CN104174309A - Method of preparing zwitterionic membrane based on amphoteric silicon copolymer - Google Patents
Method of preparing zwitterionic membrane based on amphoteric silicon copolymer Download PDFInfo
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Abstract
The invention discloses a method of preparing a zwitterionic membrane based on amphoteric silicon copolymer. The method comprises the following steps of selecting a monomer A containing a double bond and methyl halide, a monomer B containing a carboxyl, anhydride or sulfurous acid group and a monomer C containing a double bond and a silicon alkoxy group, mixing the three monomers, a solvent and an initiator, carrying out free radical copolymerization, and carrying out rotary evaporation concentration to obtain a silicon copolymer solution; and treating the silicon copolymer by two ammoniation modes, wherein one mode comprises the following steps of carrying out ammoniation on the silicon copolymer, and then mixing the silicon copolymer after ammoniation with polyvinyl alcohol (PVA), i.e. dropwise adding the silicon copolymer solution in a trimethylamine organic solution, then carrying out sol-gel reaction on the mixture and PVA, and carrying out heat treatment to form the zwitterionic membrane; and the other mode comprises the following steps of mixing the silicon copolymer and PVA, and then carrying out ammoniation on the mixture, i.e. directly dropwise adding the silicon copolymer solution in the PVA solution, then carrying out sol-gel reaction and heat treatment to form a membrane, selectively soaking the membrane with a trimethylamine aqueous solution, and then carrying out quaternization to obtain the zwitterionic membrane.
Description
Technical field
The invention belongs to film manufacturing technology field, relate to a kind of method of preparing amphion film based on the many siliceous copolymers of both sexes, be specially by colloidal sol～gel method and prepare amphion film.
Background technology
Ionic membrane is a kind of functional high molecule material, and film contains macromolecular scaffold and ion-exchange group, and ion-exchange group is divided into cation exchange group (～SO3～and～COOH) and anion exchange groups (～N+R3).In conventional cation-exchange membrane (abbreviation anode membrane), only contain cation exchange group, in conventional anion-exchange membrane (abbreviation cavity block), only contain anion exchange groups.If hold concurrently and be called amphion film containing two kinds of groups in film, amphion film in preparation process, exist complex process, the extent of reaction low, be difficult to the defects such as moulding.
< < membrane science magazine > > (Journal of Membrane Science, 376,2011,233 – 240) reported the copolymer of first preparing a kind of containing～COOH group, copolymer and polyvinyl alcohol (PVA) carry out colloidal sol～gel reaction, generate coating liquid, obtain organic～inorganic hybridization anode membrane after heat treatment, stability and the diffusion dialysis of film are respond well.But in copolymer and film, only contain single cation exchange group～COOH, and because the polarity of～COOH group is lower, cause copolymer and PVA compatibility not good, so in coating liquid, contain more precipitation, film heterogeneity.
Chinese Patent Application No. CN201010107733.7 announced a kind of organic～preparation method of inorganic hybridization anode membrane, first prepare a kind of holding concurrently containing～Si (OR)
3copolymer with～COOH (or acid anhydrides) group, after copolymer and sulfonated poly (phenylene oxide) blend, carries out original position colloidal sol～gel reaction film forming.The physical stability of film is good, stable electrical properties, but due in sulfonated poly (phenylene oxide) containing～OH base, cause lacking between sulfonated poly (phenylene oxide) and copolymer covalently cross-linked, the homogeneity of film is not enough, not enough at the application performance in diffusion dialysis field.
The preparation method of Chinese patent CN102658036A discloses a class organic～inorganic hybridization anode membrane.First prepare a kind of contain～Si (OR) that holds concurrently
3with～SO
3many silicon crosslinking agent of Na group, many silicon crosslinking agent and PVA carry out colloidal sol～gel reaction, generate coating liquid, obtain hydridization anode membrane after heat treatment.Anode membrane transparent and homogeneous, satisfactory mechanical property, stability prepared by the method are high, can be applicable to alkali and reclaim field.But only contain single ion-exchange group in copolymer and film, be～SO
3na, only has cation exchange feature, limited in application performances such as ionic adsorption and diffusion dialysis.
