CN101318836A - Method for manufacturing pH sensitive intelligent ceramic compound film - Google Patents
Method for manufacturing pH sensitive intelligent ceramic compound film Download PDFInfo
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- CN101318836A CN101318836A CNA2008101232176A CN200810123217A CN101318836A CN 101318836 A CN101318836 A CN 101318836A CN A2008101232176 A CNA2008101232176 A CN A2008101232176A CN 200810123217 A CN200810123217 A CN 200810123217A CN 101318836 A CN101318836 A CN 101318836A
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Abstract
The invention discloses a preparation method for a pH sensitive type intelligent ceramic composite membrane. The method comprises the following steps that: multifunctional-radical alkoxy silane has a polyreaction with hydroxide radicals on the surface of the ceramic membrane to form a hydrophobic vinyl chain on the surface of the ceramic membrane; then the ceramic membrane with the vinyl chain has a free radical polymerization reaction with pH sensitive functional monomer acrylic acid under the protection of nitrogen to obtain the pH sensitive type intelligent ceramic composite membrane. The method is carried out in a normal pressure status and all used reagents are conventional reagents, thereby bringing about basic equipment, low cost, and capability of industrial continuous production. The ceramic composite membrane has high mechanical strength, good stability, good pH sensitivity, great permeation flux and easy cleaning. As the aperture of the ceramic membrane can vary with the pH value, the ceramic membrane is an intelligent membrane capable of separating mixtures from different molecular weights only through one membrane via adjusting the pH value.
Description
Technical field
The present invention relates to a kind of preparation method of intelligent ceramic composite membrane, be specially a kind of Acrylic Acid Monomer (AAC) and ceramic membrane (α-Al pH sensitivity and pH response type
2O
3) preparation method of the pH sensitive intelligent ceramic compound film that obtains of graft copolymerization, belong to the membrane technique field.
Background technology
Membrane technique is contemporary high efficient separation technology, compare with traditional isolation technique chromatogram, distillation, it have separation efficiency height, energy consumption low, easy to operate, free from environmental pollution, be easy to amplify, can with outstanding advantage such as other isolation technique coupling.And in membrane separation technique, mould material is the key that realizes sepn process.Mould material has been realized commercialization, variation, seriation and normalization gradually through 100 years of development.
But progress and human deepening constantly to autonomous mechanism understanding along with science and technology, people begin to stride forward to functionalization, intelligent film direction gradually, and develop the intelligent film that can respond under the situation that extraneous environmental stimulus such as temperature, light, magnetic, pH value change.The functional membrane technology also is considered to the most promising new and high technology of 21st century.Up to now, though membrane technique has obtained significant progress, but most of product films are subjected to the change of external stimulus little to its performance impact, and this intelligent separatory membrane, its structure can reversibly change with the variation of external stimulus, cause the change of film properties such as pore size, hydrophilic and hydrophobic etc., thus the permeation flux of controlling diaphragm, the selectivity of raising film.In recent years, environmental response type intelligent switch film is used widely in fields such as medicine sustained release, chemical separation and organizational projects.
PH response type intelligent film is as a kind of in the intelligent film, and it has broad application prospects in fields such as fixing, the feed separation of drug release, enzyme, chemical valve and artificial-muscles.Vinylformic acid and derivative thereof then are the fine pH responsive materials of a class, and it changes according to the pH value, and the polymer segment configuration takes place by corresponding the variation.The vinylformic acid chain contains hydrophilic carboxyl (COOH) in addition, has good wetting ability.
At present, the pH response type intelligent film of bibliographical information, with acrylic acid or the like in response the method for the intelligent film of material mainly contain following several:
1. plasma method: people's using plasmas such as Chu Liangyin are induced the method for filling perforation graft polymerization, successfully in the fenestra internal surface grafting of polyvinylidene difluoride (PVDF) (PVDF) porous-film polymethyl acrylic acid (PMAA) grafting layer as pH induction type switch, and prepared the pH inductive switch film of a series of percentage of grafting.(referring to document: Qu Jianbo, Yang Mei, Chu Liangyin, Zhu Jiahua, Chen Wenmei, Xie Rui, plasma-induced graft polymerization legal system is equipped with pH inductive switch film, polymer material science and engineering, 2005,21 (2): 93-97).
