Novel Composite Anion Exchange Membranes Based on Quaternized

Article pubs.acs.org/IECR

Novel Composite Anion Exchange Membranes Based on Quaternized Polyepichlorohydrin for Electromembrane Application Bo Han,† Jiefeng Pan,† Shanshan Yang,† Mali Zhou,† Jian Li,‡ Arcadio Sotto Díaz,§ Bart Van der Bruggen,‡ Congjie Gao,† and Jiangnan Shen*,† †

Center for Membrane Separation and Water Science & Technology, Ocean College, Zhejiang University of Technology, Hangzhou 310014, P. R. China ‡ Department of Chemical Engineering, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium § Department of Chemical and Environmental Technology, Rey Juan Carlos University, 28933 Móstoles, Madrid, Spain

ABSTRACT: A series of semi-interpenetrating polymer network (sIPN) composite anion exchange membranes were fabricated depending on immobilized linear PVDF and cross-linked polyepichlorohydrin (PECH), 1,4-diazabicyclo[2.2.2]octane, (DABCO) network through in situ synthetic pathway. A cyclic diamine (DABCO) was used as cross-linking agent and simultaneously improved the ion-exchange capacity by amination. Scanning electron microscopy (SEM) indicated that the composite membranes exhibited a dense and homogeneous structure. Successful formation of PECH-DABCO copolymer within the sIPN membranes was also confirmed by Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). The PVDF percentage and inherent properties of membranes such as ion exchange capacity (IEC), water uptake (WR), thermal stability, mechanical property, and area resistance were investigated to evaluate their applicability in electrodialysis (ED). The experimental results showed that the composite membrane maintained a good perspective for ED application. composite membranes.14,15 Compared with cation exchange membranes (CEMs), the fabrication of common AEMs mainly consists of two steps: methyation (chloromethylation or bromomethyation) and quaternary amination. Some authors have described the disadvantages of the methylation procedure in terms of being relatively complicated and environmentally unfriendly.16,17 Especially for chloromethylation, the commonly used chloromethyl methyl ether (CEM) and bis-chloromethyl ether (BCME) are highly toxic and carcinogenic, which have been restricted since the 1970s.18,19 Ran et al.18 gave a comprehensive overview about the development of an anion exchange membrane based on PPO, which is brominated as a potential alternative to chloromethylaion. To counter this issue, there are already many solving strategies, among which, introducing mainchain carrying

1. INTRODUCTION Recently, electrodialysis (ED) has played prominent roles in various environment and energy-related fields, which has been successfully used in the wastewater treatment, chemical, and food industry.1−4 More specifically, in water and wastewater treatment, ED has attracted growing attention owing to the contribution to water purification, demineralization of drinking water, desalination, and treatment of industrial effluents.5,6 As a key component of ED, anion exchange membranes (AEMs) are applied to facilitate the selective permeation of anions.7 In order to gain long cycle life and high energy efficiency, the AEMs should be fabricated with enhanced ion conductivity, good chemical and mechanical properties, and thermal stability.8 Therefore, the preparation of new AEMs with novel stability materials remains as one of the most challengeable issues for the application of ED. During the last years considerable research efforts have been accomplished about the manufacture of AEMs, ranging from polysulfone,9,10 poly(ether ether ketone),11,12 poly(2,6-dimethyl phenylene oxide) (PPO)13 to organic−inorganic hybrid © XXXX American Chemical Society

Received: May 4, 2016 Revised: June 1, 2016 Accepted: June 15, 2016

A

DOI: 10.1021/acs.iecr.6b01736 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

Article

Industrial & Engineering Chemistry Research

purchased from Aladdin Chemicals (Shanghai, China). Polyvinylidene fluoride (PVDF) was purchased from Shanghai 3F Chemical Co., Ltd. (Shanghai, China). All other chemicals were commercially obtained and used without further purification. 2.2. Preparation of the Composite Membranes. First, PECH and PVDF were dissolved in DMSO in a roundbottomed flask, and the obtained solution was stirred at 80 °C for 3 h to ensure the mixture dissolved completely. Then the required amount solution of DABCO in DMSO was added dropwise under stirring for 40 min at 80 °C to promote crosslinking. After that, the mixture was cast onto a clean glass plate and kept in a 60 °C vacuum drying oven for 24 h to ensure the simultaneous cross-linking and quaternization reaction. Then, the yellow, flexible, and transparent membranes were peeled from the glass plate and designated as Px (x stands for the mass ratios of PVDF to PECH). The thickness of the obtained dry membranes was about 90−100 μm. In order to avoid the gelation during cross-linking, dosage of PVDF is in the range of 0.5−1.5 g, when dosage of PECH is 1 g. Dosage of DABCO is 0.6 g to obtain good membrane forming property. Finally, the obtained base membranes were immersed in an aqueous TMA solution (1 mol L−1) at 25 °C for 24 h to quaternize the chloromethyl groups adequately, and repeatedly washed with deionized water for several times. The compositions of prepared membranes are summarized in Table 1, and membrane image with semi-IPN structure prepared through linear PVDF and cross-linked (PECH-DABCO) network is shown in Figure 1.