< < deleterious material magazine > > (Journal of Hazardous Materials, 173,2010,438 – 444) reported and utilized the little molecule silane of the little molecule that contains bisgallic acid anhydride group and contain～NH～group to carry out chemical reaction, utilization～NH～group is opened cyclic acid anhydride group, product carries out quaterisation with bromoethane again, obtains Amphoteric Materials.Material prepared by the method can be applicable to adsorb Pb
2+ion.But owing to adopting little molecule to carry out chemical reaction in preparation process always ,～NH～, the activity of acid anhydrides and bromoethane is low, the extent of reaction is not high, makes product lack pliability and film forming ability, can only form the irregular material of fragility.
Summary of the invention
The present invention aims to provide the method for many siliceous copolymers of both sexes ionic membrane of a kind of cation cation exchange groups and anion exchange groups.
The present invention is achieved through the following technical solutions:
A method of preparing amphion film based on the many siliceous copolymers of both sexes, comprises following steps:
1) select a kind of monomer A that contains two keys and halomethyl, a kind of monomers B that contains carboxyl or sulfonic acid group, a kind of monomer C that contains two keys and alkoxyl silicone group;
2) mix three kinds of monomers, solvent and initators, wherein the mol ratio of monomer A and B and C is 1:0.5～8:0.5～6, the volume ratio of solvent and three kinds of monomer summations is 15～30:1, the volume ratio of initator and three kinds of monomer summations is 0.006～0.016:1, and initator is dibenzoyl peroxide (BPO) or azodiisobutyronitrile (AIBN);
3) said mixture is reacted to 12-48h under 60～80 ℃ of conditions, by rotary evaporation, remove the solvent of 60～75% volumes, make many siliceous copolymers solution;
4) under stirring condition, the mass ratio of many siliceous copolymers and polyvinyl alcohol (PVA) of take drips many siliceous copolymers in as 0.25～1.2:1 to poly-vinyl alcohol solution, wherein the mass concentration of poly-vinyl alcohol solution is 5%～10%, and temperature is 25～70 ℃, and time for adding is 0.5～2h;
5) after dropwising, continuation is at 25～70 ℃ of stirring reaction 12～36h, on matrix, film, in room temperature environment, being dried to and forming uniform and stable gel layer is diaphragm, after taking diaphragm off, heat-treat, the film obtaining after heat treatment does not soak or is immersed in mass concentration is 24～60h in 9～30% trimethylamine solution, can obtain amphion film of the present invention;
A method of preparing amphion film based on the many siliceous copolymers of both sexes, comprises following steps:
1) select a kind of monomer A that contains two keys and halomethyl, a kind of monomers B that contains carboxyl or sulfonic acid group, a kind of monomer C that contains two keys and alkoxyl silicone group;
2) mix three kinds of monomers, solvent and initators, wherein the mol ratio of monomer A and B and C is 1:0.5～8:0.5～6, the volume ratio of solvent and three kinds of monomer summations is 15～30:1, the volume ratio of initator and three kinds of monomer summations is 0.006～0.016:1, and initator is dibenzoyl peroxide (BPO) or azodiisobutyronitrile (AIBN);
3) said mixture is reacted to 12～48h under 60～80 ℃ of conditions, by rotary evaporation, remove the solvent of 60～75% volumes, make many siliceous copolymers solution;
4) take in trimethylamine and many siliceous copolymers halomethyl mol ratio splashes into many siliceous copolymers solution in trimethylamine organic solution as 3～8:1, control time for adding is that after 0.17～0.5h, blend, the mass concentration of solution is 4 – 10%, dropwise rear continuation stirring reaction 0.3 – 3h, at 0.2～2h, adding temperature is that in 25～70 ℃, the mass concentration poly-vinyl alcohol solution that is 5%～10%, wherein the mass ratio of many silicon crosslinking agent and polyvinyl alcohol is 0.25～1.2:1;
5) after adding, continue, at 25～70 ℃ of stirring reaction 12～36h, on matrix, to film, in room temperature environment, being dried to and forming uniform and stable gel layer is diaphragm, heat-treats after taking diaphragm off, can obtain amphion film of the present invention.
