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Journal of Membrane Science 304 (2007) 118124

Synthesis of AgCl/PMMA hybrid membranes and their sorption performance of cyclohexane/cyclohexene


Jiang-nan Shen a, , Xin-cun Zheng a , Hui-min Ruan a , Li-guang Wu b , Jun-hong Qiu a , Cong-jie Gao b
a

College of Chemical Engineering & Materials Science, Zhejiang University of Technology, Hangzhou 310014, PR China b National Engineering Research Center for Liquid Separation Membrane, Hangzhou 310012, PR China Received 30 April 2007; received in revised form 11 July 2007; accepted 16 July 2007 Available online 21 July 2007

Abstract AgCl//PMMA organicinorganic hybrid membrane has been fabricated by reverse microemulsion polymerization using methyl methacrylate (MMA) as oil phase. The membrane structure is analyzed by scanning electron microscope (SEM), which shows that coreshell organicinorganic hybrid materials are formed with AgCl as the core and PMMA as the shell. AgCl particulate under 2 m are uniformly dispersed in the PMMA. The swelling-sorption behavior of the cyclohexane and cyclohexene in AgCl//PMMA hybrid membrane are measured, the result indicates that the sorption capacity of cyclohexene in the hybrid membrane is enlarged comparing with pure PMMA membrane, but the sorption behavior of cyclohexane is less changed. The equilibrium swelling-sorption amount (A ) ratio of cyclohexene to cyclohexane in membranes was up to 130.4, which was larger than that in the pure PMMA membranes of 54.7. 2007 Elsevier B.V. All rights reserved.
Keywords: Microemulsion situ polymerization; AgCl/PMMA; Inorganicorganic hybrid membrane; Swelling performance

1. Introduction Compared with highly energy-intensive low-temperature distillation, olen/parafn separation by facilitated transport polymer membranes consisting of silver has attracted much interest because of its advantages of low energy consumption, compact apparatus and simple operation [14]. However, polymer membranes containing silver salts exhibit some disadvantages that prevent the commercialization of this separation process. One major drawback observed in the membranes is the gradual decrease in membrane performance with time, possibly due to the reduction of silver ions to silver particles. To our knowledge, despite the extremely high separation performance of silver polymer electrolyte membranes, the long-term stability of their separation performance is in doubt because

Corresponding author. Tel.: +86 571 8803 4718; fax: +86 571 8803 4718. E-mail addresses: jiangnan shen@126.com (J.-n. Shen), gaocjie@mail.hz.zj.cn (C.-j. Gao). 0376-7388/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.memsci.2007.07.022

silver ions can be reduced to form silver metal nanoparticles and thus lose their olen carrier activity. To improve the stability of the facilitated transport membrane, many investigations have been carried out [5,6]. It is reported by Kang that the long-term stability of silver polymer electrolyte is improved remarkably by the incorporation of an additive containing phthalates [6]. However, the practical use of this approach is limited because phthalates are known to be hazardous to human beings, and their concentration in polymer electrolytes is limited that these poor solubility in the polymer matrix. At the same time, they prepared solid polymer electrolyte membranes consisting of PEP and AgBF4 [7] and found that the membranes exhibit much long-term stability in the separation of olen/parafn mixtures than POZ/AgBF4 membrane, which is attributable to the suppression of silver ion reduction to silver metal nanoparticles. The authors also have prepared PVA/Co(CH3 COO)2 membranes to separate the cyclohexene/cyclohexane mixtures [8], the stability of the facilitated transport membranes would be improved at a degree compared to the PVA/AgNO3 . The transition metals or their ions can form the normal bond

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Fig. 1. TEM photograph of AgCl ultra-ne particles of different w. (a) w = 3; (b) w = 7; (c) w = 9.

to carbon, and in addition, the unique characteristics of the d orbitals in these metals enable them to form bonds with unsaturated hydrocarbons in a non-classical manner besides their ions. This type of bonding is broadly referred to as -complexation. For example, CuCl, which is insoluble in water, has been considered in the power form for olen/parafn separation [912]. Inorganic lled organicinorganic hybrid membranes have attracted much attention recently because they possess both advantages of the organic and inorganic membranes and the characterizations of being easy to prepare and facile reaction condition. The stability performance of the hybrid membranes which are prepared via microemulsion situ polymerization may be improved [13,14]. AgCl/PMMA poly(methyl methacrylate) inorganicorganic hybrid membranes were prepared via microemulsion situ polymerization with MMA as oil phase and AOT as emulsion solvent. The reverse micelle structure, hybrid membranes morphology and the sorption behavior of cyclohexane and cyclohexene in hybrid membranes were investigated.

