CN102658036A - Coating liquid, organic-inorganic hybrid cation exchange membrane and preparation method thereof - Google Patents
Coating liquid, organic-inorganic hybrid cation exchange membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a coating liquid, an organic-inorganic hydrid cation exchange membrane and a preparation method thereof. The coating liquid comprises polyvinyl alcohol, water and a multi-silicon cross-linking agent, wherein the mass ratio of the multi-silicon cross-linking agent and the polyvinyl alcohol is (0.75-1.34):1. The multi-silicon cross-linking agent is prepared as the following process: a monomer A, a monomer B, a solvent C and an initiator D are mixed and reacted according to the molar ratio of monomer A containing a sodium benzene sulfonate group: monomer B containing an alkoxy silicon group: solvent C: initiator D = 1: (1-2.34): (38.5-87.7): (0.020-0.036). Then, 60-75% of the solvent C is removed to produce the multi-silicon cross-linking agent solution. The hybrid cation exchange membrane is obtained from the coating liquid of the invention. The membrane has the advantages of high crosslinking degree, homogeneous transparency, good mechanical property, high swelling resistance and thermostability, and can be applied to the field of alkali recovery.
Description
Technical field
The invention belongs to the membrane technology field; Relate to particularly and a kind ofly be used to form the coating liquid of organic-inorganic hybrid cation-exchange membranes and adopt this coating liquid to prepare the method for organic-inorganic hybrid cation-exchange membranes and the organic-inorganic hybrid cation-exchange membranes of gained through sol-gel process.
Background technology
" membrane science journal (Journal of Membrane Science, 342 (2009) 221-226) has reported that elder generation carries out sulfonation to polyvinyl alcohol (PVA), carries out blend with sulfonated polyether-ether-ketone again, obtains cation-exchange membrane after the heat treatment.The ion exchange capacity of the cation-exchange membrane of this method preparation is higher, but shortage is covalently cross-linked in the film, and the stability of film is not enough.
" membrane science journal (Journal of Membrane Science; 376 (2011) 233-240) having reported that first preparation is a kind of contains-copolymer of COOH group; Copolymer and PVA carry out sol gel reaction, generate coating liquid, obtain hybrid cation-exchange membranes after the heat treatment.The cation-exchange membrane of this method preparation has good stability, and the application potential aspect diffusion dialysis is high.But the defective that has following inherence: (1) in the copolymer process because-the acid catalysis effect of COOH group, make copolymer that gelatin phenomenon usually take place, experiment is repeatable poor; (2) because-polarity of COOH group is lower, cause copolymer and PVA compatibility not good, so contain more deposition in the coating liquid, the film heterogeneity.(3) contain-acrylic acid of COOH group is volatile and have strong and stimulating, in copolymerization and evaporation process, damages operating personnel's health easily.
" materials chemistry " (Chemistry of Materials, 20 (2008) 6857-6870) have reported the Nafion basement membrane have been immersed in silane and/or the organic acid system, after the original position sol gel reaction, obtained hybrid cation-exchange membranes.Film has the moisture-retaining capacity of improvement in the intensification environment, but owing to the Nafion basement membrane costs an arm and a leg, and shortage is covalently cross-linked between interior organic facies of film and the inorganic phase, is easy to generate organic and inorganic and is separated, and it is limited that film properties improves degree.
The preparation method of a kind of organic-inorganic hybrid cation-exchange membranes of one Chinese patent application number 03131571.2 announcement utilizes the alkoxy silane that contains sulfydryl in the strand to be raw material, is prepared into colloidal sol and on inorganic matrix, films, and after the heat treatment sulfydryl is carried out oxidation.This method step is simple, and inorganic in the film-organic principle compatibility is good, but owing to adopted inorganic matrix to make supporter, makes that the carrying capacity of film is not high, lacks pliability, has limited the application of film in fields such as diffusion dialysis, electrodialysis.
One Chinese patent application CN201010107733.7 has announced a kind of preparation method of organic-inorganic hybrid cation-exchange membranes, earlier preparation a kind of double containing-Si (OR)
3Copolymer with-COOH (or acid anhydrides) group after sulfonated poly (phenylene oxide) (SPPO) blend, carries out original position sol gel reaction film forming.The physical stability of film is good, stable electrical properties, but owing to do not contain in the sulfonated poly (phenylene oxide)-OH base, causes lacking between sulfonated poly (phenylene oxide) and the copolymer covalently cross-linked, and the homogeneity of film is not enough, and is not enough at the application performance in diffusion dialysis field.
Summary of the invention
The present invention includes three purposes, purpose one provides a kind of coating liquid that is used to prepare organic-inorganic hybrid cation-exchange membranes; Purpose two provides a kind of method of using said coating liquid to prepare organic-inorganic hybrid cation-exchange membranes; Purpose three provides a kind of organic-inorganic hybrid cation-exchange membranes that formed by coating liquid of the present invention or that prepared by method of the present invention.Organic-inorganic hybrid cation-exchange membranes of the present invention has overcome the above-mentioned defective of prior art, stability covalently cross-linked as lacking in the film, film is not enough, contain more deposition in repeatable poor, the coating liquid of experiment, damage easily operating personnel health, be easy to generate that organic and inorganic is separated, film heterogeneity, film be in the application performance deficiency in diffusion dialysis field etc.
For this reason, the present invention provides following several aspect:
< 1.>a kind of coating liquid that is used to form organic-inorganic hybrid cation-exchange membranes; Said coating liquid comprises polyvinyl alcohol, water and many silicon crosslinking agent; Wherein the mass ratio of many silicon crosslinking agent and polyvinyl alcohol is (0.75-1.34): 1, and said many silicon crosslinking agent prepares by following process:
In molar ratio for containing the monomer A of benzene sulfonic acid sodium salt group: the monomers B that contains the alkoxyl silicone group: solvent C: initator D=1: (1-2.34): (38.5-87.7): proportion relation (0.020-0.036); Monomer A, monomers B, solvent C and initator D are mixed and reaction; Remove the solvent C of 60-75% afterwards, make many silicon cross-linking agent solution.