Described monomer A is 1-chloro-4-methyl-benzene (VBC), quaternized 1-chloro-4-methyl-benzene (QVBC), 3-bromopropene (BPE) and acrylamide;
Described monomers B is acrylic acid (AA), methacrylic acid (MA), styrene semi-annular jade pendant acid sodium, itaconic acid and maleic acid;
Described monomer C is methacrylic acid trimethoxy silane (KH～570), VTES (VTES), vinyltrimethoxy silane and allyltrimethoxysilanis (ALLMO);
Solvent of the present invention is N, N～dimethyl formamide (DNF), N～methyl pyrrolidone (NMP), toluene or chloroform;
Solvent in trimethylamine organic solution of the present invention comprises DMF or ethanol;
Matrix of the present invention is glass plate, polyfluortetraethylene plate or polyvinyl chloride panel;
Method of filming of the present invention is knifing, salivation or coating;
Heat-treating methods of the present invention is: diaphragm is placed in to 60～80 ℃ of environment of temperature and is warming up to 130～140 ℃ with the speed of 5～15 ℃/h, insulation 1～4h.
Beneficial effect of the present invention, for prepare the many siliceous copolymers of both sexes of a kind of double cation cation exchange groups and anion exchange groups by copolymerization method, after copolymer and polyhydroxylated polymer blend, can directly be introduced into two kinds of ion-exchange groups in film.Film preparation step is simple, and the film obtaining has the advantages such as uniformity is high, pliability good, Modulatory character is high.
The specific embodiment
Below in conjunction with embodiment, the present invention is described further, the following stated, only to preferred embodiment of the present invention, not the present invention is done to other forms of restriction, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed to the equivalent embodiment of equal variation.Every the present invention program's content that do not depart from,, all drops in protection scope of the present invention any simple modification made for any of the above embodiments or equivalent variations according to technical spirit of the present invention.
Embodiment 1
With hold concurrently containing-SO3Na and-the many siliceous copolymers of both sexes of N+ (CH3) 3Cl-group prepare amphion film.
Raw material preparation:
(1) dissolving of polyvinyl alcohol: polyvinyl alcohol is from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group, the degree of polymerization is 1750 ± 50, get 42.4g polyvinyl alcohol solid, be soaked in 760mL water one day, under stirring condition, then be warmed up to 102 ℃ with the programming rate of 8 ℃/h, at 2.5 hours (h) of 102 ℃ of insulations, obtain the solution of homogeneous transparent, standby after being cooled to 60 ℃, the mass concentration of solution is 5%;
(2) azodiisobutyronitrile (AIBN, Shanghai Chemical Reagent Co., Ltd., Sinopharm Group) recrystallization: 10g AIBN is dissolved in 100mL50 ℃ of ethanol, cryosel is bathed crystallisation by cooling, obtains crystallized product after suction filtration, and crystallized product is dried two days in vacuum room temperature environment.
(3) SSS comes from Shandong Zibo Xing Zhilian Chemical Co., Ltd., technical pure; Methacrylic acid～trimethoxy silicon propyl ester (KH-570) is from Tianzhang City, Anhui Province green chemical industry auxiliary agent Co., Ltd, chemical pure; All the other chemical reagent are all from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group.
Experimental technique:
1) preparation of the many siliceous copolymers of both sexes: add 180mL N to being equipped with in the round-bottomed flask of reflux condensing tube and drying tube, dinethylformamide (DMF), add again 8.25g SSS, stir after 2h, be warming up to 70 ℃, add successively 1.42mL VBC, 14.2mL KH-570 and 0.262g AIBN, stirring reaction 24h, by rotary evaporation, remove 120mL solvent DMF, obtain many siliceous copolymers solution, get the solution of certain volume, dry to constant weight, the concentration of measuring many siliceous copolymers solution is 0.25g/mL.
2) preparation of amphion film: get many siliceous copolymers of 39mL solution room temperature 0.5h and splash in the trimethylamine ethanolic solution that 36mL concentration is 1.11mol/L, in trimethylamine and many siliceous copolymers, the mol ratio of halomethyl is 8:1, while mechanical agitation, solution viscosity constantly increases, after dropwising, add 60mL polyvinyl alcohol, the mass concentration of controlling blended liquid is 7.4%, continue to stir 0.3h, solution is added dropwise in 0.2h in the 240mL poly-vinyl alcohol solution of 60 ℃, the mass ratio of copolymer and PVA is 0.83:1, in dropping process, keep stirring, after dropping finishes, continuation is at 60 ℃ of stirring reaction 18h, obtain the coating liquid of transparent and homogeneous.Coating liquid is coated on glass plate, in room temperature environment, aeration-drying is 2 days, making coating liquid on glass plate, form uniform and stable gel layer is diaphragm, from glass plate, scrape diaphragm, diaphragm is placed in to baking oven, since 60 ℃, with the speed of 10 ℃/h, is warming up to 130 ℃, and at 130 ℃ of insulation 4h, obtain amphion film of the present invention.