2. photo-grafting: people such as Yang Biao adopt the photo-grafting polymerization process, with the benzophenone is light trigger, benzophenone is carried the Hydrogen photoreduction under ultraviolet excitation, the hydrogen of capturing on polyethylene terephthalate (PET) nucleopore membranes generates the semipinacol free radical, thereby cause acrylic acid-grafted being aggregated on the film, form pH response type switch intelligence film.(referring to document: Yang Biao, Yang Wantai, photo-grafting prepare novel pH switch nucleopore membranes, the polymer journal, and 2003,2:272-277).
3. self-assembly method: people such as Britain scholar A.M.Mayes adopt self-assembling method that methacrylic acid (PMAA) is grafted on polyvinylidene difluoride (PVDF) (PVDF) porous-film, and the film that makes has fine sensitivity to pH.(referring to document: J.F.Hester, S.C.Olugebefola, A.M.Mayes, Preparation of pH-responsive polymer membranes by self-organization, Journal of Membrane Science, 2002,208:375-388.).
4. alkali treatment method: people such as Chen Li are with Acrylic Acid Monomer and the graft copolymerization of polyvinylidene difluoride (PVDF) (PVDF) film, adopt alkali treatment method to make the pvdf membrane surface modification, and then the monomer that contains two keys with vinylformic acid etc. generates the PVDF intelligence film with certain environment pH responsiveness in the PVDF surface reaction.(referring to patent (200410019993.3): Chen Li, Wang Wenyu, a kind of temperature sensitive polyvinylidene difluoride (PVDF) tubular fibre intelligence membrane preparation method and products thereof).
In existing report, mostly the intelligent film of preparation is that with organic membrane as basement membrane, grafting functional monomer on organic membrane is made the environment sensitive film.But organic membrane has low, the poor chemical stability of physical strength, and shortcomings such as swelling and metamorphosis take place easily, thereby can not use under some causticity conditions.A kind of as in the ceramic membrane of alumina ceramic membrane has the physical strength height, chemical stability is good, and chemically-resistant and biological attack are high temperature resistant, long service life, and pore size distribution is narrow, and the separation efficiency height is easy to advantage such as sterilization cleaning and is widely used.Thereby with alumina ceramic membrane as basement membrane, the intelligent ceramic composite membrane that makes can overcome with the organic membrane the low shortcoming of physical strength of the intelligent film that is basement membrane preparation, can also have the environmental sensitivity of grafted monomer simultaneously.But, prepare the responsive intelligent ceramic composite membrane of pH with alumina ceramic membrane as basement membrane so far and also still do not report.
Summary of the invention
At the shortage of prior art, the present invention proposes a kind of pH sensitive intelligent ceramic compound film preparation method, and the intelligent ceramic composite membrane machinery that adopts this method to obtain is highly high, and chemistry is latent qualitative good, and long service life is easy to sterilization and cleans.
Technical solution of the present invention is: with the hydroxyl polymerization reaction take place of multi-functional basic organoalkoxysilane and ceramic membrane surface, have hydrophobic vinyl chain in ceramic membrane surface formation; To have the ceramic membrane of vinyl chain and the functional monomer vinylformic acid of pH susceptibility then and issue living Raolical polymerizable, obtain having the pH sensitive intelligent ceramic compound film in nitrogen protection.
Wherein, described multi-functional basic organoalkoxysilane is the γ-propyl methacrylate base Trimethoxy silane (KH-570) with carbon-carbon double bond and methoxyl group.
Preparation method of the present invention may further comprise the steps: at first, adopt the polymer deposition method, utilize γ-propyl methacrylate base Trimethoxy silane (KH-570) to α-Al
2O
3Ceramic membrane carries out modification, makes ceramic membrane surface have hydrophobic vinyl chain; Then, adopting radical polymerization, is grafted monomer with vinylformic acid, and Potassium Persulphate is an initiator, modified alpha-Al
2O
3Film is a basement membrane, on the modified ceramic film, is prepared into the pH sensitive intelligent ceramic compound film with acrylic acid-grafted.