< 2 >. according to < 1>the described coating liquid that is used to form organic-inorganic hybrid cation-exchange membranes, the said 65-80 of being reflected at ℃ temperature conditions carried out 12-36 hour.
<3>. according to<1>Or<2>The described coating liquid that is used to form organic-inorganic hybrid cation-exchange membranes, the said chemical formulation that contains the monomer A of benzene sulfonic acid sodium salt group is CH
2=CH (R1) C
6H
3SO
3Na, R1 are H atom, halogen atom or the alkyl that contains 1-2 carbon atom; The said monomers B that contains the alkoxyl silicone group is methacrylic acid-trimethoxy silicon propyl ester, VTES, vinyltrimethoxy silane, allyltrimethoxysilanis or triethoxysilicane styrene; Said initator D is dibenzoyl peroxide or azodiisobutyronitrile.
< 4 >. a kind of method for preparing organic-inorganic hybrid cation-exchange membranes, said method comprises:
Each described coating liquid in 1 to 3 is coated on the matrix.
< 5 >. a kind of method for preparing organic-inorganic hybrid cation-exchange membranes, said method comprises the steps:
(1) preparation of many silicon crosslinking agent:
In molar ratio for containing the monomer A of benzene sulfonic acid sodium salt group: the monomers B that contains the alkoxyl silicone group: solvent C: initator D=1: (1-2.34): (38.5-87.7): proportion relation (0.020-0.036); Monomer A, monomers B, solvent C and initator D are mixed and reaction; Remove the solvent C of 60-75% afterwards, make many silicon cross-linking agent solution.
(2) preparation of coating liquid: polyvinyl alcohol (PVA) is dissolved in the water to form mass concentration be the solution of 5%-10%; The temperature range of control PVA solution is 35-75 ℃; Under stirring condition; With mass ratio is many silicon crosslinking agent: PVA=(0.75-1.34): 1 drips many silicon crosslinking agent in PVA solution, stirs simultaneously and reacts and make coating liquid; And
(3) preparation of hybrid cation-exchange membranes: the coating liquid that step (2) is made is coated on the matrix; Coating liquid being dried on matrix forming uniform and stable gel layer is diaphragm; Then diaphragm is heat-treated, can obtain organic-inorganic hybrid cation-exchange membranes of the present invention.
< 6 >. according to < 4>or < 5>described preparation method, wherein said matrix is glass plate, aluminium foil, polyfluortetraethylene plate, polyvinyl chloride panel, porous ceramics piece or nonwoven.
< 7 >. according to < 4>or < 5>described preparation method, the method that wherein coating liquid is coated on the matrix is knifing, hydrostomia, dipping or coating.
< 8. >, wherein in the preparation of the coating liquid of (2), comprise that the dropping time that in PVA solution, drips many silicon crosslinking agent is 0.5-2 hour, under 35-75 ℃ of temperature conditions stirring reaction 12-36 hour according to < 5>described preparation method.
< 9 >. according to < 5>described preparation method, described heat treatment is: (1) places the diaphragm of ribbon matrix under the temperature 60-80 ℃ condition and is warming up to temperature 120-140 ℃ with 10-20 ℃/hour speed, is incubated 1-8 hour; Or (2) scrape diaphragm from matrix, and diaphragm is placed under the temperature 60-80 ℃ condition and is warming up to temperature 130-140 ℃ with 5-15 ℃/hour speed, is incubated 1-4 hour.
< 10 >. a kind of organic-inorganic hybrid cation-exchange membranes, its use are filmed on matrix according to each described coating liquid in < 1>to < 3>and are made, or use is prepared from according to each described method in < 4>to < 9 >.
The invention has the advantages that: utilize the many silicon crosslinking agent contain the benzene sulfonic acid sodium salt group and PVA prepared class I organic-inorganic mutually between covalent cross-linking, homogeneity is good, mechanical performance is good, the diffusion dialysis performance is high hybrid cation-exchange membranes; Many silicon crosslinking agent wherein contains-SO
3The Na group has the advantage that is difficult for gel, non-volatile and high polarity, for developing practical hybrid cation-exchange membranes new approach is provided.
Description of drawings
Fig. 1 is ESEM (SEM) figure (left side, figure (c)) and digital photograph ((e) schemed on the right side) of the prepared hybrid cation-exchange membranes of embodiment 1; And
Fig. 2 is the SEM figure of hybrid cation-exchange membranes of the present invention, and wherein (1) is the prepared film that contains the nonwoven supporter of embodiment 3; (2) be the prepared film that contains ceramic supporting body of embodiment 4.
The specific embodiment
First aspect of the present invention provides a kind of coating liquid that is used to form organic-inorganic hybrid cation-exchange membranes; Said coating liquid comprises polyvinyl alcohol (PVA), water and many silicon crosslinking agent; Wherein the mass ratio of many silicon crosslinking agent and PVA is (0.75-1.34): 1; Said many silicon crosslinking agent prepares by following process: in molar ratio for containing the monomer A of benzene sulfonic acid sodium salt group: the monomers B that contains the alkoxyl silicone group: solvent C: initator D=1: (1-2.34): (38.5-87.7): proportion relation (0.020-0.036); Monomer A, monomers B, solvent C and initator D are mixed and reaction, and the solvent C of removing 60-75% afterwards makes many silicon cross-linking agent solution.
In the present invention, the degree of polymerization scope of PVA is 800-2500, and the use of PVA can be given film favorable mechanical performance and homogeneity, contained-OH base can carry out crosslinkedly with many silicon crosslinking agent on the one hand, also help the application performance that improves film on the one hand.
Preferably, contain the monomer A of benzene sulfonic acid sodium salt group, the monomers B that contains the alkoxyl silicone group, solvent C and initator D 65-80 ℃ of temperature conditions reaction 12-36 hour.