The above-mentioned amphion film making is tested as follows:
(1) film outward appearance: observe transparency and the homogeneity of film by digital photograph, measure the average thickness of film by slide measure.
(2) water content: operation is all at room temperature carried out, and weight of clip is m
1diaphragm, the scope of m1 is at 0.10～0.30 gram, is immersed in water after 2 days, takes out diaphragm, dries the water of membrane surface with filter paper, the gravimetric value obtaining after weighing is designated as m
2.The water content of diaphragm=(m
2-m
1) * 100%/m1.
(3) cation exchange capacity (IEC～sun): operation is all at room temperature carried out, and weight of clip is m
1diaphragm, the scope of m1 is at 0.15-0.40g, in the HCl that is 1mol/L in concentration, soak after 2 days, take out diaphragm, with distilled water immersion one day and change water 4 times in soak period, diaphragm is immersed in the KOH solution that 80mL concentration is 0.04mol/L to two days again, with phenolphthalein, makes indicator, the HCl that is 0.04mol/L by concentration carries out back titration to the KOH solution after soaking.IEC～sun=(molal quantity of the HCl that molal quantity-concentration of the KOH that concentration is 0.04mol/L is 0.04mol/L)/m1.
(4) anion-exchange capacity (IEC～the moon): operation is all at room temperature carried out, and weight of clip is m
1diaphragm, m
1scope at 0.15～0.25 gram, be immersed in 80mL1mol/L NaCl solution after 2 days, take out diaphragm, with distilled water immersion one day and change water 4 times between soak period, be finally soaked in 80mL0.5mol/L Na
2sO
4in solution 2 days; K with 0.05g/mL
2crO
4for indicator, use 0.1mol/L AgNO
3to soaking the Na of membrane sample
2sO
4solution carries out titration, until the color of solution becomes field gray from yellow, and the AgNO that record consumes
3volume V.IEC the moon=(0.1 * V)/m
1, the mmol/g of unit.
(5) water resistant swelling test: weight of clip is m
1diaphragm, m
1scope at 0.15～0.30g, be immersed in 80mL temperature and be in the water of 65 ℃, after certain interval of time, take out diaphragm, dry surperficial water, weighing weight in wet base is m
2.The sample that will wet dries to constant weight at 85 ℃, and again weighing dry weight is m
3.The swellbility of calculation sample is (m
2– m
3) * 100%/m
3, loss late is (m
1– m
3) * 100%/m
1.
(6) mechanical strength test: use Instron universal tester (Model1185), sample shear becomes dumb-bell shape, playing initial length is 25mm, under room temperature environment, rate of extension is 25mm/min.Hot strength (TS) and the elongation at break (E of record test
b).
(7) test of alkali application is reclaimed in diffusion dialysis: square of clip or circular membrane sample, and the areal extent of sample is 8～12cm2, wherein the region area for diffusion dialysis is 6.15cm
2.Membrane sample is fixed on to the pond central authorities that comprise two compartments, the volume that every compartment can add solution is 100mL, and a compartment is as diffusion side, and it is 1.2mol/L NaOH+0.50mol/L NaAlO that composition is equipped with in inside
2diffusion liquid, another pond is as dialysis side, distilled water is equipped with in inside.Before test, film soaks 1h in advance in diffusion liquid.When spreading test, the temperature of utilizing water bath device to control solution in two compartments is 20 ℃; Solution in two compartments is carried out to constant speed stirring, in order to eliminate concentration polarization effect simultaneously.Diffusion is carried out after 45min, and the solution in diffusion side and dialysis side is taken out and carries out titration.AlO
2 -concentration by adding excessive EDTA, then at 1-(2-pyridylazo)-beta naphthal) (PAN) under indicator, use CuSO
4back titration.OH-concentration is by adding excessive HCl, then under methyl orange indicator, uses Na
2cO
3back titration.
