CN1287888C - Prepn process of negatively charged hybridized inorganic-organic membrane - Google Patents
Prepn process of negatively charged hybridized inorganic-organic membrane Download PDFInfo
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Abstract
The present invention relates to a preparation method for negatively charged hybrid inorganic-organic membranes, which is characterized in that alkoxy silane whose chemical formula is [R<1>(SH)R<2>][p]SiX<4-p> and molecule chains comprise sulfhydryl groups, or silane halide is used as a raw material; after the raw material is dissolved in a solvent, water and a catalyst are added in the solution; the solution generates a reaction during stir; the obtained collosol is used for coating a film on a basal body, and the obtained film is dried at a room temperature; then the temperature is raised to 80 to 200 DEG C, and the temperature is kept for 1 to 12 hours under a normal pressure condition or a pressure reduction condition; the product is immersed in a water solution of oxydants and is kept for 12 to 50 hours at 20 to 80 DEG C, and the corresponding negatively charged hybrid inorganic-organic membrane is obtained. The method for preparing hybrid membranes in the present invention has the advantages of simple preparation procedure and good compatibility of the inorganic and organic constituent in the hybrid membranes.
Description
Technical field:
The invention belongs to the membrane technology field, be specifically related to adopt sol gel reaction and oxidation reaction to prepare bear electricity inorganic-organic hybridization film.
Background technology:
Because inorganic material has extraordinary chemistry and heat endurance, at the end of the seventies, the research that inorganic material is applied to film begins to cause people's extensive concern.But a very important defective of inoranic membrane is it is difficult to negative electrical charge on the lotus, so be easy to be subjected to the pollution of electronegative colloid, tannin and large biological molecule in the feed liquid and make membrane flux decline, shortening in service life at liquid separation process (micro-filtration, ultrafiltration, nanofiltration).Though the film of organic material preparation is charged easily, mechanical strength is bad, poor chemical stability, scarcely high temperature resistant, soda acid and organic solvent etc.In order to remedy the deficiency of existing membrane material characteristic, existing researcher attempts organic material is easy to charged advantages in inorganic material, prepares charged inorganic-organic hybridization material or film.
U.S. Pat 6,201,051 has reported polyfunctional group organosilicon or B, Al, Si, Sn, Ti, the sol gel reaction product of the alkoxide of Zr mixes with electrically conductive organic polymer, or B, Al, In, Si, Sn, Ti, Zr, oxide mix with electrically conductive organic polymer, obtain charged inorganic-organic hybridization material, this material can be used as coating.But because this method adopts the mechanical blending step, do not carry out chemical crosslinking, do not have strong chemical b ` between inorganic component and the organic charged component in the system, compatibility is relatively poor relatively.
U.S. Pat 5,371,154 have reported that structure is Y
3Si-X-SiY
3Compound (wherein X is the organic group that contains groups such as penylene, naphthalene, anthracene, benzhydryl, aryl, Y is alkoxy grp or halogen atom) sol gel reaction, generation contains the polysiloxanes of organic abutment, this polysiloxanes organic component X sulfonation or carboxylation under the effect of the reagent such as mixed aqueous solution of chlorosulfonic acid, sulfonic acid, sulfur trioxide or bromine and potassium hydroxide obtain can be used as the charged hybrid of solid acid catalyst.But the raw materials used Y of this method
3Si-X-SiY
3Preparation is difficulty comparatively, and highly acid that sulfonation or carboxylation step are used or strong basicity reagent can cause certain destruction to the structure of polysiloxanes, as chain rupture, reactions such as rearrangement take place.
" electrochemistry journal " (Electrochimica Acta, 1998,43 (10-11), the 1301-1306 page or leaf) reported and to contain the acidic-group alkoxy silane and contain epoxy radicals, double bond containing alkoxy silane and mix and carry out sol gel reaction, product further carries out UV-crosslinked or heat cross-linking, obtain bear electricity inorganic-organic hybridization material, the film made from this material shows that in electrochromism there is application prospect aspects such as window, battery and fuel cell.This preparation method's step is comparatively numerous and diverse, and its raw material must contain the further group of chemical crosslinking such as epoxy or two keys, so can adopt the raw material type of this method limited.
