CN103172901A - New method for preparing intelligent polymeric membrane - Google Patents
New method for preparing intelligent polymeric membrane Download PDFInfo
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- CN103172901A CN103172901A CN2013101137350A CN201310113735A CN103172901A CN 103172901 A CN103172901 A CN 103172901A CN 2013101137350 A CN2013101137350 A CN 2013101137350A CN 201310113735 A CN201310113735 A CN 201310113735A CN 103172901 A CN103172901 A CN 103172901A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a new method for preparing an intelligent polymeric membrane. The new method provided by the invention has the main characteristics that 1, a natural polymer chiston raw material is used for preparing a porous membrane and an intelligent response membrane is prepared by taking N-isopropyl acrylamide and acrylic acid as monomers and benzoyl peroxide as a free radical polymerization initiator; 2, supercritical carbon dioxide is utilized as a reaction medium; 3, in a reaction process, a reaction course can be controlled by regulating conditions such as reaction pressure and reaction time; and 4, a preparation technology is simple, operation is easy, a preparation process is safe, non-toxic and pollution-free, and a process is easy to control, so that the new method provided by the invention is a green and simple preparation method.
Description
Technical field
The invention belongs to the technical field for preparing intelligent macromolecular membrane take supercritical co as solvent.Be particularly related to the natural polymer raw materials of chitosan and prepare porous-film,
N-N-isopropylacrylamide and vinylformic acid are monomer, and benzoyl peroxide is radical initiator, and graft copolymerization prepares intelligent macromolecular membrane
Background technology
In recent years, supercutical fluid (Supercritical Fluid is abbreviated as SCF) becomes development new technique rapidly, and increasingly extensive purposes is being arranged aspect chemical separation, analysis and chemosynthesis.Due to the special property of supercutical fluid, particularly it can substitute high malicious organic solvent and make reaction medium, meets the requirement of Green Chemistry, makes it obtain more and more the application in organic synthesis
Environmental response type smart membrane is himself to contain to stimulate to external world to make the group of reversible reaction or the film of segment, thereby make the structure of film change and reversibly change with external stimulus, cause the change of film properties (as pore size, parent/hydrophobicity etc.), thereby the flux of controlling diaphragm, the selectivity of raising film.At present, the intellectuality of mould material has become a new direction of current parting material field development.Intelligent macromolecular membrane is controlled a plurality of fields such as release, chemical separation, biological medicine, chemical sensor, artificial organ, water treatment and is had important potential value at medicine
Supercritical co has nontoxic, pollution-free, easy recovery, unreactiveness, dissolving power as reaction medium and can regulate, superpolymer is had very strong swelling and diffusibility, good advantages such as the easy purifying noresidue of plastification, product, make it become the favorite of " green " medium, can utilize these character, take grafted monomer to its film inner, form evenly and after distribution, film is carried out graft modification.Especially in macromolecular polymerization reaction, be the ideal substitute of conventional organic solvents.Therefore, use green solvent---scCO
2As medium, development environment stimulates green synthesis method and the clearer production technology of multiple response type smart membrane, carry out corresponding applied basic research, not only have great scientific meaning, and the new technology and the novel process that form will realize that Sustainable development exerts far reaching influence to many industries
In recent years, adopt scCO
2Assist the solid phase grafting method to carry out the report of grafting more, mainly concentrate on polypropylene grafted modification aspect.ScCO2 only has preferably outside solvability the fluorine-containing and silicon-containing polymer of minority, can only carry out in various degree swelling to most polymers, compares scCO with conventional organic solvents
2Can be along with density and the pressure change of supercutical fluid to the swelling ability of polymkeric substance, and can directly obtain grafted products after reaction finishes.Therefore, scCO
2Become a kind of Effective medium of polymer surfaces modification and graft modification
The present invention utilizes supercritical co to be reaction solvent, and the natural polymer raw materials of chitosan prepares porous-film,
N-N-isopropylacrylamide and vinylformic acid are monomer, and benzoyl peroxide is radical initiator, and grafting prepares intelligent macromolecular membrane
Summary of the invention
The present invention provides a kind of novel method for preparing intelligent macromolecular membrane take supercritical co as the green reaction solvent;
The technical solution used in the present invention:
1. taking 0.5g chitosan (CS) is dissolved in 20 mL 2% acetic acid aqueous solutions;
2. add a certain amount of silicon-dioxide (SiO
2) as pore-creating agent, a certain amount of ethylene glycol is as softening agent, and a certain amount of 0.25% glutaraldehyde stirs as linking agent;
3. get on the sheet glass that a certain amount of solution evenly is tiled in clean dried, under room temperature, after drying, 80 ℃ of the sodium hydroxide solutions with 5% soak 10 h, remove SiO
2, make porous-film;
4. the porous-film drying that makes is weighed, and take a certain amount of
N-N-isopropylacrylamide and vinylformic acid, and benzoyl peroxide are placed in autoclave;
5. make the autoclave sealing, put into ice-water bath, then the air with in carbonic acid gas eliminating reactor is filled with a certain amount of carbonic acid gas;
6. the reactor that will be filled with carbonic acid gas is put into water-bath, and 30
oC preheating 3 h fully mix raw material in precritical carbonic acid gas.Then slowly be warming up to 80
oC reaches predetermined pressure, reaction 10 h;
7. after reaction finishes, make reactor naturally cool to room temperature, emit carbonic acid gas in still, open the film after reactor can obtain grafting.