chloromethyl groups has been proposed as an effective one. For example, polyepichlorohydrin (PECH) has been extensively studied to fabricate AEMs by different research groups.20,21 It is an elastomer having inherent chloromethyl groups that allow the incorporation of quaternary ammonium functions by nucleophilic reaction of substitution.21 It is important to point out that it has a low glass transition temperature (Tg = −21 °C), which maintains a good flexibility and facilitates ionic conduction to be up to 100 °C.20 Nevertheless, the quaternized PECH undergoes high degree of swelling and would become brittle in water, which will greatly hinder its further practical application in ED.21 For this reason, the strategy of blending with uncharged polymer matrix was proposed by some researchers. For example, Hu et al. reported the PECH membrane manufacture adopting polytetrafluoroethylene (PTFE) as the supporting material to increase the mechanical strength and stability of the membrane for fuel cells.22 Using the same effective techniques, Farrokhzad et al. obtained membranes with adequate properties by blending with polyvinylidene fluoride (PVDF),23 which has been widely used in many fields due to its outstanding chemical resistance, good thermal and mechanical properties.24,25 Research findings indicated that the intrinsic hydrophobicity of PVDF could mitigate the undesired excessive swelling ratio. However, a loss of compatibility resulted during the membrane formation in the behavior of the PVDF and PECH polymer blend. Recently, the semi-interpenetrating polymer network (sIPN) has been developed to overcome the restrictions by providing a good distribution and homogeneous mixing of the blending components.24,26,27 The sIPN is a special class of polymer composites where a linear polymer penetrates extensively into the cross-linked network of other polymers. The sIPN polymers usually show good compatibility, high mechanical strength as well as good electrochemical stability.28 Cheng et al.29 prepared the AEM based on semi-IPN structure for acid recovery via diffusion dialysis. Wang et al.26 proposed a route to fabricate an AEM based on quaternized chitosan (QCS) and polystyrene (PS). The incorporation of the hydrophobic PS based on semi-IPN morphology provided the membranes with better thermal and mechanical stabilities. In this work, a facile method is developed to prepare sIPN anion exchange membranes based on PVDF and PECH polymer matrices. For overcoming the compatibility restrictions, without affect negatively the intrinsic properties of both polymers, a tertiary diamine (DABCO) is used as effective cross-linking agent between PECH macromolecules and, meanwhile, as the “active-site” that guarantees the amount of the ion-exchange capacity by amination procedure.12,20,30,31 The composite membranes were characterized by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The effect of PVDF ratio and inherent properties of membrane such as ion exchange capacity (IEC), water uptake (WR), thermal stability, mechanical property, and area resistance were thoroughly investigated to evaluate their applicability in electrodialysis (ED).

Table 1. Compositions of Five Base Membrane Solutions Membrane

PVDF (g)

PECH (g)

DABCO(g)

DMSO(ml)

PVDF (%)

P0.5 P0.75 P1.0 P1.25 P1.5

0.5 0.75 1.0 1.25 1.5

1 1 1 1 1

0.6 0.6 0.6 0.6 0.6

25 25 25 25 25

33.3 42.8 50 55.6 60

2.3. Characterizations. 2.3.1. Ion Exchange Capacity. Ion exchange capacity (IEC) was determined by using the classical Mohr method.32 For IEC measurement, three pieces of dry membranes were accurately weighed and respectively converted to the Cl- form by immersing in a 1 mol L−1 NaCl aqueous solution for 36 h. After the membrane was washed thoroughly with deionized water, the membrane was equilibrated with a 0.5 mol L−1 Na2SO4 solution for 36 h. The released chloride ions were back-titrated by 0.1 mol L−1 AgNO3 aqueous solution. The IEC values were calculated as follows: IEC(mmolg −1) =

C AgNO VAgNO 3

Mdry

3

(1)

where CAgNO3 (M) is the concentration of the AgNO3 solution, VAgNO3 (mL) is the volume of the AgNO3 solution, and Mdry (g) is the mass of the dried membrane sample. 2.3.2. Water Uptake and Swelling Resistance.̀ The weight of the dry membrane was accurately measured after being dried at 60 °C under a vacuum for 24 h. Then, the dry membrane was immersed in deionized water at 25 °C for 24 h. Subsequently, surface of the wet membrane was wiped with