The ratio of the dialysis coefficient (U) by two kinds of compositions, can calculate a kind of composition with respect to the separation factor (S) of another kind of composition.U=M/ (At Δ C), in formula, M represents the molal quantity of transfer components, and A represents the effective area of film, and t represents that time Δ C represents the logarithmic mean concentration (mol/m between two Room
3), be defined as Δ C=(Cf
0～C
f+ C
d)/ln[C
f 0/ (C
f～C
d)].C in formula
f 0and C
frepresentative diffusion side solution is 0 and concentration when t in the time respectively, C
drepresent the concentration of dialysis side solution when time t.
Test result shows: the thickness of the film that the present embodiment is prepared is 90 μ m, and water content is 53.2%; Swellbility in 65 ℃ of water after 192h is 136.5%, and loss late is 13.6%.Film homogeneous transparent, is better than the blend film that Chinese patent CN201010107733.7 reports;
The IEC-sun of film is 1.24mmol/g, and IEC-the moon is 1.47mmol/g, and double cation cation exchange groups and anion exchange groups in film are described, shows as amphion film feature, is different from the anode membrane of patent CN102658036A report.
Mechanical strength test shows, the elongation at break of film is 21.1%, and hot strength is 26MPa.Illustrate that film has good mechanical performance, be better than the amorphous materials of Journal of Hazardous Materials (173,2010,438 – 444) report.
The test that alkali is reclaimed in diffusion dialysis shows, the alkali dialysis coefficient of film is 0.0093m/h, and separation factor is 22.1.Compare with business sulfonated poly (phenylene oxide) film (0.0029m/h, 8.2), the prepared amphion film of the present embodiment has higher dialysis coefficient and separation factor, can be applicable to alkali and reclaims field.
Comprehensive above test result, known the present embodiment has obtained the amphion film of transparent and homogeneous, and film has good water resistant swelling ability and mechanical performance, can be applicable to diffusion dialysis and reclaims alkali.
Embodiment 2
With hold concurrently containing-COOH and-the many siliceous copolymers of both sexes of N+ (CH3) 3Cl-group prepare amphion film.
The preparation of raw material:
(1) the dissolving similar embodiment 1 of PVA, but by 42.4g polyvinyl alcohol raw material soaking in 360mL water one day, the mass concentration that obtains solution was 10%;
(2) purification of AIBN is with embodiment 1, and acrylic acid and all the other chemical reagent are all from Shanghai Chemical Reagent Co., Ltd., Sinopharm Group;
(3) 1 commercially available volume trimethylamine aqueous solution is mixed with the water of 2.5 times of volumes, obtains concentration and be about 9% trimethylamine aqueous solution, then carry out following steps:
Test method:
The preparation of the many siliceous copolymers of both sexes: add 360mLDMF to being equipped with in the round-bottomed flask of reflux condensing tube and drying tube, under stirring condition, add 11mL acrylic acid, 2.84mLVBC, 4.74mLKH-570 and 0.524gAIBN, be warming up to 70 ℃ of reaction 24h, pass through rotary evaporation, remove 220mL solvent DMF, obtain many silicon cross-linking agent solution.By sampling drying weight method, get the solution of certain volume, to dry to constant weight, the concentration of measuring many silicon cross-linking agent solution is 0.12g/mL.
The preparation of amphion film: get many siliceous copolymers of 70mL solution room temperature 1h and splash in 65 ℃ of 240mL (12g) PVA solution, stir PVA solution simultaneously, after dropping finishes, continuation is at 65 ℃ of stirring reaction 24h, be coated on glass plate, under room temperature environment, aeration-drying is 2 days, until form uniform and stable gel layer on glass plate, it is diaphragm, from glass plate, scrape diaphragm, diaphragm is placed under temperature 60 C condition, then the speed with 10 ℃/h is warming up to 130 ℃, and is incubated 4h under 130 ℃ of conditions.Film is immersed in to concentration and is about in 9% trimethylamine aqueous solution one day, after taking-up, in 1 day, wash 8 times, preserve.
The various performances of film prepared by mensuration the present embodiment, comprise outward appearance, thickness, water content, IEC-sun, cloudy, anti-65 ℃ of water-soluble swollen, the diffusion dialysis NaOH separating/NaAlO of IEC-
2solution, test method is with embodiment 1.