Preferably; In molar ratio for containing the monomer A of benzene sulfonic acid sodium salt group: the monomers B that contains the alkoxyl silicone group: solvent C: initator D=1: (1-1.5): (46-58): proportion relation (0.021-0.027), mix monomer A, monomers B, solvent C and initator D.
The said unsaturated monomer A that contains the benzene sulfonic acid sodium salt group, its chemical formula can be expressed as CH
2=CH (R1) C
6H
3SO
3Na, R1 are H atom, halogen atom or the alkyl that contains 1-2 carbon atom, like SSS, 2-chloro-4-vinylbenzenesulfonic acid sodium or 2-methyl-4-vinylbenzenesulfonic acid sodium.
The said monomers B that contains the alkoxyl silicone group is methacrylic acid-trimethoxy silicon propyl ester, VTES, vinyltrimethoxy silane, allyltrimethoxysilanis or triethoxysilicane styrene.
Solvent C is the solvent of dissolved monomer A and monomers B simultaneously, for example, and N, dinethylformamide, methyl alcohol or methyl alcohol and N, the mixture of dinethylformamide.
Said initator D is dibenzoyl peroxide or azodiisobutyronitrile.
In addition, mentioned polyvinyl alcohol (PVA) can adopt and be purchased product among the present invention, for example from the polyvinyl alcohol of Shanghai Chemical Reagent Co., Ltd., Sinopharm Group.Polyvinyl alcohol is because the characteristics of its production technology; Generally still contain moisture or small molecule alcohol; Therefore in order accurately to know the reagent net weight, can adopt like the mode of putting down in writing among the embodiment and detect quantity of solvent remaining in the PVA raw material that is bought, to confirm accurate PVA addition.
Second aspect of the present invention provides a kind of method for preparing organic-inorganic hybrid cation-exchange membranes, and said method comprises that the coating liquid with above-mentioned preparation is coated on the matrix.
Particularly, the method for preparing organic-inorganic hybrid cation-exchange membranes of the present invention comprises the steps:
(1) preparation of many silicon crosslinking agent:
In molar ratio for containing the monomer A of benzene sulfonic acid sodium salt group: the monomers B that contains the alkoxyl silicone group: solvent C: initator D=1: (1-2.34): (38.5-87.7): (0.020-0.036); Preferably; In molar ratio for containing the monomer A of benzene sulfonic acid sodium salt group: the monomers B that contains the alkoxyl silicone group: solvent C: initator D=1: (1-1.5): (46-58): proportion relation (0.021-0.027); Monomer A, monomers B, solvent C and initator D are mixed and reaction; Remove the solvent C of 60-75% afterwards, make many silicon cross-linking agent solution.Wherein monomer A, monomers B, solvent C and initator D have aforesaid definition.
Wherein, the reaction temperature of monomer A, monomers B, solvent C and initator D and reaction time are by conditions such as monomer of being selected for use and initators and confirm.For example, be under the situation of SSS in monomer A, said reaction can be carried out 12-36 hour at 65-80 ℃ of temperature conditions.
(2) preparation of coating liquid: polyvinyl alcohol (PVA) is dissolved in the water to form mass concentration be the solution of 5%-10%; The temperature range of control PVA solution is 35-75 ℃; Under stirring condition; With mass ratio is many silicon crosslinking agent: PVA=(0.75-1.34): 1 drips many silicon crosslinking agent in PVA solution, make coating liquid after stirring and the reaction.
Preferably, under stirring condition, be many silicon crosslinking agent: PVA=(0.8-1) with mass ratio: 1 drips many silicon crosslinking agent in PVA solution.
Preferably, the dropping time is 0.5-2 hour, and after under the 35-75 ℃ of temperature conditions stirring reaction 12-36 hour, makes coating liquid.Wherein, the control dropping time helps obtaining homogeneous, crosslinked sufficient coating liquid; Suitable reaction temperature helps improving reaction rate; The suitable reaction time helps improving the extent of reaction, and has taken into account the cost of technology.
(3) preparation of hybrid cation-exchange membranes: the coating liquid that step (2) makes is filmed on matrix; Coating liquid being dried on matrix forming uniform and stable gel layer is diaphragm; Then diaphragm is heat-treated, can obtain organic-inorganic hybrid cation-exchange membranes of the present invention.
The instance of said matrix comprises glass plate, aluminium foil, polyfluortetraethylene plate, polyvinyl chloride panel, porous ceramics piece or nonwoven.
The instance of said method of filming comprises knifing, hydrostomia, dipping or coating.
Preferably, the heat-treating methods in the preparation of said step (3) hybrid cation-exchange membranes can for: (1) places the diaphragm of ribbon matrix under the temperature 60-80 ℃ condition and is warming up to temperature 120-140 ℃ with 10-20 ℃/hour speed, is incubated 1-8 hour; Or (2) scrape diaphragm from matrix, and diaphragm is placed under the temperature 60-80 ℃ condition and is warming up to temperature 130-140 ℃ with 5-15 ℃/hour speed, is incubated 1-4 hour, promptly obtains organic-inorganic hybrid cation-exchange membranes of the present invention.Film is carried out above heat treatment, can eliminate solvent or other volatile materials remaining in the film on the one hand, on the other hand, can promote that composition is cross-linked with each other the degree of cross linking of reinforcing membrane and stability in the film.