2. EXPERIMENTAL SECTION 2.1. Materials. Polyepichlorohydrin (PECH, average molecular weight: 700 000 Da) was purchased from J&K Scientific Ltd. (Beijing, China). Dimethyl sulfoxide (DMSO) was obtained from Wu Xi sea creatures Co., Ltd. (Jiangsu, China). 1,4-Diazabicyclo [2.2.2] octane (DABCO) was B


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Figure 1. Synthesis procedure of semi-IPN structure based membranes.

tissue paper and the wet membrane was weighed. Water uptake (WR) was calculated according to the following eq 2: WR (%) =

Wwet − Wdry Wdry

× 100% (2)

where Wdry and Wwet are the weight of dry and wet membrane samples, respectively. The swelling resistance of the membranes was also evaluated in terms of water uptake (WR′) at 65 °C in hot water. Dry membranes were accurately weighted and immersed in hot water (65 °C). Then, WR′ was calculated at different times. 2.3.3. Contact Angle Measurement. The static contact angles of the membrane surface were measured by a contact angle goniometer (OCA-20, Data-physics, Germany) at ambient temperature. The water droplet morphologies and contact angles were analyzed by an optical contact angle meter. At least three water contact angles at different positions on membrane surface were measured, and the average contact angle was adopted. 2.3.4. Morphology. The surface morphologies of the membranes were observed by scanning electron microscopy (SEM, HITACHI, S4700A).The prepared membranes were dried in a vacuum oven and then coated with gold before the measurement. 2.3.5. Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS). The surface chemical structure of the membranes was performed by FTIR (Nicolet6700). Membrane samples were scanned from 500 to 4000 cm−1 by using a Nicolet6700 spectrometer with a resolution of 4 cm−1. X-ray photoelectron spectroscopy (XPS, Kratos AXIS Ultra DLD, Japan) measurements were taken to provide information about the membrane surface elemental composition. 2.3.6. Mechanical Property and Thermal Analysis. The mechanical properties of the composite AEMs were measured at room temperature using an instrument (CTM2050, Shanghai, China) at a strain rate of 5 mm min−1. All the samples were cut to the dimension of 10 mm × 20 mm. The thermal stability of the composite membranes was evaluated with Netzsch (STA 449C, Germany) thermal analyzer under N2 flow with a heating rate of 10 °C min−1 from 30 to 700 °C. 2.3.7. Membrane Area Resistance. Membrane area resistance was determined by using the methods described previously.19,32,33 A commercial measurement setup which is schematically shown in Figure 2 was used. During the

Figure 2. Schematic diagram of membrane area resistance measurement setup.

measurement, Na2SO4 solution (0.5 mol L−1) was supplied as the rinse electrolyte in the electrode chambers, and NaCl (0.5 mol L−1) was supplied to intermediate chambers. Titanium electrode coated stainless steel sheets were used as cathode and anode, respectively. A constant current (I = 0.004A) is provided by direct current power supply and the potential between electrodes is measured by a multimeter. Membrane area resistance can be calculated according to the eq 3: U − U0 ×S (3) I where R is the area resistance of composite membrane and S is the effective area of the membrane (7.065 cm2). U and U0 represent the voltage of the membrane holder (Figure 2) with and without the membrane, respectively. 2.3.8. Electrodialysis Experiments. A schematic diagram of custom-designed ED stack is illustrated in Figure 3. The stack is composed of four compartments: two electrode cell, dilute cell, and concentrate cell. The effective membrane area is 25 cm2 and solution volume is 400 mL. The dilute and concentrate cells were fed with 200 mL (0.2 mol L−1) of NaCl solution. Meanwhile, two electrode cells were fed with (0.5 mol L−1) Na2SO4 solution and were connected together in order to avoid the pH change. In this experiment, the conductivity of NaCl solution in dilute cell was measured in every 10 min, while potential over the stack were recorded every 10 min. All R=

C


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be formed during the phase inversion, due to the solvent evaporation from the semi-IPN membrane matrix.19 3.2. FTIR Analysis and XPS Measurement. ATR-FTIR analysis was used to confirm the structure of the sIPN membranes and successful formation of PECH-DABCO copolymer. Figure 5 showed the spectra of pure PVDF and

Figure 3. Schematic setup of the ED cell.

experiments were carried out at room temperature for 3 h under a constant current of 0.2 A.