Test result shows: the prepared amphion film outward appearance yellow of the present embodiment is smoothly transparent, and thickness is 63 μ m, and water content is 139.6%; IEC～sun is 3.63mmol/g, and IEC～the moon is 2.63mmol/g, and the swellbility in 65 ℃ of water after 24h is 268.3%, and loss late is 12.1%.Film reclaims in the process of alkali in diffusion dialysis, and alkali dialysis coefficient is 0.0274m/h, and separation factor is 8.1.Compare with business sulfonated poly (phenylene oxide) film (0.0029m/h, 8.2), the prepared cation-exchange membrane of the present embodiment has higher dialysis coefficient and similar separation factor, can be applicable to alkali and reclaims field.
Comprehensive above test result, known the present embodiment has obtained the amphion film of transparent and homogeneous, and film has good water resistant swelling ability, can be applicable to diffusion dialysis field separate and reclaims alkali.
Embodiment 3
A method of preparing amphion film based on the many siliceous copolymers of both sexes, preparation technology is with embodiment 2, just the film after heat treatment is immersed in to mass concentration and is 36h in 20% trimethylamine aqueous solution, obtains amphion film.
Test result shows: the water content of film is 155.3%; IEC-sun is 3.59mmol/g, and IEC-the moon is 0.41mmol/g, and the swellbility in 65 ℃ of water after 24h is 297.5%, and loss late is 13.2%.Compare with embodiment 2, the prepared amphion film of the present embodiment has higher anion-exchange capacity and swellbility, illustrates that film is in soaking the process of trimethylamine aqueous solution, if improve concentration and the soak time of trimethylamine, can increase the ammonium degree of film, thereby increase the hydrophily of film.
Embodiment 4 prepares the many siliceous copolymers of both sexes and amphion film with ammonium 1-chloro-4-methyl-benzene (QVBC).
The preparation of raw material: 0.2mol VBC is added dropwise in 1h in the trimethylamine ethanolic solution of 0.6mol, stirs simultaneously, after dropwising, continue stirring reaction 12h, remove ethanol and remaining trimethylamine by rotary evaporation, obtain the aqueous QVBC of thickness.The dissolving similar embodiment 1 of PVA, but by 42.4g PVA raw material soaking in 493mL water one day, obtains mass concentration and is 7.5% solution.
A kind of method of preparing amphion film based on the many siliceous copolymers of both sexes, preparation technology's similar embodiment 2, its difference is that monomer A is 0.02mol QVBC (4.23g), monomers B is 0.01mol methacrylic acid (0.861g), and monomer C is 0.04mol VTES (7.6g).Solvent is 2.1mol chloroform (170mL), and initator is 0.00042mol dibenzoyl peroxide (0.102g), and 80 ℃ of reaction 12h, remove 127.5mL chloroform by rotary evaporation.In the PVA solution that concentrate to be added dropwise in 2h to volume and to be 141mL, temperature and be 70 ℃ of mass concentrations be 7.5%, after dropwising, continuation is at 70 ℃ of stirring reaction 12h, salivation is on polyfluortetraethylene plate, aeration-drying in room temperature environment, until to form uniform and stable gel layer be diaphragm, is taken diaphragm off from tetrafluoroethene plate, and diaphragm is placed in to 80 ℃ of baking ovens of temperature, then the speed with 5 ℃/h is warming up to 140 ℃, and is incubated 1h under 140 ℃ of conditions.
Test result shows, film outward appearance even compact prepared by the present embodiment, without particle or agglomeration.The water content of film is that 45%, IEC-the moon is 0.61mmol/g, and IEC-sun is 0.32mmol/g; The dialysis coefficient of film is 0.026m/h, and separation factor is 32.5, illustrates that amphion film can be applicable to separating acid field.
Embodiment 5 prepares the many siliceous copolymers of both sexes and amphion film with 3-bromopropene (BPE) and itaconic acid.
