed to 3 mol/L KOH at 60 ℃ for 120 h, the TPP and TBP modified AEMs maintained the conductivity of 81% and 69%, respectively. The results indicate that the alkaline stability of the crosslinked phosphonium-based PAEK membranes is more effectively improved than that of the uncrosslinked ones. At the same crosslinking degree, the TPP modified AEMs exhibit higher tensile stress and better alkali resistance stability than that the TBP modified ones.

Key words: Anion exchange membrane, Phosphonium, Chemistry crosslinking, Conductivity, Tensile stress, Alkali resistance stability, 1,4-Bis(diphenylphosphino)butane, Poly(aryl ether ketone)

CLC Number:

O631
O646

TrendMD:

XU Yixin, ZHANG Dengji, YE Niya, YANG Jingshuai, HE Ronghuan. Phosphonium-based Crosslinked Poly(aryl ether ketone) Anion Exchange Membranes with 1,4-Bis(diphenylphosphino)butane as the Crosslinker^†[J]. Chem. J. Chinese Universities, 2017, 38(10): 1872.

Figures/Tables 8

Schme 1 Preparation of crosslinked phosphonium-based poly(aryl ether ketone)

Fig.1 1H NMR spectrum of PAEK-Br

Fig.2 FTIR spectra of phosphonium-based poly(aryl ether ketone) membranesa. PAEK-Br; b. PAEK-TBP; c. PAEK-TBP-DPPB10; d. PAEK-TBP-DPPB20;e. PAEK-TPP; f. PAEK-TPP-DPPB10; g. PAEK-TPP-DPPB20.

Fig.3 Solubility test of PAEK-TBP-DPPBy(A) and PAEK-TPP-DPPBy(B) membranes in NMP at 80 ℃ for 12 hInsets: optical images of PAEK-TBP-DPPBy or PAEK-TPP-DPPBy.

Table 1 Water uptake, swelling and IEC of the membranes at room temperature

Membrane	Water uptake(%)	Swelling(%)		IEC/(mmol·g^-1)
Membrane	Water uptake(%)	Area	Volume	Measured	Theoretical
PAEK-TBP	42.9±3.5	23.0±2.2	48.1±3.5	1.83±0.10	2.33
PAEK-TBP-DPPB₅	33.0±3.3	20.4±1.7	39.4±2.2	1.75±0.09	2.33
PAEK-TBP-DPPB₁₀	28.8±1.2	16.6±1.7	32.2±4.0	1.60±0.11	2.33
PAEK-TBP-DPPB₂₀	15.6±2.5	10.8±2.1	21.8±2.0	1.46±0.11	2.32
PAEK-TPP	21.2±2.0	19.4±3.1	33.9±4.4	1.35±0.13	2.05
PAEK-TPP-DPPB₅	18.8±2.2	16.1±1.7	28.5±1.4	1.26±0.14	2.06
PAEK-TPP-DPPB₁₀	15.7±2.8	12.6±1.2	23.2±1.3	1.22±0.10	2.07
PAEK-TPP-DPPB₂₀	12.9±2.2	9.1±2.1	18.9±3.1	1.03±0.13	2.09

Fig.4 Tensile stress-strain curves of the PAEK-TBP-DPPBy and PAEK-TPP-DPPBy membranes in OH- form at room temperaturea. PAEK-TBP; b. PAEK-TBP-DPPB5; c. PAEK-TBP-DPPB10;d. PAEK-TBP-DPPB20; e. PAEK-TPP; f. PAEK-TPP-DPPB5;g. PAEK-TPP-DPPB10; h. PAEK-TPP-DPPB20.

Fig.5 Conductivities of the PAEK-TBP-DPPBy(A) and PAEK-TPP-DPPBy(B) membranes in water(A) a. PAEK-TBP; b. PAEK-TBP-DPPB5; c. PAEK-TBP-DPPB10; d. PAEK-TBP-DPPB20.(B) a. PAEK-TPP; b. PAEK-TPP-DPPB5; c. PAEK-TPP-DPPB10; d. PAEK-TPP-DPPB20.

Table 2 Conductivities of the membranes after immersed in 3 mol/L KOH at 60 ℃ for 120 h

Membrane	Conductivity/(mS·cm^-1)		Membrane	Conductivity/(mS·cm^-1)
Membrane	0 h	120 h	Membrane	0 h	120 h
PAEK-TBP	8.7	3.3	PAEK-TPP	4.7	2.3
PAEK-TBP-DPPB₅	8.0	4.0	PAEK-TPP-DPPB₅	4.5	2.6
PAEK-TBP-DPPB₁₀	6.8	4.2	PAEK-TPP-DPPB₁₀	4.2	3.3
PAEK-TBP-DPPB₂₀	4.9	3.4	PAEK-TPP-DPPB₂₀	3.7	3.0

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