3. RESULTS AND DISCUSSION 3.1. Membrane Morphology. The surface morphology of the prepared composite membranes was observed by SEM and the micrographs were shown in Figure 4. All the SEM pictures

Figure 5. FTIR spectra of pure PVDF and sIPN membranes with different amounts of PVDF.

sIPN membranes with different PVDF contents. Compared with the pure PVDF membrane, the composite membranes exhibited some new peaks (vibration modes). The peaks at 2874 and 2927 cm−1 were attributed to the stretching vibration of the aliphatic C−H bond on the methyl or methylene groups of PECH.22 The sharp peaks at 1640 and 3380 cm−1 were assigned to the vibration of the C−N bond on the DABCO group and the stretching vibration of the O−H bond.21 Besides, the peak at 879 and 1402 cm−1 originated from the C−F bond of PVDF,34 the peak intensity increased with the increasing PVDF content. All the observations confirmed successful blend of PECH-DABCO copolymer and PVDF in the sIPN membranes. X-ray photoelectron spectroscopy (XPS) analysis was used to further investigate the chemical compositions of the composite membrane surfaces. Pure PVDF, P0.5, P1.0, and P1.5 composite membranes were chosen for the investigation and the XPS test results were shown in Figure 6. Compared with the pure PVDF membrane, three new peaks appeared in P0.5, P1.0, and P1.5 composite membranes. The nitrogen-containing functionality (397.2 eV) peaks are clearly observed, which could be attributed to the surfaces of composite membranes containing quaternary-N after amination and simultaneous cross-linking of PECH and DABCO. The peak at 267.1 and 194.2 eV was assigned to Cl 2s and Cl 2p, respectively. The other peaks 529.7 and 680.5 eV were attributed to O 1s and F 1s, respectively, which provided further supporting evidence about the presence of PECH-DABCO copolymer in the PVDF matrix. 3.3. Ion Exchange Capacity (IEC), Water Uptake (WR), and Contact Angle. The IEC and water uptake are two important intrinsic properties of anion exchange membrane. At a certain amount of water uptake, the high IEC is very crucial for the improvement of ions transport and membrane

Figure 4. SEM images of the prepared composite membranes. (a) 33.3%PVDF-P0.5, (b) 42.8%PVDF-P0.75, (c) 50%PVDF-P1.0, and (d) 60%PVDF-P1.5.

showed a similar dense and homogeneous surface morphology without obvious phase separation, indicating the excellent compatibility of two components. This is because semiinterpenetrating polymer networks provide a good distribution and homogeneous mixing of PVDF and PECH. However, some slight differences are appreciable on the morphology of prepared membranes. It seemed that the micrographs showed rougher surface with the increase in PVDF content. Especially, the (60%PVDF-P1.5) composite membrane showed uneven and irregular size holes onto the membrane surface, that should D


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Figure 8. Static contact angles of membrane (a) P0.5, (b) P0.75, (c) P1.0, (d) P1.25, and (e) P1.5.

Figure 6. XPS spectra of pure PVDF membrane and composite membranes.

selectivity.29 The test results at 25 °C of the semi-IPN membranes were shown in Figure 7. Similar trends were

Figure 9. Swelling resistance of the sIPN membranes.

contributed to the membrane stability. Cross-linked PECHDABCO network also enhanced the membrane swelling resistance despite the good hydrophobicity of PECH. The results indicated that membranes with sIPN structure possess better swelling resistance. 3.5. Membrane Area Resistance, Mechanical Property, and Thermal Analysis. The membrane area resistance has a profound effect on the desalination efficiency, especially for the energy efficiency. As shown in Figure 10, membrane area resistance showed an increasing trend with increasing PVDF content and changed significantly when the amount of PVDF was above 50%. This is because that PVDF has no ionic

Figure 7. Ion exchange capacity (IEC) and water uptake (WR) of composite membranes at 25 °C.

observed for IEC and membrane resistance as a function of PECH content. As shown in Figure 7, there is a strong correlation between the determined IEC values (from 0.68 to1.31 mmolg−1) and PECH percentage. This effect is mainly due to the presence of more −CH2Cl of PECH and more and more quaternary ammonium groups were introduced into the membrane. The trend of water uptake (from 5.3% to 24.6%) was similar to the IEC. It is obvious that the contact angle of the membrane surface increased remarkably with the increasing of PVDF (Figure 8). This was consistent with the decrease in water uptake. The incorporation of PVDF made the membrane more hydrophobic and endowed the composite membranes have lower WR, which help the membrane maintain its mechanical property in the real application. 3.4. Swelling Resistance. Swelling resistance of the prepared membranes was characterized by water uptake at 65 °C. As shown in Figure 9, all the membrane samples reached the swelling equilibration within 10 h. However, WR values of the prepared membranes is slightly higher compare to that at 25 °C, indicating good swelling resistance in hot water. Hydrophobic PVDF immobilized in the sIPN morphology