Summary of the invention:
The present invention proposes a kind of method of utilizing sol gel reaction and oxidation reaction to prepare bear electricity inorganic-organic hybridization film, to overcome the above-mentioned defective of prior art.
The preparation method of bear of the present invention electricity inorganic-organic hybridization film is characterised in that alkoxy silane or the halosilanes to contain sulfydryl in the strand is raw material, be dissolved in the solvent after, add entry and catalyst, at 10-60 ℃ of stirring reaction; The mol ratio that above-mentioned each component is suitable is a silane: solvent: water: catalyst=1: 3-15: 3-10: 0.001-0.01;
The colloidal sol of gained is filmed on inorganic matrix; Diaphragm is dried under the environment of room temperature, relative humidity 60-90% and forms uniform and stable gel layer; Be warmed up to 80-200 ℃ with 5-20 ℃/hour speed from room temperature again, insulation is 1-12 hour under normal pressure or the reduced pressure; At last product is carried out oxidation reaction, obtain bear electricity inorganic-organic hybridization film;
Contain the alkoxy silane or the halosilanes of sulfydryl in the described strand, its chemical formula can be expressed as [R
1(SH) R
2]
pSiX
4-p, R in the formula
1For containing the alkyl or aryl of 0-10 carbon, R
2For containing the alkyl or aryl of 1-10 carbon; X is the alkoxy grp or the halogen of 1-5 carbon, and halogen refers generally to Cl; The value of P is 1-3;
Described product is carried out oxidation reaction, be meant: product is immersed in the aqueous solution of oxidant of 1-20% of pH=4-7, kept 12-50 hour at 20-80 ℃; Described oxidant comprises hydrogen peroxide, potassium permanganate, potassium bichromate or hypochlorous acid.
Described solvent species need not special qualification, methyl alcohol, ethanol, acetone, N, dinethylformamide, N, N-dimethylacetylamide, carbon tetrachloride, chloroform, benzene or the toluene of comprising commonly used.
Described catalyst comprises hydrochloric acid, sulfuric acid, trifluoroacetic acid, NaOH, ammonium chloride or ammonium fluoride.
Described inorganic matrix comprises Al
2O
3Porous ceramics, Al
2O
3Micro-filtration or milipore filter, silica or titanium dioxide.
Described filming comprises knifing, sprinkling, dipping, flows or rotates coating.
The present invention is a raw material with alkoxy silane or the halosilanes that contains sulfydryl in the strand first, earlier through sol gel reaction, carry out oxidation reaction again and make bear electricity inorganic-organic hybridization membrane material.With U.S. Pat 6,201,051 takes inorganic and organic principle are carried out the charged inorganic-organic hybridization material compared of the step preparation of mechanical blending, links by chemical bond with inorganic silicon oxide components and organic principle in the hybridized film material of the inventive method preparation, and compatibility is better; With U.S. Pat 5,371,154 adopt the charged hybrid material of highly acid reagent preparation such as chlorosulfonic acid, sulfonic acid to compare, and the oxidation step that the inventive method adopts is less to the destruction of polysiloxane structure; With " electrochemistry journal " (ElectrochimicaActa, 1998,43 (10-11), the 1301-1306 page or leaf) Bao Dao employing ultraviolet or heat cross-linking prepare charged hybridized film material compared, the present invention's coating on inorganic matrix makes bear electricity hybridized film, need not to adopt ultraviolet or heat cross-linking step, simplified the preparation process of charged membrane.
The specific embodiment:
Further describe the preparation method of bear electricity hybridized film of the present invention by the following examples.
Embodiment 1:
Get mercaptopropyl trimethoxysilane, be dissolved in the ethanol, stir adding deionized water and 0.01mol/L hydrochloric acid down, its mol ratio is a silane: ethanol: water: hydrochloric acid=1: 5: 3: 0.001; Continue to stir 30 minutes at 25 ℃, the colloidal sol that obtains is poured on the glass surface ware, get a diameter 5cm, surperficial average pore size is that the alundum (Al sheet of 0.2 μ soaked in this colloidal sol 10 seconds, after the upset, in room temperature, air humidity is 80% time placement one day, put into baking oven then, the speed with 10 ℃/h under the normal pressure is warming up to 130 ℃, keeps 3 hours, naturally cool to room temperature again, obtaining the top layer is flaxen diaphragm.This diaphragm at 45 ℃, was soaked in 3% aqueous hydrogen peroxide solution of pH=4-7 24 hours, and washing is dry, the hybridized film once that obtained dip-coating.