Method of the present invention with the monomer that contains the benzene sulfonic acid sodium salt group with contain-Si (OR)
3The monomer of group is a raw material, prepares many silicon crosslinking agent through copolyreaction, behind many silicon crosslinking agent and the PVA solution blending, carries out sol gel reaction jointly, heat-treats after filming, and promptly obtains organic-inorganic hybrid cation-exchange membranes.Wherein have concurrently in many silicon crosslinking agent-SO
3Na and-Si (OR)
3Group ,-SO
3The Na group can give film strong ion exchanging function, simultaneously-and Si (OR)
3Cross-linking reaction can take place with PVA in group, forms organic-inorganic crosslinking network structure, the stability of reinforcing membrane.Method of the present invention and " membrane science journal (Journal of Membrane Science; 342 (2009) 221-226) report carries out sulfonation, carries out blend with sulfonated polyether-ether-ketone again and the method for preparing cation-exchange membrane is compared PVA; The prepared film inside of the present invention has formed the organic and inorganic cross-linked network, and the stability of film is higher; With " membrane science journal (Journal of Membrane Science; 376 (2011) 233-240) copolymer of a kind of containing-COOH group of preparation earlier of report, carry out sol gel reaction with PVA again and the method that obtains hybrid cation-exchange membranes is compared, the present invention has prepared a kind of containing-SO earlier
3Many silicon crosslinking agent of Na group, because-SO
3The catalytic action of Na group is weak, do not have volatility, polarity is high, and therefore many silicon crosslinking agent is difficult for gel, non-volatile, and after carrying out sol gel reaction with PVA, the coating liquid transparent and homogeneous that obtains does not have deposition; With " materials chemistry " (Chemistry of Materials; 20 (2008) 6857-6870) report with application number be that the disclosed method of utilizing little molecule alkoxy silane to prepare hybrid cation-exchange membranes is compared in 03131571.2 the Chinese patent file; Many silicon crosslinking agent that the present invention uses has higher pliability, stronger crosslinked ability and the organic component content of Geng Gao, therefore prepared film mechanical performance is good, between the organic and inorganic component through covalently cross-linked, compatibility good; With application number be the disclosed a kind of double containing-Si (OR) of preparation earlier in the Chinese patent file of CN201010107733.7
3Copolymer with-COOH (or acid anhydrides) group; Carry out the method for original position sol gel reaction film forming compares with sulfonated poly (phenylene oxide) (SPPO); Many silicon crosslinking agent and PVA that the present invention uses carry out sol gel reaction, owing to contain a large amount of-OH base among the PVA, therefore can carry out covalently cross-linked with many silicon crosslinking agent; Generate the film of transparent and homogeneous, have high application performance in the diffusion dialysis field.
Embodiment
Below come illustrated in detail coating liquid of the present invention and hybrid cation-exchange membranes through specific embodiment the preparation method, these embodiment only are used to further specify the present invention, rather than limit scope of the present invention.
Embodiment 1: the many silicon crosslinking agent based on high-phenylethylene sodium sulfonate content prepares hybrid cation-exchange membranes
The preparation of raw material: (1) polyvinyl alcohol (PVA; Shanghai Chemical Reagent Co., Ltd., Sinopharm Group; The degree of polymerization is 1750 ± 50) detection of raw material: be that remaining solvent (water and ethanol etc.) is measured in the test PVA raw material; Get 2g PVA sample earlier, until constant weight, calculated weight loss is than being 5.7% 60 ℃ of oven dry; (2) dissolving of PVA: get 42.4g PVA raw material, be soaked in the 760mL water one day, under stirring condition; Again with the programming rate of 8 ℃/h; Be warmed up to about 102 ℃, and, obtain the solution of homogeneous transparent at 2.5 hours (h) of 102 ℃ of insulations; Subsequent use after being cooled to about 60 ℃, the mass concentration of solution is 5%; (3) azodiisobutyronitrile (AIBN; The production of Shanghai Chemical Reagent Co., Ltd., Sinopharm Group) recrystallization: under 50 ℃ of conditions, 10 gram azodiisobutyronitriles are dissolved in the 100mL ethanol, and cryosel is bathed crystallisation by cooling; Obtain crystallized product behind the suction filtration, crystallized product under room temperature, vacuum environment dry two days.It is worthy of note that the set-up procedure of raw material is dispensable in (1) and (3), those skilled in the art can determine whether according to the actual conditions of the raw material that is obtained to adopt.
Carry out following steps then:
(1) preparation of many silicon crosslinking agent: in the round-bottomed flask that reflux condensing tube and drying tube are housed, add 360mL N, dinethylformamide (4.63mol DMF) under the stirring condition, adds 20.62g (0.1mol) SSS (the couplet chemical industry Co., Ltd of Shandong Zibo star; Technical pure), continues to stir 2h, be warming up to 70 ℃; Add 23.7mL (0.1mol) methacrylic acid-trimethoxy silicon propyl ester (KH-570, Tianzhang City, Anhui Province green chemical industry auxiliary agent Co., Ltd, chemical pure) and 0.175g AIBN successively; Behind the reaction 12h, add 0.175g AIBN again, continue reaction 12h; Through rotary evaporation, remove 216mL solvent (DMF), obtain many silicon cross-linking agent solution; Through sampling oven dry weight method (promptly get the solution of certain volume, dry to constant weight), the concentration of measuring many silicon cross-linking agent solution is 0.24g/mL.In the present embodiment, mol ratio is SSS: KH-570: DMF: AIBN=1: 1: 46.3: 0.021.
(2) preparation of coating liquid: get many silicon of 83.3mL (20g) cross-linking agent solution, in 1h, drop in 400mL (20g) the PVA solution, in the dropping process, keep stirring; The temperature of control PVA solution is 60 ℃; After dripping end, continue to obtain the coating liquid of transparent and homogeneous at 60 ℃ of stirring reaction 18h.
(3) preparation of hybrid cation-exchange membranes: the coating liquid of gained is coated on the glass plate; Aeration-drying is 2 days under the room temperature environment, and making coating liquid on glass plate, form uniform and stable gel layer is diaphragm, scrapes diaphragm from glass plate; Diaphragm is placed under 60 ℃ of conditions of temperature; Speed with 10 ℃/h is warming up to 130 ℃ of temperature then, and under 130 ℃ of conditions, is incubated 4h, promptly obtains organic-inorganic hybrid cation-exchange membranes of the present invention.
In the preparation process of above-mentioned many silicon crosslinking agent, parallel test gelatin phenomenon all do not occur three times, and solution evaporation property is low, pollution is little; In the preparation process of above-mentioned coating liquid, parallel test all can obtain the solution of transparent and homogeneous for three times.With " membrane science journal (Journal of Membrane Science, 376 (2011) 233-240) is compared, and the preparation process of many silicon crosslinking agent of present embodiment is safer controlled, and coating liquid is homogeneous more.
