CN1579604A - Positive charged organic-inorganic hybrid membrane preparing method - Google Patents
Positive charged organic-inorganic hybrid membrane preparing method Download PDFInfo
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Abstract
The invention relates to an approach of producing positive charge organic-inorganic hybridization membrane. Its characters are as follows: making alkoxy silane and macromolecular compound containing ester group or epoxy lateral group or end group amine analyzing, alcoholysis or ring opening reaction, conducting quaterisation on production to get positive charge reaction sol-gel precursor, conducting sol-gel reaction on the precursor and finally getting positive charge organic-inorganic hybridization membrane. In the invention, poisonous esters compound containing carbimide need not adopting. It can use multifarious macromolecular compounds for crosslinking with alkoxy silane, which makes materials source be wider. Using manifold bracing matters makes forms and constructions multiple. Production of the invention has a high organic content, good flexibility and compatibility.
Description
Technical field:
The invention belongs to the membrane technology field, particularly relate to the method that adopts sol-gel process to prepare positively charged hybrid organic-inorganic film.
Background technology:
Aspects such as the recovery of Positively charged membrane useful metal in as seawater (brackish water) desalination, running water hard-off, sewage, electrophoretic paint waste water processing, electrochemical sensor have a wide range of applications.At present widely used is lotus positive electricity high-molecular organic material film, because organic material self, common mechanical strength of these films and chemical stability are relatively poor, scarcely high temperature resistant, soda acid and organic solvent, thus limited application in some field.An approach that improves organic these defectives of film of lotus positive electricity be with inorganic material mechanical strength and good stability, chemically-resistant and advantages such as bioerosion, long service life in the positive electric material of organic lotus, promptly prepare the hybrid inorganic-organic materials film of lotus positive electricity.Existing researcher attempts the research of lotus positive electricity hybrid material or film.
U.S. Pat 6,201,051 has reported that the sol gel reaction product with the alkoxide of polyfunctional group organosilicon or B, Al, Si, Sn, Ti or Zr mixes with lotus positive electricity organic polymer, or B, Al, Si, Sn, Ti or Zr, oxide mix with lotus positive electricity organic polymer, obtain can be used as the positively charged hybrid organic-inorganic material of coating.Because this method adopts the mechanical blending step, does not carry out chemical crosslinking, does not have strong chemical b ` between inorganic component and the organic lotus positive electricity component in the system, compatibility is relatively poor relatively.
" membrane science magazine " (Journal of Membrane Science, 1997,126,161-169) with " chemical material " (Chemical Material, 2001,13,1124-1130) reported the little molecule alkoxy silane sol gel reaction of lotus positive electricity, behind the inorganic matrix face coat, make lotus positive electricity hybridized film.This preparation method is a raw material with little molecule alkoxy silane, and sol-gel product organic component content is less, and pliability is not high, so must be supporter with the inorganic matrix, this have limited the application of prepared film.
" membrane science magazine " (Journal of Membrane Science, 2003,216 (1-2), 269-278) reported that the alkoxy silane that contains primary amine and secondary amine group is linked on the peg molecule chain of isocyanide ester base end-blocking by hydrogen transfer reaction, product carries out sol gel reaction then, the quaternized again positively charged hybrid organic-inorganic film that obtains after filming.The raw material sources that use in this preparation hybridized film process are quite limited, and TDI toxicity is bigger.
Summary of the invention:
The invention provides a kind of preparation method of positively charged hybrid organic-inorganic film, to overcome the above-mentioned defective of prior art.