Fig. 2. Absorption spectra of AgCl ultra-ne particles in different microemulsion system as the particles size is steady.

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2. Experimental 2.1. Materials Methyl methacrylate (MMA) was obtained from Shanghai Coral Chemical Co., Ltd. (Shanghai, China) and used after puried. Aerosol diisooctyl succinate (AOT) was obtained from Fluka. 2,2-Azobisibobutyronitrile (AIBN), cyclohexene and cyclohexane were obtained from Shanghai Chemical Reagent and was used directly without further purication. All other reagents and chemicals were of analytical grade. 2.2. Preparation of AgCl/PMMA hybrid membranes MMA microemulsion was prepared according to Roy and Devi [15] by weighing the MMA and AOT were added into a three-necked ask, and then put into a bath. Quantitative water or NaCl solution was added into the MMA/AOT mixture solution with stirring by magnetic stirring apparatus. Ultimately, the MMA microemulsion conductivity was measured to analyze its stability. AgCl/PMMA hybrid membranes were prepared as follow: rstly, dissolving quantitative AOT into MMA, then AgNO3 or NaCl was added into the AOT/MMA solution to prepare microemulsion with ultrasonic stirring, respectively, the AgCl/PMMA microemulsion was obtained by blending the two microemulsion quickly. Ultimately, the AIBN was added into the AgCl/PMMA microemulsion to start polymerization at 65 C, the polymerization solution was fallen into clean glass plate when the solution viscosity reached quantitative degree. Different thickness AgCl/PMMA hybrid membranes were obtained by covering another clean glass plate coated with silicone oil to continue reaction for 12 h by adjusting the brass wires. 2.3. Characterization of AgCl/PMMA hybrid membranes The growth of AgCl nanoparticles were investigated by UVvis absorption spectra (spectrumlab54). The AgCl nanoparticles size were analyzed by laser particles size analysis instrument (BI-90Plus, made in BROOKHAVEN Instrument Company, America). The refractive index of MMA is 1.4001, the viscosity is 5.8 103 Pa s (5.8 cP). The AgCl nanoparticles diameter attribution and congures of the AgCl nanoparticles were characterized by TEM (Transmission Electron Microscope, made in JEOL Company, Japan). Drop the AgCl microemulsion on the cupper net, then put the cupper net in the instrument to observe the AgCl nanoparticles diameter attribution and congures. The SEM (scanning electron microscope, SIRION) was used to observe the surface and crosssection morphologies of AgCl/PMMA hybrid membranes. The AgCl/PMMA hybrid membranes were treated by drying, the surface and cross-section (the membrane sample was broken in the liquid nitrogen) was spun by gold. 2.4. Sorption behavior of the cyclohexane/cyclohexene in AgCl/PMMA hybrid membranes The swelling behavior of the cyclohexane/cyclohexene in pure PMMA membrane and AgCl/PMMA hybrid membrane

at a given time were dened by the following equation [16,17]: A (mg/g) = m m0 1000 m (1)

where m0 and m are the weights of dry and solvent swollen membranes, respectively. The swelling experiments were carried out at constant temperatures, and the membranes were weighed at room temperature. The free liquid on the surface of the swollen membrane must be removed carefully by using lter paper before being weighed. 3. Results and discussion 3.1. TEM and SEM analysis TEM photograph of AgCl ultra-ne particles is shown in Fig. 1. TEM shows that the size of AgCl ultra-ne particles is under 50 nm. Other things being equal, the larger the w (H2 O-tosurfactant mole ratio as preparing the reverse microemulsion) is, the larger the size is, which is consistent with the results of the UVvis absorption spectra shown in Fig. 2. The phenomenon above may be because AOT reverse micelle interface changes with an increase in w.