Above-mentioned hybrid cation-exchange membranes to making is tested as follows:
(1) water content: operation is all at room temperature carried out, and weight of clip is m
1Diaphragm, m
1Scope restrain at 0.10-0.30, be immersed in the water after 2 days, take out diaphragm, dry the water of membrane surface with filter paper, the gravimetric value that obtains after the weighing is designated as m
2The water content of diaphragm=(m
2-m
1) * 100%/m
1
(2) ion exchange capacity (IEC): operation is all at room temperature carried out, and weight of clip is m
3Diaphragm, m
3Scope restrain at 0.15-0.40; After concentration is to soak 2 days among the HCl of 1mol/L; Take out diaphragm, with distilled water immersion 16 hours and in soak period, change water 4 times, again diaphragm is immersed in the KOH solution that 80mL concentration is 0.04mol/L two days; Make indicator with phenolphthalein, use concentration the KOH solution after soaking to be carried out back titration as the HCl of 0.04mol/L.IEC=(concentration is that molal quantity-concentration of the KOH of 0.04mol/L is the molal quantity of the HCl of 0.04mol/L)/m
3
(3) anti-swelling test: weight of clip is m
4Diaphragm, m
4Scope restrain at 0.15-0.30, be immersed in the 80mL temperature and be in 65 ℃ the water, whenever took out diaphragm at a distance from 6 hours, dry the water on surface, after the weighing diaphragm is put into 65 ℃ of water again and continues immersions.Make weight change percentage curve over time, the time when weight increase percentage reaches maximum is designated as swelling time.
(4) mechanical strength test: use Instron universal tester (Model 1185), sample shear becomes dumb-bell shape, and playing initial length is 25mm, and room temperature environment stretched speed is 25mm/min.The hot strength (TS) and the elongation at break (E of record test
b).
(5) hot analytical test: use the heat endurance of Shimadzu TGA-50H analyzer specimen, heating rate is 10 ℃ of min under the air atmosphere
-1
(6) ESEM (SEM): observe the film pattern through SEM (SEM), film is quenched in liquid nitrogen and is had no progeny gold-platedly, observes the section of film.The instrument model of using is XT30 ESEM-TMPPHILIP.
(7) test that alkali is used is reclaimed in diffusion dialysis: square of clip or circular membrane sample, the areal extent of sample is 8-12cm
2, the region area that wherein is used for diffusion dialysis is 6cm
2Membrane sample is fixed on the pond central authorities that comprise two compartments, and the volume that every compartment can add solution is 100mL, and a compartment is as the diffusion side, and it is 1mol/L NaOH+0.40mol/LNa that composition is equipped with in inside
2WO
4Diffusion liquid, another pond is as the dialysis side, distilled water is equipped with in inside.Before test, film soaked 1 day in diffusion liquid in advance.When spreading test, utilizing the temperature of solution in two compartments of water-bath device control is 20 ℃; Simultaneously solution in two compartments is carried out constant speed and stir, in order to eliminate the concentration polarization effect.After diffusion is carried out 1 hour, the solution in diffusion side and the dialysis side is taken out,, can calibrate the contained OH of solution in the both sides if with the titration of HCl solution
-Ion concentration; If adopt mixture of sulfuric phosphoric acid titration and AAS, can calibrate the contained WO of solution in the both sides
4 2-Ion concentration.
The ratio of the dialysis coefficient (U) through two kinds of compositions can calculate the separation factor (S) of a kind of composition with respect to another kind of composition.U can pass through computes: U=M/ (At Δ C).M represents the molal quantity of transfer components in the formula, and A represents the effective area (m of film
2), t represent the time (hour), Δ C represents the logarithmic mean concentration (mol/m between two Room
3), be defined as Δ C=(C
f 0-C
d t-C
f t)/ln [(C
f 0-C
d t)/C
f t].C in the formula
f 0And C
f tRepresentative diffusion side solution is 0 concentration with t the time in the time respectively, C
d tRepresent the concentration of dialysis side solution when time t.It should be noted that (C
f 0-C
d t-C
f t) do not equal zero, because there is moisture transmission to cross film, cause the variation of two Room solution inner volumes.
Test result shows: the water content of the hybrid cation-exchange membranes that present embodiment is prepared is 54.8%; IEC is 1.05mmol/g, and the swellbility in 65 ℃ of water behind the 216h is 115%.
Mechanical strength test: the elongation at break of film is 21.1%, and hot strength is 26MPa.Explain that film has the favorable mechanical performance, be superior to application number and be the support film of 03131571.2 Chinese patent report.
ESEM shown in Fig. 1 (left side), shows that the prepared cation-exchange membrane homogeneous of present embodiment is smooth, no noted phase separation phenomena from the section of microcosmic observation film.Digital photograph shown in Fig. 1 (right side), shows the cation-exchange membrane water white transparency from the surface of macroscopic view observation film.These observations show that all the homogeneity of the hybrid cation-exchange membranes that present embodiment is prepared is better than membrane science magazine (Journal of Membrane Science, 376 (2011) 233-240) and Chinese patent (application number CN201010107733.7) report film.
Hot analytical test: the short term thermal stability of film in air atmosphere is 237 ℃, and explaining that film has should be through covalently cross-linked between the organic and inorganic composition in the good heat endurance, film.
The test of alkali is reclaimed in diffusion dialysis: during room temperature (20 ℃), the alkali dialysis coefficient of film is 0.0103m/h, separation factor (S
OH/WO4) be 17.3.Compare with commercial sulfonated poly (phenylene oxide) film (0.0014m/h, 36) and the commercial DF-120 film (0.009m/h, 18) that is applied to the acid recovery field, the prepared cation-exchange membrane of present embodiment has higher dialysis coefficient, can be applicable to alkali and reclaims the field.