Measure the diaphragm cation exchange capacity with the method for routine, the streaming potential under pure water flux and the different pH value environment, and estimate the average pore size of film according to pure water flux.
Diaphragm is cleaned, after the drying, repeats above-mentioned dip-coating, and dry heat is handled and the step of oxidation, obtains the hybridized film of dip-coating secondary.After this diaphragm performance measurement, by identical step dip-coating three times, four times, all carry out the mensuration of performance at every turn, and with the measurement result (number of times of filming is designated as 0) of the alundum (Al sheet of 0.2 μ relatively.
Table 1 has provided cation exchange capacity, the flux of hybridized film and 0.2 μ alundum (Al supporter and the average pore size of being estimated by flux:
| The number of times of filming | 0 | 1 | 2 | 3 | 4 |
| Cation exchange capacity (* 10 2meq/cm -2) | 0.74 | 1.37 | 1.26 | 1.89 | 2.26 |
| Flux (L/ (hm 2bar) | 1800 | 390 | 119 | 96 | 23 |
| Average pore size (μ m) | 0.22 | 0.10 | 0.056 | 0.051 | 0.025 |
Table 2 has provided the streaming potential of hybridized film and 0.2 μ alundum (Al supporter:
From table 1 and table 2 as can be known, the film that dip-coating is 1-4 time all has certain cation exchange capacity, and in the pH scope of being investigated, streaming potential all is a negative value, does not have the charge conversion point.Illustrate that the film that makes is all the bear electrolemma.
Scrape a little powder from the film surface of dip-coating four times, carry out heat after drying dewaters and analyze and infrared test.Heat the analysis showed that powder in blanket of nitrogen, and 250 ℃ of beginnings are weightless, and 390 ℃ of weightlessness reach maximum.1100cm in the infrared spectrum
-1Near the strong characteristic peak of Si-O-Si, 2910cm are arranged
-1Near methylene-CH absworption peak is arranged.This film that shows preparation contains alkyl, and inorganic Si-O-Si chain exists in a large number simultaneously, is the inorganic-organic hybridization thing.
The above analysis result, the diaphragm that obtains of present embodiment is the inorganic-organic hybridization film of bear electricity as can be known, and compares (serviceability temperature generally is lower than 80 ℃) with organic charged membrane, and higher heat endurance is arranged.According to the average pore size of the film that estimates, the film that present embodiment obtains can be used for micro-filtration and ultrafiltration field simultaneously.
Embodiment 2:
Get mercaptopropyl trimethoxysilane, be dissolved in the ethanol, stir adding deionized water and 0.01mol/L trifluoroacetic acid down, its mol ratio is a silane: ethanol: water: trifluoroacetic acid=1: 7: 3: 0.001.Prepare hybridized film by embodiment 1 identical step, measure the cation exchange capacity of film, flux and streaming potential, and according to flux estimation film average pore size.
The average pore size that table 3 has provided hybridized film cation exchange capacity, flux and estimated by flux:
| The number of times of filming | 1 | 2 | 3 | 4 |
| Cation exchange capacity (* 10 2meq/cm -2) | 1.11 | 1.3 | 1.73 | 2.19 |
| Flux (L/ (hm 2bar) | 23 | 17 | 2.1 | 0.23 |
| Average pore size (μ m) | 0.025 | 0.021 | 0.007 | 0.002 |
Table 4 is the hybridized film streaming potential:
Through above-mentioned analysis as can be known, the diaphragm that present embodiment obtains has certain cation exchange capacity, and in the pH scope of being investigated, except that other, streaming potential all is a negative value, so be all the bear electrolemma.