The preparation method of positively charged hybrid organic-inorganic film of the present invention, it is characterized in that multiple functional radical alkoxy silane and the macromolecular compound that contains ester group or epoxy side group or end group are carried out aminolysis, alcoholysis or ring-opening reaction, then product is carried out quaterisation, obtain lotus positive electricity sol gel reaction precursor; This precursor is carried out sol gel reaction, promptly obtain positively charged hybrid organic-inorganic film;
Described multiple functional radical alkoxy silane, its chemical formula can be expressed as [XR
1YR
2]
4-pSiY "
pOr [(X ' R
1)
2Y ' X ' R
2]
4-pSiY "
p, wherein X, Y, X ', Y ' are respectively primary amine, secondary amine, hydroxyl, tertiary amine group; R
1And R
2For containing the alkyl or aryl of 1-10 carbon; Y " is the alkoxy grp of 1-5 carbon; The value of p is 1-3;
The described macromolecular compound that contains ester group side group or end group comprises PMA, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate or both copolymer or copolymer of methyl methacrylatestyrene or MBS among them;
The described macromolecular compound that contains epoxy side group or end group comprises bisphenol-s epoxy resin, glycidyl ester type epoxy resin, novolac epoxy resin or tetraphenolethane epoxy resin;
Described aminolysis reaction is meant under inert gas shielding, 40-80 ℃, and multiple functional radical alkoxy silane [XR
1YR
2]
4-pSiY "
pWith the macromolecular compound solution stirring reaction that contains ester group side group or end group to the required degree of cross linking; Wherein the mol ratio of silane and the macromolecular compound that calculates with ester group is 1-20: 1; Unreacted alkoxy silane is removed in washing of precipitate, is drying to obtain the aminolysis reaction product;
Described alcoholysis reaction is meant under inert gas shielding, 40-80 ℃, and multiple functional radical alkoxy silane [(X ' R
1)
2Y ' X ' R
2]
4-pSiY "
pWith the macromolecular compound solution stirring reaction that contains ester group side group or end group to the required degree of cross linking; Wherein the mol ratio of silane and the macromolecular compound that calculates with ester group is 1-20: 1; Unreacted alkoxy silane is removed in washing of precipitate, is drying to obtain the alcoholysis reaction product;
Described ring-opening reaction is meant under inert gas shielding, 40-100 ℃, and under the catalysis of trace triphenyl phasphine, multiple functional radical alkoxy silane [XR
1YR
2]
4-pSiY '
pWith contain epoxy side group or end group macromolecular compound solution stirring reaction to the required degree of cross linking; Wherein the mol ratio of silane and the macromolecular compound that calculates with epoxy is 1-20: 1; Unreacted alkoxy silane is removed in washing of precipitate, is drying to obtain the epoxy reaction product;
Described quaterisation, be meant that with above-mentioned aminolysis alcoholysis or epoxy reaction product are dissolved in the solvent, add excessive halogenated hydrocarbons, back flow reaction 4-36 hour, the accessory substance that unreacted halogenated hydrocarbons and generation are removed in decompression distillation promptly got lotus positive electricity sol gel reaction precursor; Halogenated hydrocarbons comprises bromoethane, chloroethanes, 1,2-Bromofume, 1,2-dichloroethanes or their mixture;
Described sol gel reaction is meant above-mentioned lotus positive electricity sol gel reaction precursor is dissolved in the solvent, adds entry, methyl silicate or ethyl orthosilicate, catalyst, at 40-80 ℃ of stirring reaction, obtains colloidal sol; The mol ratio that each component is suitable is precursor (with the cubage of silicon): solvent: water: methyl silicate or ethyl orthosilicate: catalyst=1: 5-15: 1-10: 0-5: 0.001-0.01; The colloidal sol of gained is filmed on 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 ℃ from room temperature with 5-20 ℃/hour speed again, insulation is 1-12 hour under normal pressure or the reduced pressure, promptly obtains positively charged hybrid organic-inorganic film; As long as solubility property is good, solvent species need not special qualification, and that commonly used is methyl alcohol, ethanol, N, dinethylformamide, N, N-dimethylacetylamide, methyl-sulfoxide, benzene or toluene; Described catalyst comprises hydrochloric acid, sulfuric acid, trifluoroacetic acid, NaOH, ammonium chloride or ammonium fluoride; Described matrix comprises inorganic and organic matrix, and inorganic matrix comprises Al
2O
3Porous ceramics, Al
2O
3Micro-filtration or milipore filter, glass plate; Organic matrix comprises polyethylene film, polyfluortetraethylene plate, woven dacron, polyamide fabric, glass fabric, nylon cloth or nonwoven; Described method of filming comprises knifing, sprinkling, dipping, flows, rotates coating.