Comprehensive above test result, but knowledge capital embodiment has obtained the organic-inorganic hybrid cation-exchange membranes of transparent and homogeneous, and film has favorable mechanical performance and heat endurance, and can be applicable to the diffusion dialysis field, carries out alkali and reclaims.
Embodiment 2: the many silicon crosslinking agent based on low-styrene sodium sulfonate content prepares hybrid cation-exchange membranes
The set-up procedure of raw material is carried out following steps then with embodiment 1:
(1) preparation of many silicon crosslinking agent: in the round-bottomed flask that reflux condensing tube and drying tube are housed, add 385mL DMF, under the stirring condition, add the 12.36g SSS; Continue to stir 2h, be warming up to 70 ℃, add 33.2mL KH-570 and 0.175g AIBN successively; Behind the reaction 12h, add 0.175g AIBN again, continue reaction 12h; Through rotary evaporation, remove 255mL solvent (DMF), obtaining concentration is many silicon cross-linking agent solution of 0.26g/mL.In the present embodiment, mol ratio is SSS: KH-570: DMF: AIBN=1: 2.3: 82.5: 0.035.
(2) preparation of coating liquid: get many silicon of 76.9mL (20g) cross-linking agent solution, in 1h, be added dropwise in 400mL (20g) the PVA solution, in the dropping process, keep stirring; The temperature of control PVA solution is 65 ℃; After dripping end, continue to obtain the coating liquid of transparent and homogeneous at 65 ℃ of stirring reaction 35h.
(3) preparation of hybrid cation-exchange membranes: with the coating liquid hydrostomia in glass plate; Aeration-drying is 2 days under the room temperature environment, and making coating liquid on glass plate, form uniform and stable gel layer is diaphragm, takes diaphragm off; Place under 60 ℃ of conditions of temperature; Speed with 5 ℃/h is warming up to 140 ℃ of temperature then, and under 140 ℃ of conditions, is incubated 1h, promptly gets organic-inorganic hybrid cation-exchange membranes of the present invention.
In the preparation process of above-mentioned many silicon crosslinking agent, parallel test gelatin phenomenon all do not occur four times; In the preparation process of above-mentioned coating liquid, parallel test all can obtain the solution of transparent and homogeneous for four times, explains that the controllable process property of present embodiment is good.
Cation-exchange membrane to present embodiment makes is tested, and the result shows:
The water content of film is 30%; IEC is 0.72mmol/g; Swellbility in 65 ℃ of water behind the 216h is 46%; With " membrane science journal (Journal of Membrane Science; 342 (2009) 221-226) water content (can reach 78% or 110%) of report is compared, and the cation-exchange membrane of present embodiment preparation has higher anti-swelling ability.
Mechanical strength test: the elongation at break of film is 13.7%, and hot strength is 9.1MPa.
ESEM and digital photograph observation: film transparent and homogeneous, no noted phase separation phenomena.
Hot analytical test: the short term thermal stability of film in air atmosphere is up to 273 ℃; Be higher than " Chinese patent that peak (263 ℃) under the same test method of membrane science journal (Journal of Membrane Science, 376 (2011) 233-240) report and application number are CN201010107733.7 openly is worth (262 ℃).
The diffusion dialysis test: during room temperature (20 ℃), the dialysis coefficient of alkali is 0.0111m/h, and separation factor is 18.5, explains that film can be applied to alkali and reclaim the field.
Comprehensive above test result, but knowledge capital embodiment has obtained the organic-inorganic hybrid cation-exchange membranes of transparent and homogeneous, and film has high anti-swelling ability and heat endurance, and can be applied to the diffusion dialysis field, carries out alkali and reclaims.
Embodiment 3: the preparation of the hybrid cation-exchange membranes of nonwoven supporter
The preparation of raw material: (1) methyl alcohol is soaked in anhydrous Na
2SO
4In 2 days; (2) 84.8g technical grade 17-99 type PVA was soaked in the 720mL water one day, under stirring condition, again with the programming rate of 10 ℃/h; Be warming up to 95 ℃, and, obtain the solution of homogeneous transparent at 95 ℃ of insulation 4h; Subsequent use after being cooled to 35 ℃, the formation mass concentration is 10% PVA solution; (3) the 10 thick dibenzoyl peroxides of gram (BPO) are dissolved in the 40mL chloroform, the elimination insoluble matter, and filtrating is poured 100mL in advance with in the salt-cooled methyl alcohol of ice, promptly has crystallization to separate out, and obtains crystallized product after the filtration, and the room temperature vacuum drying is one day in the presence of calcium chloride.Carry out following steps then:
(1) preparation of many silicon crosslinking agent: in the round-bottomed flask that serpentine condenser and drying tube are housed, add 200mL DMF and 180mL methyl alcohol, under the stirring condition, add 19.32g 2-chloro-4-vinylbenzenesulfonic acid sodium; Be warming up to 80 ℃ subsequently; Add 0.12mol allyltrimethoxysilanis and 0.525g BPO successively, stirring reaction 12h is through the method for decompression distillation after the first air-distillation; Remove the 240mL solvent, obtain many silicon cross-linking agent solution.In the present embodiment, mol ratio is a 2-chloro-4-vinylbenzenesulfonic acid sodium: allyltrimethoxysilanis: (DMF and methyl alcohol): BPO=1: 1.5: 87.7: 0.027.
(2) preparation of coating liquid: get many silicon of 10g crosslinking agent, in 2h, be added dropwise in the 7.5g PVA solution, vigorous stirring under 35 ℃ of conditions after dropping finishes, continues to obtain the coating liquid of transparent and homogeneous at 35 ℃ of stirring reaction 36h.
(3) preparation of hybrid cation-exchange membranes: with the coating liquid knifing on nonwoven; Aeration-drying is 3 days under the room temperature environment; Making coating liquid on nonwoven, form uniform and stable gel layer is diaphragm, and diaphragm is placed under 80 ℃ of conditions of temperature together with nonwoven, and the speed with 20 ℃/h is warming up to 120 ℃ of temperature then; And under 120 ℃ of conditions, be incubated 8h, promptly get organic-inorganic hybrid cation-exchange membranes of the present invention.
