含氟磺化双三蝶烯型聚芳醚砜质子交换膜的制备及性能

doi:10.7503/cjcu20130605

摘要/Abstract

摘要：

利用3,3,4,4-四氟二苯砜、十氟联苯、 6F-双酚A及6,13-双三蝶烯二酚, 通过亲核取代共聚及后磺化方法制备了2个系列不同磺化度的磺化双三蝶烯型聚芳醚砜, 并通过氢核磁共振波谱(¹H NMR)对其化学结构进行了表征. 研究发现, 所得磺化聚芳醚砜均表现出了优异的热稳定性. 此类膜材料具有优良的机械性能、尺寸稳定性、氧化稳定性及高温低湿度条件下高的质子传导率. 透射电子显微镜的结果表明, 聚合物主链中大量氟原子的引入显著改善了聚合物的相分离结构, 并且随着聚合物主链中氟含量的增加, 亲水区域明显增大. 这也是含氟磺化双三蝶烯型聚芳醚砜质子交换膜材料在高温低湿度条件下具有高质子传导率的主要原因.

关键词: 磺化双三蝶烯基, 低湿度, 质子交换膜, 聚芳醚砜, 含氟磺酸膜

Abstract:

Two series of poly(aryl ether sulfone)s[SPES-x-PPD(10F) and SPES-x-PPD(4F)] containing sulfonated pentiptycene groups were synthesized through nucleophilic aromatic substitution polycondensation using pentiptycene-6,13-diol, decafluorobiphenyl, 4,4'-(hexafluoroisopropylidene)diphenol, and 3,3',4,4'-tetrafluorodiphenyl sulfone, followed by postsulfonation with chlorosulfonic acid. The structures of polymers were characterized by ¹H NMR spectra. These ionomers generally show high thermal stability. The correspon-ding membranes generally show good mechanical properties, excellent dimensional changes, good oxidative stability and high proton conductivity under high temperature and low humidity. Transmission electron microscopic photos reveal that the microphase separated structures of SPES-x-PPD(10F) and SPES-x-PPD(4F) membranes are improved greatly after fluorine atoms introducing. Meanwhile, the hydrophilic domain enlarged when the contents of fluorine atoms in polymer backbone increased. This is just the main reason of high conductivity for these membranes.

Key words: Sulfonated triptycene group, Low humidity, Proton exchange membrane, Poly(arylene ether sulfone)s, Fluoride sulfonic acid membrane

中图分类号:

O631

TrendMD:

宫飞祥, 齐永红, 薛群翔. 含氟磺化双三蝶烯型聚芳醚砜质子交换膜的制备及性能. 高等学校化学学报, 2014, 35(2): 433.

GONG Feixiang, QI Yonghong, XUE Qunxiang. Synthesis and Properties of Fluorinated Poly(arylene ether sulfone)s with Sulfonated Pentiptycene Pendants as Proton Exchange Membranes^†. Chem. J. Chinese Universities, 2014, 35(2): 433.

图/表 10

Scheme 1 Synthesis of SPES-x-PPD(4F) and SPES-x-PPD(10F) copolymers

Table 1 Physical properties of PES-x-PPD copolymers

Polymer	n(PPD)/ mmol	n(6F-BPA)/ mmol	n(TFDPS) or n(DFBP)/ mmol	10^-4 M_n	PDI	$η in h a$ / (dL·g^-1)	$η in h b$ / (dL·g^-1)
PES-30-PPD(4F)	1.5	3.5	5	6.5	2.1	0.42	0.59
PES-35-PPD(4F)	1.75	3.25	5	6.8	2.2	0.45	0.65
PES-32-PPD(10F)	1.6	3.4	5	7.3	2.5	0.51	0.73
PES-36-PPD(10F)	1.8	3.2	5	7.5	2.3	0.52	0.75

Table 1 Physical properties of PES-x-PPD copolymers

Polymer	n(PPD)/ mmol	n(6F-BPA)/ mmol	n(TFDPS) or n(DFBP)/ mmol	10^-4 M_n	PDI	$η in h a$ / (dL·g^-1)	$η in h b$ / (dL·g^-1)
PES-30-PPD(4F)	1.5	3.5	5	6.5	2.1	0.42	0.59
PES-35-PPD(4F)	1.75	3.25	5	6.8	2.2	0.45	0.65
PES-32-PPD(10F)	1.6	3.4	5	7.3	2.5	0.51	0.73
PES-36-PPD(10F)	1.8	3.2	5	7.5	2.3	0.52	0.75