The present invention takes earlier that multiple functional radical is alkoxy silane cross linked to the macromolecular compound strand, carry out quaterisation then, to obtain the sol gel reaction precursor of the higher lotus positive electricity of organic content, carry out sol gel reaction with this precursor again, thereby make the pliability of the positively charged hybrid organic-inorganic film that makes better.The inventive method and U.S. Pat 6,201, the 051 positively charged hybrid organic-inorganic material compared of taking that inorganic and organic principle are carried out the mechanical blending preparation, because link by chemical bond with inorganic silicon oxide components and organic principle in the hybridized film of the inventive method preparation, compatibility is better; With " membrane science magazine " (Journal ofMembrane Science, 1997,126,161-169), " chemical material " (Chemical material, 2001,13,1124-1130) report is that raw material carries out the method that sol gel reaction prepares lotus positive electricity hybridized film and compares with little molecule alkoxy silane, sol gel reaction precursor of the present invention is a macromolecular compound, and organic content can be higher, and pliability can be better, therefore can use multiple support body material, the film form and the structure that obtain have more diversity; With " membrane science magazine " (Journal of Membrane Science, 2003,216 (1-2), 269-278) report is alkoxy silane cross linked to the peg molecule chain of isocyanide ester base end-blocking with little molecule, carry out sol gel reaction again, the quaternized method that obtains lotus positive electricity hybridized film in back of filming is compared, the present invention prepare need not in the lotus positive electricity hybridized film process to adopt toxicity bigger contain the isocyanide ester compounds, and it is crosslinked to adopt multiple macromolecular compound and alkoxy silane to carry out, and raw material sources are more extensive.
The specific embodiment:
Further describe the preparation method of lotus positive electricity hybridized film of the present invention by the following examples.
Embodiment 1
Employing is equipped with the magneton agitator, is had the 250ml four-necked bottle reactor of nitrogen inlet and dropping funel, methyl-sulfoxide (DMSO) solution that adds PMA (Mn=8360), be added dropwise to N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan (A-1120), 60 ℃ of stirring reactions under stirring.The mol ratio of each component is PMA (with the cubage of ester group): A-1120: DMSO=1: 10: 10.At any time infrared test ,～1735cm are carried out in sampling
-1The absworption peak of place's ester group reduces～1640cm gradually
-1With～1570cm
-1Acid amides peak, place strengthens gradually, shows that aminolysis reaction carries out smoothly.When disappearing substantially, the ester group peak stops reaction.
With ethyl acetate and the petroleum ether precipitation of the mixing material in the reactor with 2/1 (volume ratio), after the washing for several times, drying is got 5.0g (being calculated as 0.018mol with silicone content) and is dissolved in the 15mL methyl-sulfoxide, add 8.8mL (0.09mol) bromoethane, 65 ℃ were reacted 12 hours down.The accessory substance of methyl-sulfoxide, unreacted bromoethane and generation is removed in decompression distillation.
Above-mentioned product is dissolved in 13.8mlN, in the dinethylformamide (0.18mol), is added dropwise to 2.0mL0.1mol/L hydrochloric acid and 4mL ethyl orthosilicate (0.018mol) under stirring, 40 ℃ were stirred 1 hour.Be coated on then on the polyfluortetraethylene plate, room temperature, relative humidity are 80% to place after 24 hours, are warmed up to 140 ℃ from room temperature with 15 ℃/hour speed, normal pressure insulation 5 hours down.The film that obtains is scraped from the tetrafluoroethene plate with scalpel, carry out infrared, hot analytical test, scanning electron microscope observation is also measured ion exchange capacity.
