Synthesis and Properties of Comb-shaped Sulfonated Poly(ether ether ketone) as Cation Exchange Membrane by RAFT†

doi:10.7503/cjcu20130937

Abstract

Abstract:

A series of comb-like sulfonated poly(ether ether ketone)(g-SPEEK) with well-defined structures was prepared via reversible addition-fragmentation chain transfer(RAFT) polymerization using PEEK containing dithiobenzoate as macro RAFT agent and sulfonated styrene(SST) as monomer. The graft rate, chain length and molecular structure were tailored by the molar ratio of SST to RAFT agent and the reaction time of RAFT. The membranes of g-SPEEK were prepared by solution cast. The mixture solvent of water and NMP was used to adjust the membrane morphology. The structure and morphology of g-SPEEK membrane were cha-racterized by Fourier transform infrared spectroscopy(FTIR), ¹H NMR, TGA and scanning electron microscopy(SEM). The synthesized g-SPEEK have high hydrophilic/hydrophobic phase separation. With the increase in grafting degree of StSO₃Na, the ion exchange capacity(IEC) and water content increase from 0.638 mmol/g to 1.312 mmol/g and 20.19% to 43.51%, respectively. However, its swelling ratio is 5.05% which is lower than that of Nafion membrane(11.50%). Otherwise, comb-shaped SPEEK has a better H⁺ permeability than main-chain SPEEK membrane with the same IEC value.

Key words: Reversible addition-fragmentation chain transfer(RAFT), Sulfonated poly(ether ether ketone), Cation exchange capacity

CLC Number:

O631

TrendMD:

LIN Yifeng, HUANG Xuehong, ZHENG Rongxue, LIN Juan, DING Fuchuan, LING Qidan. Synthesis and Properties of Comb-shaped Sulfonated Poly(ether ether ketone) as Cation Exchange Membrane by RAFT^†[J]. Chem. J. Chinese Universities, 2014, 35(3): 633.

Figures/Tables 8

Scheme 1 Synthesis of g-SPEEK grafting copolymer via RAFT

Fig.1 FTIR spectra of PEEK(a) and g-SPEEK(b)

Fig.2 TGA curves of PEEK(a) and g-SPEEK(b)

Fig.3 1H NMR spectrum of g-SPEEK

Fig.4 SEM images of PEEK(A), g-SPEEK(B) and SPEEK membranes(C)

Table 1 RAFT polymerization under different conditions*

Sample	t/h	Molar ratio of M/CTA/I	T/℃	IEC/ (mmol·g^-1)	Water uptake(%)	Swelling ratio(%)	Oxidative stability/h	SD
g-SPEEK1	24	50:4:1	60	0.682	21.52	1.70	>5	0.7048
g-SPEEK2	24	50:4:1	70	1.312	43.51	5.05	4.5	1.5972
g-SPEEK3	24	50:4:1	80	0.837	22.40	2.15	>5	0.8985
g-SPEEK4	24	50:4:1	90	0.732	20.72	1.98	>5	0.7657
g-SPEEK5	12	50:4:1	70	0.638	20.19	1.54	>5	0.6525
g-SPEEK6	18	50:4:1	70	1.202	41.93	4.20	>5	1.4192
g-SPEEK7	24	25:4:1	70	1.071	34.75	3.50	>5	1.2208
g-SPEEK8	24	75:4:1	70	1.077	35.34	3.52	>5	1.2295
Nafion117				0.910	18.80	11.50	>5

Fig.5 H+ permeability of SPEEK(a,b) and g-SPEEK2(c,d) membrane under various current densitiesCurrent density/(mA·cm-2): a, c. 5; b, d. 10.

Fig.6 H+ permeability of SPEEK(a—c) and g-SPEEK2(d—f) membrane under various H2SO4 concentra-tionsConcentration of H2SO4/(mol·L-1): a, d. 0.5; b, e. 2; c, f. 3.

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