Preparation method of the present invention comprises following concrete steps:
(1) ceramic membrane KH-570 modification: the toluene solution that in reactor, adds ceramic diaphragm and mass concentration 5-20%KH-570, sonic oscillation makes its dissolving evenly, in 80 ℃ of following back flow reaction of temperature, after reaction finishes diaphragm is cleaned with toluene, acetone, ethanol, water successively, diaphragm after the cleaning is at room temperature dry earlier, and then dry down at 120 ℃; Wherein, 1cm
2The ceramic diaphragm of specific surface area needs KH-570 toluene solution 2-4ml.
(2) Potassium Persulphate and deionized water are packed in the reactor, ultrasonic for some time gets the millesimal solution of mass concentration, add Acrylic Acid Monomer again, the mass ratio of itself and deionized water is 5-15%, feed nitrogen and above-mentioned modified ceramic diaphragm is added, heat 50-100 ℃, isothermal reaction 30-120min; Wherein, 1cm
2The ceramic diaphragm of specific surface area needs Acrylic Acid Monomer 0.48-1.3ml.
(3) washed with de-ionized water diaphragm, and ultrasonic cleaning several times, diaphragm promptly obtains the pH sensitive intelligent ceramic compound film 80-100 ℃ of down oven dry.
Preparation method of the present invention controls percentage of grafting by control reaction temperature, time, monomer concentration, prepares different pH sensitive intelligent ceramic compound films.
Preparation method of the present invention selects α-Al for use
2O
3Ceramic membrane is fit to SiO equally as basement membrane
2Ceramic membrane, ZrO
2Ceramic membrane also is fit to other olefines organic membrane; Used vinylformic acid is responsive materials.
The present invention has the following advantages: 1. carry out under atmospheric pressure state, used reagent is conventional reagent, basic equipment, and cost is low, can carry out industrial continuous production; 2. intelligent ceramic film physical strength height, good stability, pH susceptibility are good, permeation flux big, be easy to clean; 3. the pH sensitive intelligent ceramic compound film be vinylformic acid (AAC) with basement membrane between the method that combines by chemical bond prepare, vinylformic acid has hydrophilic radicals such as COOH, make and return to hydrophilic film again through hydrophobic ceramic membrane after the KH-570 modification, also making the aperture of ceramic membrane change and change along with the pH value, is that a kind of only reaching by adjusting pH value can be carried out isolating intelligent film to the different molecular weight mixture with a kind of film.
Embodiment
Further describe pH sensitive intelligent ceramic film of the present invention by the following examples, should be understood that these embodiment just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Embodiment 1:
Prepare the pH sensitive intelligent ceramic compound film according to following steps:
(1) ceramic membrane KH-570 modification: in Erlenmeyer flask, add specific surface area 6.15cm
2SiO
2The toluene solution 12.3ml of ceramic diaphragm and mass concentration 10%KH-570, sonic oscillation make its dissolving evenly, in 80 ℃ of following back flow reaction of temperature; After reaction finishes diaphragm is cleaned with toluene, acetone, second alcohol and water successively, the diaphragm after the cleaning is at room temperature dry earlier, and then dry down at 120 ℃;
(2) 0.05g Potassium Persulphate and 50ml deionized water are packed in the reactor, ultrasonic for some time makes solution even, adds the 3ml Acrylic Acid Monomer again, feeds nitrogen and above-mentioned modified ceramic diaphragm is added, and heats 50 ℃, isothermal reaction 30min;
(3) washed with de-ionized water diaphragm, and with ultrasonic cleaning several times, diaphragm promptly obtains the pH sensitive intelligent ceramic compound film 80 ℃ of oven dry down.