Among the infrared test result ,～1100cm
-1The strong characteristic peak that Si-O-Si is arranged ,～2910cm
-1The methylene absworption peak is arranged ,～1640cm
-1With～1570cm
-1There is the acid amides peak at the place.This film that shows preparation contains alkyl, organic principles such as acid amides, and inorganic Si-O-Si chain exists in a large number simultaneously, is organic-inorganic hybrid.
Hot analysis result shows that hybridized film begins to have weightless peak near 250 ℃.
Scanning electron microscope observation shows, film surfacing homogeneous has small white granule evenly to distribute.This shows that the oxide component of organic component and inorganic silicon is uniformly dispersed in the hybridized film that makes.
The anion-exchange capacity that ion exchange capacity is measured hybrid is 2.1 * 10
-4Mol/g.Illustrate that film is a lotus positive electricity.
Comprehensive above analysis result, the film that obtains of present embodiment is the hybrid organic-inorganic film of lotus positive electricity as can be known.And compare with organic Positively charged membrane, higher heat endurance is arranged.
Embodiment 2
Adopt similarly to Example 1 device and operating process, replace PMA with polymethyl methacrylate (Mn=9600), obtain positively charged hybrid organic-inorganic film, anion-exchange capacity is 1.0 * 10
-4Mol/g.
Embodiment 3
Adopt similarly to Example 1 device and operating process, with methyl methacrylate methyl acrylate copolymer (Mn=11000, methyl acrylate content 35%) replace PMA, obtain positively charged hybrid organic-inorganic film, anion-exchange capacity is 1.5 * 10
-4Mol/g.
Embodiment 4
Employing is equipped with the magneton agitator, is had the 250ml four-necked bottle reactor of nitrogen inlet and dropping funel, methyl-sulfoxide (DMSO) solution that adds PMA (Mn=8360), stir and drip N down, N '-two (beta-hydroxyethyl) gamma-aminopropyl-triethoxy-silane (A-1111), 60 ℃ of stirring reactions 3 days receive the little molecule of byproduct of reaction by a pipework condensation simultaneously.The mol ratio of each component is PMA (with the cubage of ester group): A-1111: DMSO=1: 10: 10.At any time infrared test ,～1100cm are carried out in sampling
-1The strong characteristic peak that Si-O-C occurs illustrates A-1111 by alcoholysis reaction, and successful is linked on the polyester molecule chain.
With ethyl acetate and the petroleum ether precipitation of mixing material in the reactor with 2: 1 (volume ratio), after the washing for several times, drying is dissolved in the methyl-sulfoxide, and it is excessive 1 to add, 1: 1 (volume ratio) mixture of 2-Bromofume and bromoethane, 65 ℃ of reactions 20 hours down.Methyl-sulfoxide, unreacted 1, the accessory substance of 2-Bromofume and bromoethane and generation are removed in decompression distillation.
Above-mentioned product is dissolved in N, in the dinethylformamide (DMF), is added dropwise to the 0.01mol/L trifluoroacetic acid under stirring, 40 ℃ were stirred 1 hour.The each component mol ratio is product (with the cubage of silicon): DMF: water: trifluoroacetic acid=1: 8: 4: 0.005.To be coated on the nonwoven after the colloidal sol deaeration that obtain then, room temperature, relative humidity be 75% place 24 hours after, be warmed up to 130 ℃ from room temperature with 10 ℃/hour speed, normal pressure insulation 5 hours down.The film that obtains is carried out infrared test, and scanning electron microscope observation is also measured ion exchange capacity.
Among the infrared test result ,～1100cm
-1The strong characteristic peak that Si-O-Si is arranged ,～2910cm
-1The methylene absworption peak is arranged ,～1730cm
-1There is the carbonyl peak of ester at the place.This shows that the film of preparation contains organic principles such as alkyl, carbonyl, and inorganic Si-O-Si chain exists in a large number simultaneously, is organic-inorganic hybrid.