In conjunction with the embodiments in 1 to the infrared analysis result of film, the diaphragm that obtains of present embodiment is the inorganic-organic hybridization film of bear electricity as can be known, and along with the increase of the number of times of filming, water flux successively decreases, according to the average pore size of the film that estimates, the film that present embodiment obtains can be used for ultrafiltration and nanofiltration field.
Embodiment 3:
Get mercaptopropyl trimethoxysilane, be dissolved in the ethanol, stir adding deionized water and 0.01mol/L trifluoroacetic acid down, its mol ratio is a silane: ethanol: water: trifluoroacetic acid=1: 9: 3: 0.001.Prepare hybridized film by embodiment 1 identical step, measure the cation exchange capacity of film, flux and streaming potential, and according to flux estimation film average pore size.
The average pore size that table 5 has provided hybridized film cation exchange capacity, flux and estimated by flux:
| The number of times of filming | 1 | 2 | 3 | 4 |
| Cation exchange capacity (* 10 2meq/cm -2) | 1.03 | 1.32 | 1.73 | 2.05 |
| Flux (L/ (hm 2bar) | 0.61 | 0.38 | 0.23 | 0.046 |
| Average pore size (μ m) | 0.004 | 0.003 | 0.002 | 0.001 |
Table 6 is the hybridized film streaming potential:
Through above-mentioned analysis as can be known, the diaphragm that present embodiment obtains has certain cation exchange capacity, and in the pH scope of being investigated, except that other, streaming potential all is a negative value, so be all the bear electrolemma.
In conjunction with the embodiments in 1 to the infrared analysis result of film, the diaphragm that obtains of present embodiment is the inorganic-organic hybridization film of bear electricity as can be known.And along with the increase of the number of times of filming, water flux successively decreases, and according to the average pore size of the film that estimates, the film that present embodiment obtains can be used for ultrafiltration and nanofiltration field.
Embodiment 4:
Get the mercapto propyltrichlorosilan, be dissolved in the ethanol, stir adding deionized water and 0.01mol/L trifluoroacetic acid down, its mol ratio is a silane: ethanol: water: trifluoroacetic acid=1: 11: 3: 0.001.Prepare hybridized film by embodiment 1 identical step, measure the cation exchange capacity of film, flux and streaming potential, and according to flux estimation film average pore size.
The average pore size that table 7 has provided hybridized film cation exchange capacity, flux and estimated by flux:
| The number of times of filming | 1 | 2 | 3 | 4 |
| Cation exchange capacity (* 10 2meq/cm -2) | 0.97 | 1.15 | 1.87 | 1.79 |
| Flux (L/ (hm 2bar) | 1.53 | 0.10 | 0.051 | 0.062 |
| Average pore size (μ m) | 0.006 | 0.002 | 0.001 | 0.001 |
Table 8 is the hybridized film streaming potential:
Through above-mentioned analysis as can be known, the diaphragm that present embodiment obtains has certain cation exchange capacity, and in the pH scope of being investigated, except that other, streaming potential all is a negative value, so be all the bear electrolemma.
In conjunction with the embodiments in 1 to the infrared analysis result of film, the diaphragm that obtains of present embodiment is the inorganic-organic hybridization film of bear electricity as can be known.And along with the increase of the number of times of filming, water flux successively decreases, and according to the average pore size of the film that estimates, the film that present embodiment obtains can be used for ultrafiltration and nanofiltration field.
Embodiment 5:
Employing is equipped with the magneton agitator, is had the 250ml four-necked bottle reactor of nitrogen inlet and condenser pipe, add 21.3g (0.10mol) 3-methyl chloride propyl group dimethoxy silane, 50ml absolute ethyl alcohol and 0.1g KBr, be added dropwise to 7.6g (0.10mol) thiocarbamide under stirring, be warming up to 85 ℃, stirring reaction 24 hours.After the question response liquid cooling but, stop logical nitrogen, stir down and feed ammonia, separate out white precipitate from air intake.Filter, fractionation filtrate obtains a kind of flaxen liquid, i.e. 3-methyl mercaptopropyl trimethoxysilane; The productive rate of above-mentioned reaction is 60%.