Above-mentioned hybrid cation-exchange membranes to making is tested, and the result is following:
The water content of film is 37%; IEC is 0.57mmol/g, and the swellbility in 65 ℃ of water behind the 216h is 56%, and the test result of comparative example 1 and embodiment 2 explains that nonwoven has reduced the IEC of film as supporter, has improved the anti-swelling ability of film.
Mechanical strength test: the elongation at break of film is 46%, and hot strength is 64MPa, explains that nonwoven has improved the mechanical performance of film as supporter.
Similar " membrane science journal (the Journal of Membrane Science of the method for testing of ESEM; 376 (2011) 233-240) institute's reported method; Just in the present embodiment, because sample contains nonwoven, it is disconnected to be difficult to quench; Therefore when sample preparation, cut off sample, the section of observation sample with scissors.The result shows: non-woven fabrics fiber is wrapped in the hybrid inorganic-organic layer, and flawless in the hybrid layer is shown in Fig. 2 (1).
The test of alkali is reclaimed in diffusion dialysis: during room temperature (20 ℃), the alkali dialysis coefficient of film is 0.067m/h, separation factor (S
OH/WO4) be 16.8, explain that the use of nonwoven has reduced the efficient of the recovery alkali of film.
Comprehensive above test result, but to have obtained with the nonwoven be the organic-inorganic hybrid cation-exchange membranes of supporter to knowledge capital embodiment, and the use of nonwoven has reduced the IEC and the alkali recovery efficiency of film, but has improved the mechanical performance and the anti-swelling ability of film.
Embodiment 4: the preparation of the hybrid cation-exchange membranes of ceramic supporting body
The preparation of the preparation of raw material, many silicon crosslinking agent, the preparation of coating liquid obtain coating liquid with embodiment 3.Coating liquid is carried out following steps:
With the top layer composition is Al
2O
3Porous ceramics piece impregnated in the coating liquid 25 seconds, aeration-drying is 1 day under the room temperature environment, once more potsherd impregnated in the coating liquid 25 seconds; Aeration-drying is 2 days under the room temperature environment; Making coating liquid on potsherd, form uniform and stable gel layer is diaphragm, and diaphragm is placed under 60 ℃ of conditions of temperature together with potsherd, and the speed with 10 ℃/h is warming up to 140 ℃ of temperature then; And under 140 ℃ of conditions, be incubated 1h, promptly get organic-inorganic hybrid cation-exchange membranes of the present invention.
Behind the 216h, mass loss is merely 0.8% to the prepared cation-exchange membrane of present embodiment in 65 ℃ of water, explains with potsherd to have high anti-swelling ability as the cation-exchange membrane of supporter.
The method of testing of ESEM is with " membrane science journal (Journal of Membrane Science; 376 (2011) 233-240), just in the present embodiment since sample with potsherd as supporter; It is disconnected to be difficult to quench; Therefore when sample preparation, cut membrane sample with mechanical force, the section of observation sample is shown in Fig. 2 (2).The result shows: hybrid inorganic-organic layer homogeneous is fine and close and adsorbed close is surperficial in potsherd, so film is fit to be applied to nanofiltration.
The result of embodiment 3 and embodiment 4 has proved that further there are mating reaction in coating liquid of the present invention and different matrix, and this effect coating liquid not of the prior art can obtain.
Embodiment 5: the preparation of the hybrid cation-exchange membranes of low many silicon dosage of crosslinking agent
The preparation of raw material: (1) DMF is immersed in the molecular sieve two days; (2) 67.84g analyzes pure PVA and was soaked in the 740mL water one day, under stirring condition, again with the programming rate of 8 ℃/h; Be warmed up to 90 ℃, and, obtain the solution of homogeneous transparent at 90 ℃ of insulation 4h; Subsequent use after being cooled to 75 ℃, the formation mass concentration is 8% PVA solution; (3) method of purification of AIBN is with embodiment 1.
(1) preparation of many silicon crosslinking agent: in the round-bottomed flask that reflux condensing tube is housed, add 120mL DMF, under nitrogen protection and the stirring condition; Add 0.04mol 2-methyl 4-vinylbenzenesulfonic acid sodium, be warming up to 65 ℃ subsequently, add 0.06mol VTES and 0.196gBPO successively; Stirring reaction 36h; Through rotary evaporation, remove the 90mL solvent, obtaining concentration is many silicon cross-linking agent solution of 0.43g/mL.In the present embodiment, mol ratio is a 2-methyl 4-vinylbenzenesulfonic acid sodium: VTES: DMF: BPO=1: 1.5: 38.6: 0.020.
(2) preparation of coating liquid: get many silicon of 7.5g crosslinking agent, in 0.5h, be added dropwise in the 10g PVA solution, keep solution under 75 ℃ of conditions, to stir, after dropping finishes, continue to obtain the coating liquid of transparent and homogeneous at 75 ℃ of stirring reaction 12h.
(3) preparation of hybrid cation-exchange membranes: coating liquid is coated on the polyvinyl chloride panel; Aeration-drying is 2 days under the room temperature environment, and making coating liquid on polyvinyl chloride panel, form uniform and stable gel layer is diaphragm, scrapes diaphragm with blade; Diaphragm is placed under 80 ℃ of conditions of temperature; Speed with 15 ℃/h is warming up to 135 ℃ of temperature then, and under 135 ℃ of conditions, is incubated 3h, promptly gets organic-inorganic hybrid cation-exchange membranes of the present invention.
Above-mentioned hybrid cation-exchange membranes to making is tested, and method of testing is with reference to " membrane science journal (Journal of Membrane Science, 376 (2011) 233-240) and Chinese patent (application number CN201010107733.7).The result is following:
The water content of film is 45%, and IEC is 0.80mmol/g, and the swellbility in 65 ℃ of water behind the 216h is 142%.