Scanning electron microscope observation shows that film surfacing homogeneous has small white particle evenly to distribute.This shows that the oxide component of organic component and inorganic silicon is uniformly dispersed in the hybridized film that makes.
The anion-exchange capacity that ion exchange capacity is measured hybrid is 3.5 * 10
-4Mol/g.Illustrate that film is a lotus positive electricity.
Comprehensive above analysis result, the film that obtains of present embodiment is the hybrid organic-inorganic film of lotus positive electricity as can be known.
Embodiment 5
Adopt similarly to Example 4 device and operating process, replace PMA with polymethyl methacrylate (Mn=9600), obtain positively charged hybrid organic-inorganic film, anion-exchange capacity is 1.7 * 10
-4Mol/g.
Embodiment 6
Adopt similarly to Example 4 device and operating process, with methyl methacrylate methyl acrylate copolymer (Mn=11000, methyl acrylate content 35%) replace PMA, obtain positively charged hybrid organic-inorganic film, anion-exchange capacity is 2.1 * 10
-4Mol/g.
Embodiment 7
Employing is equipped with the magneton agitator, is had the 250ml four-necked bottle reactor of nitrogen inlet and dropping funel, add bisphenol-s epoxy resin (low-molecular-weight, epoxide equivalent is 190) methyl-sulfoxide (DMSO) solution and trace triphenyl phasphine, be added dropwise to ethylenediamine base propyl trimethoxy silicane (A-1120), 60 ℃ of stirring reactions under stirring.The mol ratio of each component is epoxy resin (with the cubage of epoxy radicals): A-1120: DMSO=1: 10: 10.At any time infrared test ,～1100cm are carried out in sampling
-1The strong characteristic peak that Si-O-C occurs, 1250,950-810cm
-1Near the characteristic peak of epoxide group weakens gradually.A-1120 is by ring-opening reaction in this explanation, and successful is linked on the epoxy resin strand.When disappearing substantially, the epoxy base peak stops reaction.
The product methanol extraction, after the washing for several times, drying is dissolved among the DMSO again, adds excessive bromoethane then, 70 ℃ of stirring reactions 24 hours.The accessory substance of methyl-sulfoxide, unreacted bromoethane and generation is removed in decompression distillation.
Get this quaternized products of part and be dissolved among the DMSO, add entry and 0.1mol/L trifluoroacetic acid.The each component mol ratio is product (with the cubage of silicon): DMSO: water: trifluoroacetic acid=1: 10: 1: 0.001.After 1 hour, taking a morsel drips on 1 * 1cm silicon chip, rotates 5 seconds with the speed of 1500r/s, forms homogeneous film at 60 ℃ of stirring reactions.Remaining part is coated on the woven dacron.
With silicon chip and woven dacron room temperature, relative humidity be 90% place 24 hours after, be warmed up to 120 ℃ with 15 ℃/hour speed, normal pressure insulation 5 hours down.Film on the silicon chip that obtains carries out scanning electron microscope observation.The film that applies on the woven dacron carries out infrared and the ion exchange capacity test.
Among the infrared test result ,～1100cm
-1The strong characteristic peak that Si-O-Si is arranged ,～2910cm
-1The methylene absworption peak is arranged ,～3400cm
-1Amido and hydroxyl absworption peak are arranged.This shows that the film of preparation contains organic principles such as alkyl, amido, and inorganic Si-O-Si chain exists in a large number simultaneously, is organic-inorganic hybrid.
The scanning electron microscope observation surface, the smooth homogeneous of the film on the silicon chip has nano level white granule evenly to distribute.This shows that the oxide component of organic component and inorganic silicon is uniformly dispersed in the hybridized film that makes.
The anion-exchange capacity that ion exchange capacity is measured hybridized film is 1.1 * 10
-2Mmol/g.Illustrate that film is a lotus positive electricity.