Get above-mentioned synthetic 3-methyl mercaptopropyl trimethoxysilane, be dissolved in the ethanol, stir adding deionized water and 0.01mol/L ammonium fluoride down, its mol ratio is a silane: ethanol: water: ammonium fluoride=1: 9: 7: 0.006.40 ℃ of stirring reactions 0.5 hour, pour into then on the glass surface ware, drying at room temperature was warmed up to 100 ℃ with 20 ℃/hour speed after 12 hours, reduced pressure (5mmHg) insulation 5 hours; Product soaked 48 hours in 10% aqueous hydrogen peroxide solution of pH=4-7 at 60 ℃; 120 ℃ of dryings of product dewater, and obtain faint yellow solid.
Through infrared spectrum analysis, product 2570cm
-1The characteristic peak of sulfydryl disappears, 1100cm
-1Near have-SO
3The characteristic peak of H and Si-O-Si, 2970cm
-1And 1370cm
-1Near can observe methyl absworption peak ,～2850cm
-1,～1450cm
-1Methylene-CH absworption peak is obvious.
Through above-mentioned analysis as can be known, contain sulfonic group and alkyl in the present embodiment product, inorganic Si-O-Si chain exists in a large number simultaneously, is sulfonic acid type bear electricity inorganic-organic hybridization thing.
Embodiment 6:
Get the 3-methyl mercaptopropyl trimethoxysilane that embodiment 5 synthesizes, be dissolved in the ethanol, stir adding deionized water down, the 0.01mol/L ammonium fluoride, its mol ratio is a silane: ethanol: water: ammonium fluoride=1: 9: 5: 0.006.40 ℃ of stirring reactions 20 minutes, the colloidal sol that obtains is coated on the titanium dioxide silicon chip, and rotation forms uniform rete.Room temperature, air humidity are to place one day for 70% time, put into baking oven then, are warming up to 140 ℃ with the speed of 15 ℃/h, keep 5 hours; Product soaked 24 hours in the 10% hypochloric acid water solution of pH=4-7 at 40 ℃, and washing repeats twice above-mentioned dip-coating, dry heat processing and oxidation step again after 120 ℃ of dryings, obtain being coated with three times hybridized film.
Measuring the diaphragm cation exchange capacity is 2.01 * 10
-2Meq/cm
-2, institute thinks the bear electrolemma.
Scrape a little powder from the film surface, carry out infrared test after drying dewaters.Through infrared spectrum analysis, this powder 1100cm
-1Near the strong characteristic peak of Si-O-Si, 2900cm are arranged
-1And 1400cm
-1Near methyl and methylene absworption peak are arranged.This film that shows preparation contains alkyl, and inorganic Si-O-Si chain exists in a large number simultaneously, is the inorganic-organic hybridization thing.
The above analysis as can be known, the diaphragm that present embodiment obtains is the inorganic-organic hybridization film of bear electricity.
Embodiment 7:
Device similarly to Example 5 and operating process, replace 3-methyl chloride propyl trimethoxy silicane with right-chloromethyl phenyl triethoxysilane, thiocarbamide with 1: 1 mol ratio under 85 ℃ reacts, feed ammonia then, filter, obtain right-mercapto ethylphenyl triethoxysilane after the fractionation, productive rate is 45%.
Get above-mentioned synthetic right-thiopurine methyltransferase phenyl triethoxysilane, be dissolved in the ethanol, stir adding deionized water and 0.01mol/L ammonium fluoride down, its mol ratio is a silane: ethanol: water: ammonium fluoride=1: 7: 4: 0.006.40 ℃ of stirring reactions 1 hour, it is poured on the glass surface ware then, get a diameter 5cm, the surface average pore size is that the alundum (Al sheet of 0.2 μ soaked in this colloidal sol 10 seconds, after the upset, room temperature, air humidity are 80% time placement one day, put into baking oven then, speed with 15 ℃/h is warming up to 150 ℃, keeps 5 hours; Product soaked 24 hours in 10% potassium dichromate aqueous solution of pH=4-7 at 40 ℃, and washing repeats twice above-mentioned dip-coating, dry heat processing and oxidation step again after 120 ℃ of dryings, obtain being coated with three times hybridized film.