Embodiment 2:
(1) ceramic membrane KH-570 modification: in Erlenmeyer flask, add specific surface area 6.15cm
2ZrO
2The toluene solution 18.5ml of ceramic diaphragm and mass concentration 15%KH-570, sonic oscillation make its dissolving evenly, in 80 ℃ of following back flow reaction of temperature; After reaction finishes with diaphragm with cleaning with toluene, acetone, second alcohol and water successively, the diaphragm after the cleaning is at room temperature dry earlier, and then dry down at 120 ℃;
(2) 0.05g Potassium Persulphate and 50ml deionized water are packed in the reactor, ultrasonic for some time makes solution even, adds the 5ml Acrylic Acid Monomer again, feeds nitrogen and above-mentioned modified ceramic diaphragm is added, and is heated to 70 ℃, isothermal reaction 70min;
(3) washed with de-ionized water diaphragm, and with ultrasonic cleaning several times, diaphragm promptly obtains the pH sensitive intelligent ceramic compound film 90 ℃ of oven dry down.
Embodiment 3:
(1) ceramic membrane KH-570 modification: in Erlenmeyer flask, add specific surface area 6.15cm
2α-Al
2O
3The toluene solution 24.6ml of ceramic diaphragm and mass concentration 5%KH-570, sonic oscillation make its dissolving evenly, in 80 ℃ of following back flow reaction of temperature; After reaction finishes diaphragm is cleaned with toluene, acetone, second alcohol and water successively, the diaphragm after the cleaning is at room temperature dry earlier, and then dry down at 120 ℃;
(2) 0.05g Potassium Persulphate and 50ml deionized water are packed in the reactor, ultrasonic for some time makes solution even, adds the 8ml Acrylic Acid Monomer again, feeds nitrogen and above-mentioned modified ceramic diaphragm is added, and is heated to 100 ℃, isothermal reaction 120min.
(3) washed with de-ionized water diaphragm, and with ultrasonic cleaning several times, diaphragm promptly obtains pH sensitive intelligent ceramic film 100 ℃ of oven dry down.
Claims (5)
1. the preparation method of a pH sensitive intelligent ceramic compound film is characterized in that: with the hydroxyl polymerization reaction take place of multi-functional basic organoalkoxysilane and ceramic membrane surface, have hydrophobic vinyl chain in ceramic membrane surface formation; To have the ceramic membrane of vinyl chain and the functional monomer vinylformic acid of pH susceptibility then and issue living Raolical polymerizable, obtain having the pH sensitive intelligent ceramic compound film in nitrogen protection.
2. the preparation method of a kind of pH sensitive intelligent ceramic compound film according to claim 1 is characterized in that: wherein, described multi-functional basic organoalkoxysilane is the γ-propyl methacrylate base Trimethoxy silane with carbon-carbon double bond and methoxyl group.
3. the preparation method of a kind of pH sensitive intelligent ceramic compound film according to claim 2 is characterized in that the preparation method may further comprise the steps: at first, adopt the polymer deposition method, utilize γ-propyl methacrylate base Trimethoxy silane to α-Al
2O
3Ceramic membrane carries out modification, makes ceramic membrane surface have hydrophobic vinyl chain; Then, adopting radical polymerization, is grafted monomer with vinylformic acid, and Potassium Persulphate is an initiator, modified alpha-Al
2O
3Film is a basement membrane, on the modified ceramic film, is prepared into the pH sensitive intelligent ceramic compound film with acrylic acid-grafted.
4. the preparation method of a kind of pH sensitive intelligent ceramic compound film according to claim 3 is characterized in that the preparation method comprises following concrete steps:
(1) ceramic membrane KH-570 modification: the toluene solution that in reactor, adds ceramic diaphragm and mass concentration 5-20%KH-570, sonic oscillation makes its dissolving evenly, in 80 ℃ of following back flow reaction of temperature, after reaction finishes diaphragm is cleaned with toluene, acetone, ethanol, water successively, diaphragm after the cleaning is at room temperature dry earlier, and then dry down at 120 ℃; 1cm
2The ceramic diaphragm of specific surface area needs KH-570 toluene solution 2-4ml;
(2) Potassium Persulphate and deionized water are packed in the reactor, ultrasonic for some time gets the millesimal solution of mass concentration, add Acrylic Acid Monomer again, the mass ratio of itself and deionized water is 5-15%, feed nitrogen and above-mentioned modified ceramic diaphragm is added, heat 50-100 ℃, isothermal reaction 30-120min; Wherein, 1cm
2The ceramic diaphragm of specific surface area needs Acrylic Acid Monomer 0.48-1.3ml;
(3) washed with de-ionized water diaphragm, and ultrasonic cleaning several times, diaphragm promptly obtains the pH sensitive intelligent ceramic compound film 80-100 ℃ of down oven dry.
