聚砜基质中Gemini分子原位引发聚合构筑有序排列阳离子活性位导电通道

doi:10.7503/cjcu20170769

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (8): 1829.doi: 10.7503/cjcu20170769

聚砜基质中Gemini分子原位引发聚合构筑有序排列阳离子活性位导电通道

杨佳睿, 王一夫, 王吉林(), 王璐璐, 封瑞江

辽宁石油化工大学化学化工与环境学部, 石油化工学院, 抚顺 113001

收稿日期:2017-11-27 出版日期:2018-08-10 发布日期:2018-06-11
作者简介:联系人简介: 王吉林, 男, 副教授, 主要从事聚合物电解质研究, E-mail: wangjilin1978@163.com
基金资助:
辽宁省科技厅博士启动项目(批准号: 20141126)、辽宁省教育厅科学研究一般项目(批准号: L2013153)、辽宁石油化工大学博士启动基金(批准号: 2013XJJ-006)和辽宁石油化工大学国家级科研项目培育计划资助.

In situ Initiation, Polymerization and Construction of Cationic Active Sites of Gemini Molecules in Polysulfone Substrates^†

YANG Jiarui, WANG Yifu, WANG Jilin^*(), WANG Lulu, FENG Ruijiang

School of Petroleum and Chemical Technology, College of Chemistry, Chemical Engineering and Environment Engineering, Liaoning Shihua University, Fushun 113001, China

Received:2017-11-27 Online:2018-08-10 Published:2018-06-11
Contact: WANG Jilin E-mail:E-mail: wangjilin1978@163.com;wangjilin1978@163.com
Supported by:
† Supported by the Fundamental Research Funds for the Doctoral of Liaoning Provincial(No.20141126), the Scientific Research Fund of Liaoning Provinceial Education Department of China(No.L2013153), the Doctoral Project of Liaoning Shihua University of China(No.2013XJJ-006) and the National Research Project Training Plan of Liaoning Shihua University of China.

摘要/Abstract

摘要：

将Gemini型可聚合阳离子表面活性剂单体[顺丁烯二酸二乙酯撑基双(辛烷基)二甲基氯/溴化铵(G_8-2-8)、顺丁烯二酸二乙酯撑基双(十二烷基二甲基氯/溴化铵)(G_12-2-12)、顺丁烯二酸二乙酯撑基双(十六烷基二甲基氯/溴化铵)(G_16-2-16)]引入聚砜(PSF)聚合物的氯仿铸膜液中, 以过硫酸钾(KPS)作为引发剂, 原位引发Gemini分子聚合, 制得具有有序排列阳离子活性位导电通道的Gemini/聚砜阴离子交换膜, 并对其进行结构表征和性能测试. 结果表明, 随着Gemini引入量的增加, 含水率、溶胀度、离子交换量及电导率等均呈上升趋势. 随着Gemini结构中疏水碳链的增长, 含水率、溶胀度、离子交换量、电导率及断裂伸长率等降低, 膜材料的拉伸强度随之增加. 当Gemini引入质量分数为20%、疏水碳链的碳数为8时, 含水率为12.35%, 溶胀度仅为10.13%, 离子交换量为0.61 mmol/g, 80 ℃时的电导率为3.776 mS/cm. 在80 ℃及6 mol/L KOH碱性环境下考察了G_8-2-8-PSF系列膜的耐碱稳定性, 结果表明, 膜在碱中浸泡240 h后, 电导率下降幅度最高仅为2.0%, 表现出较好的耐碱稳定性能.

关键词: 聚砜, Gemini型表面活性剂, 阴离子交换膜, 耐碱稳定性

Abstract:

Gemini-type polymerizable cationic surfactant monomer(maleate diethyl bis [octyl(dodecyl, hexadecyl)dimethyl chloride/ammonium bromide])(G_8-2-8, G_12-2-12, G_16-2-16) was introduced into a chloroform casting solution of a polysulfone(PSF) polymer, with the help of potassium persulfate(KPS) initiator, in situ initiation of the aforementioned Gemini molecule polymerization, thereby preparing a Gemini/polysulfone anion exchange membrane with an ordered array of cationic active sites. The anion conductive film was subjected to structural characterization and performance testing. The results showed that with the increase of Gemini content, the indexes of water uptake, swelling ratio, ion exchange capacity and electrical conductivity showed an increasing trend. With the growth of hydrophobic carbon chains in the Gemini structured, the water uptake, swelling ratio, ion exchange capacity, conductivity, elongation at break and so on decrease, the tensile strength of the membrane material increased. When the mass fraction of Gemini was 20% and the carbon number of hydrophobic hydrocarbon chain was 8, the water uptake was 12.35%, the swelling ratio was only 10.13%, the ion exchange capacity was 0.61 mmol/g, and the conductivity was 3.776 mS/cm at 80 ℃. Alkali resistance of G_8-2-8-PSF series membranes was investigated at 80 ℃ and 6 mol/L KOH alkaline, the results showed that after 240 h of alkali-bubble, the highest decrease in conductivity was only 2.0%, showing a good alkali stability.