The present invention has prepared a kind of biological activity intelligent response film with temperature and pH doubling sensitivity, its preparation method is convenient, efficient and reaction process control is easy to be nontoxic, pollution-free, the easy purifying noresidue of product is a kind of eco-friendly " green " new synthetic method.
Description of drawings
Fig. 1 grafting intelligent macromolecular membrane infrared spectrum
Fig. 2 is that different pressures is on the impact of percentage of grafting
Embodiment
In order to make technique means of the present invention, creation characteristic, to reach purpose and effect and be easy to understand and understand, below by specific embodiment, the present invention is explained in further detail.
Embodiment 1
1. taking 0.5g chitosan (CS) is dissolved in 20 mL 2% acetic acid aqueous solutions;
2. add a certain amount of silicon-dioxide (SiO
2) as pore-creating agent, a certain amount of ethylene glycol is as softening agent, and a certain amount of 0.25% glutaraldehyde stirs as linking agent;
3. get on the sheet glass that a certain amount of solution evenly is tiled in clean dried, under room temperature, after drying, 80 ℃ of the sodium hydroxide solutions with 5% soak 10 h, remove SiO
2, make porous-film;
4. the porous-film drying that makes is weighed, and take a certain amount of
N-N-isopropylacrylamide and vinylformic acid, and benzoyl peroxide are placed in autoclave;
5. make the autoclave sealing, put into ice-water bath, with the air in carbonic acid gas eliminating reactor, then be filled with the carbonic acid gas of 60g;
6. the reactor that will be filled with carbonic acid gas is put into water-bath, and 30
oC preheating 3 h fully mix raw material in precritical carbonic acid gas.Then slowly be warming up to 90
oC reaches predetermined pressure, reaction 10 h;
7. after reaction finishes, make reactor naturally cool to room temperature, emit carbonic acid gas in still, open the film after reactor can obtain grafting.
Embodiment 2
1. taking 0.5g chitosan (CS) is dissolved in 20 mL 2% acetic acid aqueous solutions;
2. add a certain amount of silicon-dioxide (SiO
2) as pore-creating agent, a certain amount of ethylene glycol is as softening agent, and a certain amount of 0.25% glutaraldehyde stirs as linking agent;
3. get on the sheet glass that a certain amount of solution evenly is tiled in clean dried, under room temperature, after drying, 80 ℃ of the sodium hydroxide solutions with 5% soak 10 h, remove SiO
2, make porous-film;
4. the porous-film drying that makes is weighed, and take a certain amount of
N-N-isopropylacrylamide and vinylformic acid, and benzoyl peroxide are placed in autoclave;
5. make the autoclave sealing, put into ice-water bath, with the air in carbonic acid gas eliminating reactor, then be filled with the carbonic acid gas of 65g;
6. the reactor that will be filled with carbonic acid gas is put into water-bath, and 30
oC preheating 3 h fully mix raw material in precritical carbonic acid gas.Then slowly be warming up to 90
oC reaches predetermined pressure, reaction 10 h;
7. after reaction finishes, make reactor naturally cool to room temperature, emit carbonic acid gas in still, open the film after reactor can obtain grafting.