Figure 10. Area resistance of the composite membranes. E


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could be due to the decomposition of the unreacted −CH2Cl of PECH.21 The last loss of weight at ∼455 °C was associated with the decomposition of PVDF backbone.23 The investigation indicated that the sIPN membranes possessed good thermal stability, which could be used under below temperature of 250 °C. 3.6. Desalination Efficiency. The prepared sIPN membranes for electromembrane applications were evaluated in a continuous-mode ED cell in terms of the desalination performances, and compared with the commercial membrane (Table 2 lists the different characteristics of commercial AEM

transport properties and only enhances the membrane mechanical properties. As expected, the composite membranes have area resistance values in the range of 1.854−5.282 Ωcm2, that is a basic requirement for ED application. The mechanical properties of prepared sIPN membranes were measured at room temperature. As illustrated in Figure 11.

Table 2. Properties of Commercial AEM Used in ED Test thickness

IEC

water uptake

area resistance

sample

(μm)

(mmol g−1)

(%)

(Ω cm2)

AEM

130−140

1.3−1.6

24−32

1.8−4

commonly used in ED.) under the same salt removal experiment condition. The conductivity of desalination solution in dilute chamber and potential over the stack was measured during the test. The final desalination rate values were shown in Table 3 and temporal measurements were plotted in Figure 13.

Figure 11. Tensile strength (TS) and elongation break (Eb) of the composite membranes.

Table 3. Final Desalination Rate of the Prepared and Commercial Membranes after 150 min

The tensile strength values (from 7 to 25.5 MPa) increased with the increasing of PVDF mass ratio, which may be attributed to the good mechanical property of PVDF and the sIPN network. The membranes showed the high elongation break values from 259.4% to 89%, presenting the high flexibility, since the PECH as an elastomer could guarantee its flexibility. Hence, blending of PECH with PVDF enhances the membrane flexibility and mechanical stability. As an example, the thermal stability of pure PVDF, 50% PVDF-P1.0 were evaluated by thermogravimetric analysis (TGA, Figure 12). A slight weight loss from 30 to 100 °C

membrane

final NaCl removal (%)

P0.5 P0.75 P1.0 P1.25 Neosepta AMX

89.8 87.6 82.3 79.8 86.4

Figure 13a showed that the conductivity of NaCl solution decreased with the time, P0.5 and P0.75 composite membranes exhibited better desalination performance than the commercial Neosepta membrane. Figure 13b showed the potential over during ED test. The potential increases significantly within last 40 min because of low salt content of dilute chamber. As the experiment performed, ions (Na+ and Cl−) were migrated toward the opposite direction. However, the potential over the stack equipped with P0.5 and P0.75 was lower than other membranes, indicating lower energy consumption. Hence, P0.5 and P0.75 composite membranes showed the best comprehensive properties, implying a great potential in ED application.

4. CONCLUSION Novel composite anion exchange membranes with sIPN morphology were successfully fabricated based on PVDF and cross-linked (PECH-DABCO) network. FTIR and XPS confirmed the successful blend of PECH-DABCO copolymer and PVDF in the sIPN membranes. SEM images indicated that composite membranes displayed dense and homogeneous surface morphology. The introduction of PVDF significantly enhanced mechanical properties, thermal stability, and reduced excessive water swelling. Compared to the commercial membrane, the sIPN membranes (P0.5 and P0.75) exhibited better desalination efficiency and lower energy consumption. This work demonstrated that the composited membrane with sIPN network can be potentially applied for ED process.

Figure 12. TGA curves of Pure PVDF, 50%PVDF-P1.0 composite membranes.

was mainly due to the evaporation of some free water absorbed in the membrane or residual solvent. Compared to pure PVDF membrane, the composite membrane showed a three-step degradation process. The first weight loss at ∼250 °C, which was ascribed to the degradation of the quaternary ammonium groups.21 The second weight loss at approximately 300 °C F


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Figure 13. Electrodialysis test: the change of (a) conductivity in dilute chamber and (b) potential over stack vs time.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The research was supported by the National High Technology Research and Development Program 863 (No. 2015AA030502), Natural Science Foundation of Zhejiang Province (No.LY16B060013), Zhejiang province department of public welfare projects (2015C31050).

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Novel Composite Anion Exchange Membranes Based on Quaternized

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