可逆加成-断裂链转移自由基聚合法合成梳型磺化聚醚醚酮

doi:10.7503/cjcu20130937

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (3): 633.doi: 10.7503/cjcu20130937

可逆加成-断裂链转移自由基聚合法合成梳型磺化聚醚醚酮

林艺凤, 黄雪红(), 郑榕学, 林娟, 丁富传, 凌启淡()

福建师范大学材料科学与工程学院, 福建省高分子材料重点实验室, 福州 350007

收稿日期:2013-09-25 出版日期:2014-03-10 发布日期:2019-08-01
作者简介:联系人简介: 凌启淡, 男, 博士, 教授, 主要从事光电功能聚合物研究. E-mail: qdling@fjnu.edu.cn; 黄雪红, 女, 博士, 研究员, 主要从事功能高分子研究. E-mail: xhhuang64@fjnu.edu.cn
基金资助:
国家自然科学基金(批准号: 61250016, 60976019)、福建省自然科学基金(批准号: 2013J01172)和福建省教育厅项目(批准号: JB12042, JK2013009)资助

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

LIN Yifeng, HUANG Xuehong^*(), ZHENG Rongxue, LIN Juan, DING Fuchuan, LING Qidan^*()

College of Materials Science and Engineering, Fujian Normal University, Fujian Key Laboratory of Polymer Materials, Fuzhou 350007, China

Received:2013-09-25 Online:2014-03-10 Published:2019-08-01
Contact: HUANG Xuehong,LING Qidan E-mail:xhhuang64@fjnu.edu.cn;qdling@fjnu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.61250016, 60976019), the Fujian Natural Science Foundation of China(No.2013J01172) and the Foundation of Fujian Educational Committee, China(Nos.JB12042, JK2013009)

摘要/Abstract

摘要：

以带双硫酯取代基聚醚醚酮为大分子链转移剂, 采用可逆加成-断裂链转移自由基聚合(RAFT)法合成不同接枝率的磺化聚醚醚酮(g-SPEEK), 并对其结构进行表征. 在单体/链转移剂/引发剂的投料比(摩尔比)为50:4:1, 温度为70 ℃, 反应24 h, 得到聚合物膜的离子交换容量和吸水率分别为1.312 mmol/g和43.51%, 其溶胀率为5.05%, 低于Nafion膜的11.50%. 热重分析(TGA)结果表明该梳型g-SPEEK具有较好的热力学稳定性, 且该聚合物膜具有与Nafion膜相当的抗氧化性. 在相同的离子交换容量下, 梳型g-SPEEK比主链型SPEEK具有更好的H⁺离子透过性能.

关键词: 可逆加成-断裂链转移自由基聚合, 磺化聚醚醚酮, 苯乙烯磺酸钠, 离子交换容量

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

中图分类号:

O631

TrendMD:

林艺凤, 黄雪红, 郑榕学, 林娟, 丁富传, 凌启淡. 可逆加成-断裂链转移自由基聚合法合成梳型磺化聚醚醚酮. 高等学校化学学报, 2014, 35(3): 633.

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^†. Chem. J. Chinese Universities, 2014, 35(3): 633.

图/表 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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可逆加成-断裂链转移自由基聚合法合成梳型磺化聚醚醚酮

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

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可逆加成-断裂链转移自由基聚合法合成梳型磺化聚醚醚酮

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

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