Fig. 3. 90 Plus particle size analysis of AgCl in MMA. (a) w = 3; (b) w = 9.

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Fig. 4. Absorption spectra of AgCl ultra-ne particles in different microemulsion system. (a) w = 3; (b) w = 7; (c) w = 9.

90 Plus particle size analysis of AgCl in MMA is shown in Fig. 3. It can be seen from Fig. 3, the AgCl particles size increase step by step with time at w = 3 and w = 9. For the system of w = 3, the difference of particles size is obvious. However, the particles distribution appears obvious overlap for the system of w = 9. The reason may be that as follow: the concentration of the disperse phase is large at w = 9, which result in increasing probability of material exchange caused by the collision among the reverse micelle, it lends itself to accelerate the velocity of the particles growth. At this condition, some particles have arrived at a certain size, but other particles is developing, this phenomenon is consonant with the result of the UVvis absorption spectra shown in Fig. 4, the velocity of going to steady of the particles is quick at larger w. Fig. 5 shows TEM image of AgCl particle in MMA and SEM images of upper surface and cross-section of the AgCl/PMMA membrane. From this gure, AgCl particle is dispersed in the PMMA and a coreshell structure of AgCl/PMMA (AgCl as the core and PMMA as the shell), this is the same as the result obtained by Xi [18]. By comparison between before and after polymerization, the size of AgCl particle after polymerization is larger than that before polymerization, which may be because

the interface energy between monomer and surfactant is replaced by that of polymer/surfactant at before and after polymerization resulting in the changing of interface energy and AgCl particle agglutination. 3.2. Degree of swelling (DS) The degree swelling (DS) of cyclohexane/cyclohexene in AgCl/PMMA hybrid membrane were measured at a constant temperature, the results are presented in Fig. 6. The cyclohexane solubility in AgCl/PMMA hybrid membrane can be readily described by a simple Henry mode. The DS of cyclohexane in the AgCl/PMMA hybrid membrane decreases with increasing the carrier concentration. This may be AgCl relative content increasing with increasing carrier concentration, which results in PMMA content decreasing. The curves of the cyclohexene solubility in AgCl/PMMA hybrid membrane becomes concave to the ordinate with the 1/2 , indicating the presence of the second mode sorption. The second mode sorption is evidently due to the interaction between AgCl and cyclohexene molecules and it can also be described by a simple Langmuir model. The DS of cyclohexene in the AgCl/PMMA hybrid membrane increases

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Fig. 5. TEM image of AgCl particle in MMA and SEM images of surface and cross-section of the AgCl/PMMA membrane. (a) AgCl/PMMA hybrid membrane surface; (b) AgCl particle in PMMA; (c) cross-section; (d) AgCl particle in MMA.

with increasing the carrier concentration. This is due to the xed sites which increases with increasing the carrier concentration. The equilibrium swelling-sorption amount (A ) ratio of cyclohexene to cyclohexane in hybrid membranes which was up to 130.4, was larger than that in the pure PMMA membranes of 54.7. The result is shown in Table 1. The domination of sorption selectivity is due to the afnity between the double bonds of cyclohexene molecule and the polar groups of the polymeric membrane. That is, cyclohexene has electrons, which show stronger afnity to polar molecules and reversible coordination
Table 1 Equilibrium swelling-sorption amount (A ) of cyclohexene and cyclohexane in membranes Membrane M0 M10 M30 Acyclohexene (mg/g) 979.4 993.9 1017.5 Acyclohexane (mg/g) 17.9 15.1 7.8 Acyclohexene / Acyclohexane 54.7 65.8 130.4

The volume of NaCl and AgNO3 are 0, 10, 3010 L, respectively, in the preparation the hybrid membrane of different carrier content, the resulted membrane is marked as M0, M10, M30, respectively.