Fig.1 1H NMR spectra of PES-32-PPD(10F)(A) and SPES-32-PPD(10F)(B) in DMSO-d6

Table 2 IEC and mechanical properties of SPES-x-PPD(10F) and SPES-x-PPD(4F) membranes

Polymer	IEC/(mmol·g^-1)			σ_max/MPa(r.t., 60%RH)	ε(%)	E/GPa
Polymer	Calcd.			σ_max/MPa(r.t., 60%RH)	¹H NMR	Titration
SPES-30-PPD(4F)	1.66	1.65	1.66	46.2	7.8	1.145
SPES-35-PPD(4F)	1.88	1.85	1.87	42.5	14	0.916
SPES-32-PPD(10F)	1.65	1.65	1.65	44.7	13	0.989
SPES-36-PPD(10F)	1.82	1.79	1.81	37.7	28	0.710

Fig.2 TGA curves of SPES-35-PPD(4F)(a), SPES-30-PPD(4F)(b), SPES-36-PPD(10F)(c) and SPES-32-PPD(10F)(d) copolymers

Table 3 Water uptake(WU) and swelling ratio of SPES-x-PPD(10F) and SPES-x-PPD(4F) copolymers

Polymer	IEC/(mmol·g^-1)	WU(%)(80 ℃)		Swelling ratio(%)
Polymer	IEC/(mmol·g^-1)	34%RH	94%RH	Δl(20 ℃)	Δt(80 ℃)
SPES-30-PPD(4F)	1.66	7.9	17.6	3.5	7.3
SPES-35-PPD(4F)	1.88	9.8	29.9	6.3	11.6
SPES-32-PPD(10F)	1.65	6.7	13.9	3.1	6.5
SPES-36-PPD(10F)	1.82	8.5	25.2	5.6	10.4
SPES-25-PPD^[27]	1.67	9.3	31.8	11.8	15.6
SPES-30-PPD^[27]	1.92	10.9	39.3	13.7	18.8
Nafion 117	0.91	6.6	11.6

Table 4 Water uptake(WU) and conductivity of SPES-x-PPD(10F), SPES-x-PPD(4F) and Nafion 117 membranes

Polymer	IEC/(mmol·g^-1)	WU(%)(80 ℃)		σ/(S·cm^-1)(80 ℃)
Polymer	IEC/(mmol·g^-1)	34%RH	94%RH	34%RH	94%RH
SPES-30-PPD(4F)	1.66	7.9	17.6	8.56×10⁴	0.173
SPES-35-PPD(4F)	1.88	9.8	29.9	1.46×10³	0.191
SPES-32-PPD(10F)	1.65	6.7	13.9	1.21×10³	0.181
SPES-36-PPD(10F)	1.82	8.5	25.2	2.25×10³	0.213
Nafion 117		6.6	11.6	3.0×10³	0.110

Fig.3 Humidity dependence of the proton conductivity of Nafion 117(a), SPES-36-PPD(10F)(b), SPES-35-PPD(4F)(c), SPES-32-PPD(10F)(d), and SPES-30-PPD(4F)(e) membranes at 80 ℃

Fig.4 TEM images of SPES-30-PPD(4F)(IEC=1.66 mmol/g)(A), SPES-32-PPD(10F)(IEC=1.65 mmol/g)(B), SPES-35-PPD(4F)(IEC=1.88 mmol/g)(C) and SPES-36-PPD(10F)(IEC=1.82 mmol/g)(D)

Table 5 Oxidative stability results of SPES-x-PPD(10F) and SPES-x-PPD(4F) membranes

Polymer	IEC/(mmol·g^-1)	Oxidative stability^a
Polymer	IEC/(mmol·g^-1)	Decrease in mass(%)	Decrease in η_inh(%)
SPES-30-PPD(4F)	1.66	0^a; 7^b	2
SPES-35-PPD(4F)	1.88	2^a; 18^b	7
SPES-32-PPD(10F)	1.65	0^a; 0^b	1
SPES-36-PPD(10F)	1.82	1^a; 10^c	5
Nafion 117	0.91	0^a; 0^b

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