A kind of method of preparing amphion film based on the many siliceous copolymers of both sexes, preparation technology is with embodiment 2, its difference is that monomer A is 0.1mol3-bromopropene (12.1g), monomers B is 0.1mol itaconic acid (13.1g), and monomer C is 0.05mol allyltrimethoxysilanis (8.1g).Solvent be 3.75mol 1-METHYLPYRROLIDONE (NMP) (360.8mL), initator is 0.0025mol AIBN (0.411g), 60 ℃ reaction 48h, by rotary evaporation, remove 216.5mL solvent, obtain concentrate.Get the concentrate containing 8g solute, in the PVA solution that to be added dropwise to volume and to be 640mL, temperature in 1h and be 25 ℃ of mass concentrations be 5%, after dropwising, continuation, at 25 ℃ of stirring reaction 36h, is coated on polyvinyl chloride panel, and aeration-drying under room temperature environment is until to form uniform and stable gel layer be diaphragm, from polyvinyl chloride panel, take diaphragm off, diaphragm is placed under temperature 70 C condition, and then the speed with 15 ℃/h is warming up to 130 ℃ of temperature, and is incubated 4h under 130 ℃ of conditions.It is 60h in 30% trimethylamine aqueous solution that film is immersed in to mass concentration, and after taking out, water intermittently washs until cleaning solution is neutral.
Test result shows, the water content of the prepared film of the present embodiment is that 105%, IEC-the moon is 0.11mmol/g, and IEC-sun is 0.35mmol/g.By diffusion dialysis NaOH separating/NaAlO
2dialysis coefficient be 0.0105m/h, separation factor is 14.1, illustrates that the prepared amphion film of the present embodiment can be applicable to separated alkali field.
Embodiment 6 prepares the many siliceous copolymers of both sexes and amphion film with VBC and maleic anhydride.
A kind of method of preparing amphion film based on the many siliceous copolymers of both sexes, preparation technology is with embodiment 1, its difference is that monomer A is 0.05mol VBC (7.1mL), monomers B is 0.15mol maleic anhydride (14.71g), and monomer C is 0.1mol vinyltrimethoxy silane (15.3mL).Solvent is 6mol DMF (466.6mL), initator is 0.003mol AIBN (0.493g), 70 ℃ of reaction 24h, by rotary evaporation, remove 326.6mL solvent, in the trimethylamine DMF solution that concentrate to be added dropwise in 0.17h to volume and to be 50mL, concentration be 3mol/L, after dropwising, add DMF until the mass concentration of solution is 10%, continue stirring reaction 3h.
In the PVA solution that solution to be added dropwise in 0.5h to volume and to be 400mL, temperature and be 45 ℃, mass concentration be 5%, after dropwising, continuation is at 45 ℃ of stirring reaction 24h, be coated on glass plate, aeration-drying in room temperature environment, until to form uniform and stable gel layer be diaphragm, is taken diaphragm off from glass plate, diaphragm is placed in to the baking oven of temperature 60 C, then the speed with 10 ℃/h is warming up to 130 ℃, and is incubated 4h under 130 ℃ of conditions.
The film outward appearance even compact that the present embodiment is prepared and transparent, test shows the cloudy 0.32mmol/g of being of IEC-, IEC-sun is 1.12mmol/g, illustrates and has successfully prepared amphion film.The water content of film is 105%.By diffusion dialysis NaOH separating/NaAlO
2dialysis coefficient be 0.0177m/h, separation factor is 12.3.
Embodiment 7 prepares the many siliceous copolymers of both sexes and amphion film with VBC and maleic anhydride.
A kind of method of preparing amphion film based on the many siliceous copolymers of both sexes, preparation technology is with embodiment 6, it is in 50mL, the concentration trimethylamine DMF solution that is 5mol/L that its difference is added dropwise to volume by the concentrate after rotary evaporation in 0.3h, after dropwising, add DMF until the mass concentration of solution is 4%, continue stirring reaction 2h.In the identical mode of embodiment 6, be added dropwise in PVA solution, knifing, on glass plate, obtains amphion film after super-dry and heat treatment again.
Through repeatedly repeating experiment, show, change above ingredient proportion and reaction condition, can make ammoniumization reaction more steady and even, can effectively prevent from occurring gelatin phenomenon in many siliceous copolymers of both sexes preparation process.Test shows, the character of the amphion film that the present embodiment is prepared is consistent with film character in embodiment 6.
