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

doi:10.7503/cjcu20170769

Abstract

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

CLC Number:

O631.5

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2018, 39(8): 1829.

Figures/Tables 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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