Comprehensive above analysis result, the film that obtains of present embodiment is the hybrid organic-inorganic film of lotus positive electricity as can be known.
Embodiment 8
Adopt similarly to Example 4 device and operating process, (epoxide number 0.58～0.66 equivalent/100g) replace bisphenol-s epoxy resin obtains positively charged hybrid organic-inorganic film, and anion-exchange capacity is 2.0 * 10 with glycidyl ester type epoxy resin
-2Mmol/g.
Embodiment 9
Adopt similarly to Example 4 device and operating process, replace bisphenol-s epoxy resin with novolac epoxy resin, obtain positively charged hybrid organic-inorganic film, anion-exchange capacity is 1.5 * 10
-4Mol/g.
Claims (1)
1, a kind of preparation method of positively charged hybrid organic-inorganic film, it is characterized in that multiple functional radical alkoxy silane and the macromolecular compound that contains ester group or epoxy side group or end group are carried out aminolysis, alcoholysis or ring-opening reaction, then product is carried out quaterisation, obtain lotus positive electricity sol gel reaction precursor; This precursor is carried out sol gel reaction, promptly obtain positively charged hybrid organic-inorganic film;
Described multiple functional radical alkoxy silane, its chemical formula can be expressed as [XR
1YR
2]
4-pSiY "
pOr [(X ' R
1)
2Y ' X ' R
2]
4-pSiY "
p, wherein X, Y, X ', Y ' are respectively primary amine, secondary amine, hydroxyl, tertiary amine group; R
1And R
2For containing the alkyl or aryl of 1-10 carbon; Y " is the alkoxy grp of 1-5 carbon; The value of p is 1-3;
The described macromolecular compound that contains ester group side group or end group comprises PMA, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate or both copolymer or copolymer of methyl methacrylatestyrene or MBS among them;
The described macromolecular compound that contains epoxy side group or end group comprises bisphenol-s epoxy resin, glycidyl ester type epoxy resin, novolac epoxy resin or tetraphenolethane epoxy resin;
Described aminolysis reaction is meant under inert gas shielding, 40-80 ℃, and multiple functional radical alkoxy silane [XR
1YR
2]
4-pSiY "
pWith the macromolecular compound solution stirring reaction that contains ester group side group or end group to the required degree of cross linking; Wherein the mol ratio of silane and the macromolecular compound that calculates with ester group is 1-20: 1; Unreacted alkoxy silane is removed in washing of precipitate, is drying to obtain the aminolysis reaction product;
Described alcoholysis reaction is meant under inert gas shielding, 40-80 ℃, and multiple functional radical alkoxy silane [(X ' R
1)
2Y ' X ' R
2]
4-pSiY "
pWith the macromolecular compound solution stirring reaction that contains ester group side group or end group to the required degree of cross linking; Wherein the mol ratio of silane and the macromolecular compound that calculates with ester group is 1-20: 1; Unreacted alkoxy silane is removed in washing of precipitate, is drying to obtain the alcoholysis reaction product;
Described ring-opening reaction is meant under inert gas shielding, 40-100 ℃, and under the catalysis of trace triphenyl phasphine, multiple functional radical alkoxy silane [XR
1YR
2]
4-pSiY '
pWith contain epoxy side group or end group macromolecular compound solution stirring reaction to the required degree of cross linking; Wherein the mol ratio of silane and the macromolecular compound that calculates with epoxy is 1-20: 1; Unreacted alkoxy silane is removed in washing of precipitate, is drying to obtain the epoxy reaction product;