Key words: Polysulfone, Gemini surfactant, Anionic exchange membrane, Alkali resistance stability

中图分类号:

O631.5

TrendMD:

杨佳睿, 王一夫, 王吉林, 王璐璐, 封瑞江. 聚砜基质中Gemini分子原位引发聚合构筑有序排列阳离子活性位导电通道. 高等学校化学学报, 2018, 39(8): 1829.

YANG Jiarui, WANG Yifu, WANG Jilin, WANG Lulu, FENG Ruijiang. In situ Initiation, Polymerization and Construction of Cationic Active Sites of Gemini Molecules in Polysulfone Substrates^†. Chem. J. Chinese Universities, 2018, 39(8): 1829.

图/表 9

Fig.1 ATR spectra of PSF(a), G8-2-8(20%)-PSF(b) and G8-2-8(20%)-PSF/NaOH(c)

Fig.2 TGA curves of PSF(a), G16-2-16(20%)-PSF(b), G12-2-12(20%)-PSF(c) and G8-2-8(20%)- PSF(d)

Fig.3 Water uptake(A) and swelling ratio(B) of Gemini-PSF anion exchange membranesa. G8-2-8(w%)-PSF; b. G12-2-12(w%)- PSF; c. G16-2-16(w%)- PSF.

Table 1 Physical-chemical properties of Gemini-PSF anion exchange membranes

Membrane	Tensile strength/MPa	Elongation at break(%)	IEC/( mmol·g^-1)
G_8-2-8(5%)-PSF	19.77±0.75	6.02±0.21	0.17±0.020
G_8-2-8(10%)-PSF	17.07±0.73	5.55±0.25	0.33±0.015
G_8-2-8(15%)-PSF	14.45±0.69	4.34±0.23	0.44±0.020
G_8-2-8(20%)-PSF	8.97±0.74	2.29±0.22	0.61±0.010
G_12-2-12(5%)-PSF	36.76±0.77	4.98±0.19	0.14±0.015
G_12-2-12(10%)-PSF	30.35±0.76	4.23±0.21	0.27±0.020
G_12-2-12(15%)-PSF	25.57±0.74	3.07±0.22	0.37±0.010
G_12-2-12(20%)-PSF	17.07±0.75	1.75±0.20	0.56±0.020
G_16-2-16(5%)-PSF	56.49±0.78	3.75±0.20	0.12±0.020
G_16-2-16(10%)-PSF	44.38±0.76	2.78±0.19	0.21±0.015
G_16-2-16(15%)-PSF	36.67±0.72	2.02±0.22	0.30±0.020
G_16-2-16(20%)-PSF	24.87±0.76	1.42±0.23	0.48±0.010

Fig.4 Anionic conductivity of G8-2-8-PSF anion exchange membranesa. G8-2-8(20%)-PSF; b. G8-2-8(15%)-PSF;c. G8-2-8(10%)-PSF; d. G8-2-8( 5%)-PSF.

Fig.5 Arrhenius plots for G8-2-8-PSF anion exchange membranesa. G8-2-8(20%)-PSF, Ea=5.75 kJ/mol; b. G8-2-8(15%)-PSF, Ea=8.10 kJ/mol; c. G8-2-8(10%)-PSF, Ea=9.84 kJ/mol; d. G8-2-8( 5%)-PSF, Ea=13.73 kJ/mol.

Fig.6 Anionic conductivity of Gemini-PSF anion exchange membranesa. G8-2-8(w%)-PSF; b. G12-2-12(w%)- PSF; c. G16-2-16(w%)- PSF.

Table 2 IEC and conductivity values reported in the literature for different anionic exchange membranes

Membrane	IEC/(mmol·g^-1)	Conductivity/(mS·cm^-1)	Con/IEC	Ref.
G_8-2-8(5%)-PSF	0.17	1.73(30 ℃)	10.20	This Reaserch
G_8-2-8(5%)-PSF	0.17	3.78(80 ℃)	22.20	This Reaserch
Polystyrene(ethylene utylenes)	0.57	0.69(30 ℃)	1.21	[27]
Silica/poly(2,6-dimethyl-1,4-phenylene oxied	2.01	12.00(30 ℃)	5.96	[28]
Poly(MMA-co-BA-co-VBC)	1.25	5.20(80 ℃)	7.80	[29]
Poly(arylene ether sulfone)	2.62	15.00(80 ℃)	10.20	[30]

Fig.7 Alkali resistance of G8-2-8-PSF anion exchange membranes after immersion in 6 mol/L NaOH solution at 80 ℃ for 240 ha. G8-2-8(5%)-PSF; b. G8-2-8(10%)-PSF;c. G8-2-8(15%)-PSF; d. G8-2-8(20%)-PSF.

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聚砜基质中Gemini分子原位引发聚合构筑有序排列阳离子活性位导电通道

In situ Initiation, Polymerization and Construction of Cationic Active Sites of Gemini Molecules in Polysulfone Substrates^†

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聚砜基质中Gemini分子原位引发聚合构筑有序排列阳离子活性位导电通道

In situ Initiation, Polymerization and Construction of Cationic Active Sites of Gemini Molecules in Polysulfone Substrates†

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In situ Initiation, Polymerization and Construction of Cationic Active Sites of Gemini Molecules in Polysulfone Substrates^†