Measuring the diaphragm cation exchange capacity is 1.89 * 10
-2Meq/cm
-2, PH=1-8 scope interior diaphragm streaming potential all is a negative value, institute thinks the bear electrolemma.The pure water flux of measuring diaphragm is 0.042L/ (hm
2Bar), average pore size is about 0.001 μ m.
Scrape powder from the film surface, through infrared spectrum analysis, powder 1100cm
-1Near the characteristic peak of Si-O-Si, 3070cm are arranged
-1And 2870cm
-1Near be respectively phenyl ring and methylene-the CH absworption peak.This shows that the film of preparation contains aryl and alkyl, and inorganic Si-O-Si chain exists in a large number simultaneously, is the inorganic-organic hybridization thing.
The above analysis as can be known, the diaphragm that present embodiment obtains is the inorganic-organic hybridization film of bear electricity.
Claims (2)
1, the preparation method of a kind of bear electricity inorganic-organic hybridization film is characterised in that alkoxy silane or the halosilanes to contain sulfydryl in the strand is raw material, be dissolved in the solvent after, add entry and catalyst, at 10-60 ℃ of stirring reaction, obtain colloidal sol; The mol ratio that above-mentioned each component is suitable is a silane: solvent: water: catalyst=1: 3-15: 3-10: 0.001-0.01; The colloidal sol of gained is filmed on inorganic matrix; Diaphragm is to be dried under the environment of 60-90% to form uniform and stable gel layer in room temperature, relative humidity; Be warmed up to 80-200 ℃ with 5-20 ℃/hour speed from room temperature again, insulation is 1-12 hour under normal pressure or the reduced pressure; At last product is carried out oxidation reaction, that is: product is immersed in the aqueous solution of oxidant of 1-20% of pH=4-7, kept 12-50 hour at 20-80 ℃;
Contain the alkoxy silane or the halosilanes of sulfydryl in the described strand, its chemical formula can be expressed as [R
1(SH) R
2]
PSiX
4-p, R in the formula
1For containing the alkyl or aryl of 0-10 carbon, R
2For containing the alkyl or aryl of 1-10 carbon; X is the alkoxy grp or the halogen of 1-5 carbon; The value of P is 1-3;
Described catalyst is hydrochloric acid, sulfuric acid, trifluoroacetic acid, NaOH, ammonium chloride or ammonium fluoride;
Described inorganic matrix is Al
2O
3Porous ceramics, Al
2O
3Micro-filtration or milipore filter, silica or titanium dioxide;
Described coating method is knifing, sprinkling, dipping, flows or the rotation coating;
Described oxidant is hydrogen peroxide, potassium permanganate, potassium bichromate or hypochlorous acid.
2, according to claim 1 the bear electricity inorganic-preparation method of hybrid films, be characterised in that described halogen is Cl.
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| CN100479905C (en) * | 2005-05-21 | 2009-04-22 | 中国科学技术大学 | A hybridized amphion membrane containing different acid groups and method for preparing the same |
| CN1305553C (en) * | 2005-06-22 | 2007-03-21 | 南京工业大学 | Process for preparing organic and inorganic composite film by autoassembling tech |
| US8277661B2 (en) * | 2006-01-16 | 2012-10-02 | Stichting Energieonderzoek Centrum Nederland | Microporous molecular separation membrane with high hydrothermal stability |
| CN101091878B (en) * | 2007-04-15 | 2012-12-12 | 合肥学院 | Membrane material of inorganic - organic hybrid pair of amphoteric ion, and preparation method |
| CN101113207B (en) * | 2007-06-27 | 2011-05-18 | 中国科学技术大学 | Preparation method of sol-gel ultraviolet/heat cross-linking of hybridized anion exchange membrane |
| US7892435B2 (en) * | 2008-05-21 | 2011-02-22 | Honeywell International Inc. | System and method for recycling using nanoceramics |
| CN102029116A (en) * | 2010-10-27 | 2011-04-27 | 合肥学院 | Preparation method of polyvinyl alcohol pervaporation hybrid membrane |
| CN103992505B (en) * | 2014-05-26 | 2016-11-23 | 常州大学 | A kind of hydrophilic improving polypropylene lithium ion battery separator and the method for heat stability |
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