interaction between cyclohexene and carrier. Therefore, a polymer possessing polar or carrier groups facilitates the permeation of cyclohexene through the membrane [19,20]. It can also be seen from Fig. 7, Effect of the emulsifying agent content on the hybrid membrane is less than that of the carrier content, and by comparing the AOT content between 0.75 g/10 mL and 1.125 g/10 mL, the cyclohexene sorption velocity in the hybrid membrane increase quickly at the range of 300500 s1/2 , which may be the size and amount of the cavity after the removal of the emulsifying agent. The membrane cross-section morphology before and after removal of the emulsifying agent is shown in Fig. 8. In order to examine the effect of feed composition on diffusion inside membranes, sorption kinetics was investigated for the pure PMMA and the hybrid membranes. Figs. 9 and 10 show cyclohexene and cyclohexane uptake in the pure PMMA and the organicinorganic hybrid membrane plotted against cyclohexene content in the cyclohexene/cyclohexane mixtures. The results indicate that the cyclohexene uptake was signicantly greater than the cyclohexane uptake. The two types membranes showed some degree of sorption preference favoring cyclohex-

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Fig. 8. (a) Membrane cross-section morphology after removal of the emulsifying agent; (b) membrane cross-section morphology before removal of the emulsifying agent. Fig. 6. (a) Swell characteristic of membranes in cyclohexane; (b) swell characteristic of membranes in cyclohexene (CNaCl = 0.05 mol/L, CAgNO3 = 0.05 mol/L, the volume of NaCl and AgNO3 are 0 L, 10 L, 30 L, respectively in the preparation the hybrid membrane of different carrier content, AOT/MMA = 1.5 g/10 mL, 30 C).

ene in the binary solutions probably due to interaction between cyclohexene and polar groups in the PMMA membrans and reversible coordination interaction between cyclohexene and AgCl in the hybrid membranes. Villaluenga and Tabemohammadi [21] suggested that a polar membrane is suitable for benzene/cyclohexene separation since benzene electrons have a strong afnity for polar molecules, which gives it a higher adsorption selectivity than cyclohexane. Note that cyclohexene

Fig. 7. Swell characteristic of membranes in cyclohexene at different surfactant content (CNaCl = 0.05 mol/L, CAgNO3 = 0.05 mol/L, the volume of NaCl and AgNO3 are 30 L, respectively, in the preparation the hybrid membrane of different AOT content, AOT/MMA = 1.5 g/10 mL, 30 C).

Fig. 9. Effect of cyclohexene content in the feed on sorption performance of cyclohexene and cyclohexane in pure PMMA membrane.

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Fig. 10. Effect of cyclohexene content in the feed on sorption performance of cyclohexene and cyclohexane in the hybrid membrane (CNaCl = 0.05 mol/L, CAgNO3 = 0.05 mol/L, the volume of NaCl and AgNO3 are 30 L, respectively, in the preparation the hybrid membrane, AOT/MMA = 1.5 g/10 mL, 30 C).

uptake in the hybrid membrane was higher than in the pure PMMA membrane. This demonstrates that in addition to the interaction between cyclohexene and polar groups in the membrane described above, specic interaction between cyclohexene and Ag+ ions must play a crucial role in cyclohexene sorption [22]. It has been shown that silver ions form coordination complexes with olen double bond [23]. Moreover, the carrier content is less than 0.016 mg/g dry membrane in the current hybrid membrane, which results in cyclohexene uptake in the hybrid membrane was slightly higher than in the pure PMMA membrane. 4. Conclusion AgCl/PMMA (poly(methyl methacrylate)) inorganic organic hybrid membranes were prepared via microemulsion situ polymerization. The reverse micelle structure, hybrid membranes morphology and the sorption behavior of cyclohexane and cyclohexene in hybrid membranes were investigated. The results showed that all the AgCl nanoparticles in MMA microemulsion were sphere-like, the size was below 80 nm and its attribution relatively narrow, the inorganicorganic hybrid materials had coreshell structure (AgCl as the core and PMMA as the shell) after microemulsion polymerization and AgCl nanoparticles were evenly dispersed in the PMMA matrix and the equilibrium swelling-sorption amount (A ) ratio of cyclohexene to cyclohexane in membranes was up to 130.4, was larger than that in the pure PMMA membranes of 54.7. The surfactant content would inuence the sorption performance of cyclohexene in the organicinorganic hybrid membranes. Acknowledgements This research has been supported by Post-doctor Science Foundation of Zhejiang Province (20061206) and Supported by the State Key Development Program for Basic Research of China (No. 2003CB615700) and Scientic Research Fund of Zhejiang Provincial Education Department (20060803).