Described quaterisation, be meant that with above-mentioned aminolysis alcoholysis or epoxy reaction product are dissolved in the solvent, add excessive halogenated hydrocarbons, back flow reaction 4-36 hour, the accessory substance that unreacted halogenated hydrocarbons and generation are removed in decompression distillation promptly got lotus positive electricity sol gel reaction precursor; Halogenated hydrocarbons comprises bromoethane, chloroethanes, 1,2-Bromofume, 1,2-dichloroethanes or their mixture;
Described sol gel reaction is meant above-mentioned lotus positive electricity sol gel reaction precursor is dissolved in the solvent, adds entry, methyl silicate or ethyl orthosilicate, catalyst, at 40-80 ℃ of stirring reaction, obtains colloidal sol; The mol ratio that each component is suitable is, the precursor that calculates with silicone content: solvent: water: methyl silicate or ethyl orthosilicate: catalyst=1: 5-15: 1-10: 0-5: 0.001-0.01; The colloidal sol of gained is filmed on 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 ℃ from room temperature with 5-20 ℃/hour speed again, insulation is 1-12 hour under normal pressure or the reduced pressure, promptly obtains positively charged hybrid organic-inorganic film; Described catalyst comprises hydrochloric acid, sulfuric acid, trifluoroacetic acid, NaOH, ammonium chloride or ammonium fluoride; Described matrix comprises inorganic and organic matrix, and inorganic matrix comprises Al
2O
3Porous ceramics, Al
2O
3Micro-filtration or milipore filter, glass plate; Organic matrix comprises polyethylene film, polyfluortetraethylene plate, woven dacron, polyamide fabric, glass fabric, nylon cloth or nonwoven.
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| CN1298414C (en) * | 2005-04-06 | 2007-02-07 | 南京工业大学 | Organic-inorganic substances compound membrane and its preparation method |
| CN100518914C (en) * | 2006-10-27 | 2009-07-29 | 中国科学技术大学 | Organic-inorganic hybridized anion exchange membrane preparation method |
| CN101239256B (en) * | 2007-11-22 | 2011-01-12 | 南京工业大学 | Oil gas separation ceramic compound film tube and component and preparation thereof |
| 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 |
| CN102210985A (en) * | 2010-04-06 | 2011-10-12 | 中国科学院过程工程研究所 | Organic-inorganic hybrid positive charge separation membrane |
| CN102658036A (en) * | 2012-03-06 | 2012-09-12 | 中国科学技术大学 | Coating liquid, organic-inorganic hybrid cation exchange membrane and preparation method thereof |
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| CN1298414C (en) * | 2005-04-06 | 2007-02-07 | 南京工业大学 | Organic-inorganic substances compound membrane and its preparation method |
| CN100518914C (en) * | 2006-10-27 | 2009-07-29 | 中国科学技术大学 | Organic-inorganic hybridized anion exchange membrane 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 |
| CN101239256B (en) * | 2007-11-22 | 2011-01-12 | 南京工业大学 | Oil gas separation ceramic compound film tube and component and preparation thereof |
| CN102210985A (en) * | 2010-04-06 | 2011-10-12 | 中国科学院过程工程研究所 | Organic-inorganic hybrid positive charge separation membrane |
| CN102210985B (en) * | 2010-04-06 | 2013-05-01 | 中国科学院过程工程研究所 | Organic-inorganic hybrid positive charge separation membrane |
| CN102658036A (en) * | 2012-03-06 | 2012-09-12 | 中国科学技术大学 | Coating liquid, organic-inorganic hybrid cation exchange membrane and preparation method thereof |
| CN102827546A (en) * | 2012-09-09 | 2012-12-19 | 郭子钰 | Method for designing and manufacturing novel material |
| CN105435657A (en) * | 2014-07-22 | 2016-03-30 | 中国石油化工股份有限公司 | Composite nanofiltration membrane and preparation method thereof |
| CN105435657B (en) * | 2014-07-22 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof |
| CN109847592A (en) * | 2019-01-04 | 2019-06-07 | 广州汉至蓝能源与环境技术有限公司 | A kind of organic-inorganic hybrid films preparation method |
| CN114377556A (en) * | 2022-01-19 | 2022-04-22 | 西南石油大学 | Temperature-resistant composite water treatment membrane and preparation method thereof |
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