Claims (6)
1. based on the many siliceous copolymers of both sexes, prepare a method for amphion film, it is characterized in that comprising following steps:
1) select a kind of monomer A that contains two keys and halomethyl, a kind of monomers B that contains carboxyl or sulfonic acid group, a kind of monomer C that contains two keys and alkoxyl silicone group;
2) mix three kinds of monomers, solvent and initators, wherein the mol ratio of monomer A and B and C is 1:0.5～8:0.5～6, the volume ratio of solvent and three kinds of monomer summations is 15～30:1, the volume ratio of initator and three kinds of monomer summations is 0.006～0.016:1, and initator is dibenzoyl peroxide or azodiisobutyronitrile;
3) said mixture is reacted to 12～48h under 60～80 ℃ of conditions, by rotary evaporation, remove the solvent of 60～75% volumes, make many siliceous copolymers solution;
4) under stirring condition, take many siliceous copolymers and polyvinyl alcohol mass ratio drips many siliceous copolymers in the poly-vinyl alcohol solution that 0.25～1.2 ﹕ 1 is 5%～10% to mass concentration, keeping poly-vinyl alcohol solution temperature is 25～70 ℃, and time for adding is 0.2～2h;
5) after dropwising, continuation is at 25～70 ℃ of stirring reaction 12～36h, on matrix, film, in room temperature environment, being dried to and forming uniform and stable gel layer is diaphragm, after taking diaphragm off, heat-treat, the film obtaining after heat treatment does not soak or is immersed in mass concentration is 24～60h in 9～30% trimethylamine solution, can obtain amphion film of the present invention.
2. based on the many siliceous copolymers of both sexes, prepare a method for amphion film, it is characterized in that comprising following steps:
1) select a kind of monomer A that contains two keys and halomethyl, a kind of monomers B that contains carboxyl or sulfonic acid group, a kind of monomer C that contains two keys and alkoxyl silicone group;
2) mix three kinds of monomers, solvent and initators, wherein the mol ratio of monomer A and B and C is 1:0.5～8:0.5～6, the volume ratio of solvent and three kinds of monomer summations is 15～30:1, the volume ratio of initator and three kinds of monomer summations is 0.006～0.016:1, and initator is dibenzoyl peroxide or azodiisobutyronitrile;
3) said mixture is reacted to 12～48h under 60～80 ℃ of conditions, by rotary evaporation, remove the solvent of 60～75% volumes, make many siliceous copolymers solution;
4) take in trimethylamine and many siliceous copolymers halomethyl mol ratio splashes in trimethylamine organic solution or N by many siliceous copolymers solution as 3～8:1, in dinethylformamide solution or trimethylamine or ethanolic solution, control time for adding is that after 0.17～0.5h, blend, the mass concentration of solution is 4～10%, dropwise rear continuation stirring reaction 0.3～3h, at 0.2～2h, adding temperature is that in 25～70 ℃, the mass concentration poly-vinyl alcohol solution that is 5%～10%, wherein the mass ratio of many silicon crosslinking agent and polyvinyl alcohol is 0.25～1.2 ﹕ 1;
5) after adding, continue, at 25～70 ℃ of stirring reaction 12～36h, on matrix, to film, in room temperature environment, being dried to and forming uniform and stable gel layer is diaphragm, heat-treats after taking diaphragm off, can obtain amphion film of the present invention.
3. a kind of method of preparing amphion film based on the many siliceous copolymers of both sexes according to claim 1 and 2, is characterized in that:
Described monomer A is a kind of in 1-chloro-4-methyl-benzene, quaternized 1-chloro-4-methyl-benzene, 3-bromopropene or acrylamide;
Described monomers B is a kind of in acrylic acid, methacrylic acid, styrene semi-annular jade pendant acid sodium, itaconic acid or maleic acid;
Described monomer C is a kind of in methacrylic acid trimethoxy silane, VTES, vinyltrimethoxy silane, allyltrimethoxysilanis or triethoxysilicane styrene.
4. a kind of method of preparing amphion film based on the many siliceous copolymers of both sexes according to claim 1 and 2, is characterized in that: the solvent described in step (2) is a kind of in DMF, 1-METHYLPYRROLIDONE, toluene or chloroform.
5. a kind of method of preparing amphion film based on the many siliceous copolymers of both sexes according to claim 2, is characterized in that: the matrix described in step (5) is glass plate, polyfluortetraethylene plate or polyvinyl chloride panel.
6. a kind of method of preparing amphion film based on the many siliceous copolymers of both sexes according to claim 1 and 2, it is characterized in that: the heat treatment described in step (5) is for diaphragm being placed in to 60～80 ℃ of environment of temperature and being warming up to 130～140 ℃ with the speed of 5～15 ℃/h, and at 130～140 ℃ of insulation 1-4h.
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