The elongation at break of film is 29%, and hot strength is 32MPa.
The smooth homogeneous of the section of film, the surface transparent degree of film is high;
The test shows of alkali is reclaimed in diffusion dialysis, and during room temperature, the alkali dialysis coefficient of film is 0.098m/h, separation factor (S
OH/WO4) be 26.
Comprehensive above test result, but knowledge capital embodiment has obtained the organic-inorganic hybrid cation-exchange membranes of transparent and homogeneous, and film can be applicable to diffusion dialysis and reclaims the alkali field.
Claims (10)
1. coating liquid that is used to form organic-inorganic hybrid cation-exchange membranes; Said coating liquid comprises polyvinyl alcohol, water and many silicon crosslinking agent; Wherein the mass ratio of many silicon crosslinking agent and polyvinyl alcohol is 0.75-1.34: 1, and said many silicon crosslinking agent prepares by following process:
In molar ratio for containing the monomer A of benzene sulfonic acid sodium salt group: the monomers B that contains the alkoxyl silicone group: solvent C: the proportion relation of initator D=1: 1-2.34: 38.5-87.7: 0.020-0.036; Monomer A, monomers B, solvent C and initator D are mixed and reaction; Remove the solvent C of 60-75% afterwards, make many silicon cross-linking agent solution.
2. the coating liquid that is used to form organic-inorganic hybrid cation-exchange membranes according to claim 1, the said 65-80 of being reflected at ℃ temperature conditions carried out 12-36 hour.
3. the coating liquid that is used to form organic-inorganic hybrid cation-exchange membranes according to claim 1 and 2, the said chemical formulation that contains the monomer A of benzene sulfonic acid sodium salt group is CH
2=CH (R1) C
6H
3SO
3Na, R1 are H atom, halogen atom or the alkyl that contains 1-2 carbon atom; The said monomers B that contains the alkoxyl silicone group is methacrylic acid-trimethoxy silicon propyl ester, VTES, vinyltrimethoxy silane, allyltrimethoxysilanis or triethoxysilicane styrene; Said initator D is dibenzoyl peroxide or azodiisobutyronitrile.
4. method for preparing organic-inorganic hybrid cation-exchange membranes, said method comprises:
Each described coating liquid in the claim 1 to 3 is coated on the matrix.
5. method for preparing organic-inorganic hybrid cation-exchange membranes, said method comprises the steps:
(1) preparation of many silicon crosslinking agent:
In molar ratio for containing the monomer A of benzene sulfonic acid sodium salt group: the monomers B that contains the alkoxyl silicone group: solvent C: the proportion relation of initator D=1: 1-2.34: 38.5-87.7: 0.020-0.036; Monomer A, monomers B, solvent C and initator D are mixed and reaction; Remove the solvent C of 60-75% afterwards, make many silicon cross-linking agent solution.
(2) preparation of coating liquid: polyvinyl alcohol (PVA) is dissolved in the water to form mass concentration be the solution of 5%-10%; The temperature range of control PVA solution is 35-75 ℃; Under stirring condition; With mass ratio is many silicon crosslinking agent: PVA=0.75-1.34: 1 drips many silicon crosslinking agent in PVA solution, stirs simultaneously and reacts and make coating liquid; And
(3) preparation of hybrid cation-exchange membranes: the coating liquid that step (2) is made is coated on the matrix; Coating liquid being dried on matrix forming uniform and stable gel layer is diaphragm; Then diaphragm is heat-treated, can obtain organic-inorganic hybrid cation-exchange membranes of the present invention.
6. according to claim 4 or 5 described preparation methods, wherein said matrix is glass plate, aluminium foil, polyfluortetraethylene plate, polyvinyl chloride panel, porous ceramics piece or nonwoven.
7. according to claim 4 or 5 described preparation methods, the method that wherein coating liquid is coated on the matrix is knifing, hydrostomia, dipping or coating.
8. preparation method according to claim 5 wherein in the preparation of the coating liquid of (2), comprises that the dropping time that in PVA solution, drips many silicon crosslinking agent is 0.5-2 hour, under 35-75 ℃ of temperature conditions stirring reaction 12-36 hour.
9. preparation method according to claim 5, described heat treatment is: (1) places the diaphragm of ribbon matrix under the temperature 60-80 ℃ condition and is warming up to temperature 120-140 ℃ with 10-20 ℃/hour speed, is incubated 1-8 hour; Or (2) scrape diaphragm from matrix, and diaphragm is placed under the temperature 60-80 ℃ condition and is warming up to temperature 130-140 ℃ with 5-15 ℃/hour speed, is incubated 1-4 hour.
10. organic-inorganic hybrid cation-exchange membranes, it uses to film on matrix according to each described coating liquid in the claim 1 to 3 and makes, or uses and be prepared from according to each described method among the claim 4-9.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102908915A (en) * | 2012-10-31 | 2013-02-06 | 中国科学技术大学 | Diffusion and dialysis membrane for alkali recovery as well as preparation method and application of same |
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| CN103752177A (en) * | 2013-12-17 | 2014-04-30 | 中国科学技术大学 | Method for improving separation performance of crystalline polymer based cation exchange membrane on multivalent cation |
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| CN103864977A (en) * | 2014-03-19 | 2014-06-18 | 中国科学技术大学 | Preparation method of polysilicon cross-linking agent and special anionic membrane for diffusion dialysis of polysilicon cross-linking agent |
| CN108452688A (en) * | 2018-04-13 | 2018-08-28 | 重庆海通环保科技有限公司 | A kind of novel reverse osmosis membrane and preparation method thereof |
| CN114192000A (en) * | 2020-09-17 | 2022-03-18 | 中国石油化工股份有限公司 | Ion exchange membrane and preparation method and application thereof |
| CN114192000B (en) * | 2020-09-17 | 2024-03-26 | 中国石油化工股份有限公司 | Ion exchange membrane and preparation method and application thereof |
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