5. the preparation method of a kind of pH sensitive intelligent ceramic compound film according to claim 1 is characterized in that: α-Al
2O
3, SiO
2Or ZrO
2Ceramic membrane is as basement membrane.
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| CNA2008101232176A CN101318836A (en) | 2008-06-13 | 2008-06-13 | Method for manufacturing pH sensitive intelligent ceramic compound film |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059059A (en) * | 2010-11-16 | 2011-05-18 | 南京工业大学 | Preparation method of protein adsorption resistant ceramic composite membrane |
| CN105771683A (en) * | 2016-04-26 | 2016-07-20 | 南京工业大学 | Method for improving stability of SAPO-34 molecular sieve membrane in water vapor environment |
| CN107641898A (en) * | 2016-05-27 | 2018-01-30 | 天津工业大学 | A kind of modified polyvinilidene fluoride nanofiber smart membrane |
| CN107684834A (en) * | 2017-09-19 | 2018-02-13 | 北京航空航天大学 | A kind of graphene-based seperation film of intelligent response type for mixed molecules separation and preparation method thereof |
| CN108479435A (en) * | 2018-04-16 | 2018-09-04 | 哈尔滨工业大学 | A kind of preparation method of ceramic base polyvinyl acetate composite membrane |
| CN109078503A (en) * | 2018-08-17 | 2018-12-25 | 东华大学 | PET precision transfusion filters nucleopore membranes hydrophilicity-imparting treatment technique |
| CN113480263A (en) * | 2021-07-24 | 2021-10-08 | 陕西秦汉恒盛新型建材科技股份有限公司 | 3D printing concrete prepared from recycled aggregate and preparation method thereof |
| CN114538960A (en) * | 2021-11-26 | 2022-05-27 | 南京工业大学 | Polyacrylic acid modified ceramic membrane, preparation method and application |
-
2008
- 2008-06-13 CN CNA2008101232176A patent/CN101318836A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059059A (en) * | 2010-11-16 | 2011-05-18 | 南京工业大学 | Preparation method of protein adsorption resistant ceramic composite membrane |
| CN105771683A (en) * | 2016-04-26 | 2016-07-20 | 南京工业大学 | Method for improving stability of SAPO-34 molecular sieve membrane in water vapor environment |
| CN105771683B (en) * | 2016-04-26 | 2019-02-19 | 南京工业大学 | Method for improving stability of SAPO-34 molecular sieve membrane in water vapor environment |
| CN107641898A (en) * | 2016-05-27 | 2018-01-30 | 天津工业大学 | A kind of modified polyvinilidene fluoride nanofiber smart membrane |
| CN107684834A (en) * | 2017-09-19 | 2018-02-13 | 北京航空航天大学 | A kind of graphene-based seperation film of intelligent response type for mixed molecules separation and preparation method thereof |
| CN108479435A (en) * | 2018-04-16 | 2018-09-04 | 哈尔滨工业大学 | A kind of preparation method of ceramic base polyvinyl acetate composite membrane |
| CN109078503A (en) * | 2018-08-17 | 2018-12-25 | 东华大学 | PET precision transfusion filters nucleopore membranes hydrophilicity-imparting treatment technique |
| CN113480263A (en) * | 2021-07-24 | 2021-10-08 | 陕西秦汉恒盛新型建材科技股份有限公司 | 3D printing concrete prepared from recycled aggregate and preparation method thereof |
| CN114538960A (en) * | 2021-11-26 | 2022-05-27 | 南京工业大学 | Polyacrylic acid modified ceramic membrane, preparation method and application |
| CN114538960B (en) * | 2021-11-26 | 2023-03-14 | 南京工业大学 | Polyacrylic acid modified ceramic membrane, preparation method and application |
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