Embodiment 3
1. taking 0.5g chitosan (CS) is dissolved in 20 mL 2% acetic acid aqueous solutions;
2. add a certain amount of silicon-dioxide (SiO
2) as pore-creating agent, a certain amount of ethylene glycol is as softening agent, and a certain amount of 0.25% glutaraldehyde stirs as linking agent;
3. get on the sheet glass that a certain amount of solution evenly is tiled in clean dried, under room temperature, after drying, 80 ℃ of the sodium hydroxide solutions with 5% soak 10 h, remove SiO
2, make porous-film;
4. the porous-film drying that makes is weighed, and take a certain amount of
N-N-isopropylacrylamide and vinylformic acid, and benzoyl peroxide are placed in autoclave;
5. make the autoclave sealing, put into ice-water bath, with the air in carbonic acid gas eliminating reactor, then be filled with the carbonic acid gas of 70g;
6. the reactor that will be filled with carbonic acid gas is put into water-bath, and 30
oC preheating 3 h fully mix raw material in precritical carbonic acid gas.Then slowly be warming up to 90
oC reaches predetermined pressure, reaction 10 h;
7. after reaction finishes, make reactor naturally cool to room temperature, emit carbonic acid gas in still, open the film after reactor can obtain grafting.
Embodiment 4
1. taking 0.5g chitosan (CS) is dissolved in 20 mL 2% acetic acid aqueous solutions;
2. add a certain amount of silicon-dioxide (SiO
2) as pore-creating agent, a certain amount of ethylene glycol is as softening agent, and a certain amount of 0.25% glutaraldehyde stirs as linking agent;
3. get on the sheet glass that a certain amount of solution evenly is tiled in clean dried, under room temperature, after drying, 80 ℃ of the sodium hydroxide solutions with 5% soak 10 h, remove SiO
2, make porous-film;
4. the porous-film drying that makes is weighed, and take a certain amount of
N-N-isopropylacrylamide and vinylformic acid, and benzoyl peroxide are placed in autoclave;
5. make the autoclave sealing, put into ice-water bath, with the air in carbonic acid gas eliminating reactor, then be filled with the carbonic acid gas of 75g;
6. the reactor that will be filled with carbonic acid gas is put into water-bath, and 30
oC preheating 3 h fully mix raw material in precritical carbonic acid gas.Then slowly be warming up to 90
oC reaches predetermined pressure, reaction 10 h;
7. after reaction finishes, make reactor naturally cool to room temperature, emit carbonic acid gas in still, open the film after reactor can obtain grafting.
Embodiment 5
1. taking 0.5g chitosan (CS) is dissolved in 20 mL 2% acetic acid aqueous solutions;
2. add a certain amount of silicon-dioxide (SiO
2) as pore-creating agent, a certain amount of ethylene glycol is as softening agent, and a certain amount of 0.25% glutaraldehyde stirs as linking agent;
3. get on the sheet glass that a certain amount of solution evenly is tiled in clean dried, under room temperature, after drying, 80 ℃ of the sodium hydroxide solutions with 5% soak 10 h, remove SiO
2, make porous-film;
4. the porous-film drying that makes is weighed, and take a certain amount of
N-N-isopropylacrylamide and vinylformic acid, and benzoyl peroxide are placed in autoclave;
5. make the autoclave sealing, put into ice-water bath, with the air in carbonic acid gas eliminating reactor, then be filled with the carbonic acid gas of 80g;
6. the reactor that will be filled with carbonic acid gas is put into water-bath, and 30
oC preheating 3 h fully mix raw material in precritical carbonic acid gas.Then slowly be warming up to 90
oC reaches predetermined pressure, reaction 10 h;
7. after reaction finishes, make reactor naturally cool to room temperature, emit carbonic acid gas in still, open the film after reactor can obtain grafting.
The present invention has prepared a kind of biological activity intelligent response film with temperature and pH doubling sensitivity, its preparation method is convenient, efficient and reaction process control is easy to be nontoxic, pollution-free, the easy purifying noresidue of product is a kind of eco-friendly " green " new synthetic method.
Claims (3)
1. novel method for preparing intelligent macromolecular membrane comprises the following steps:
(1) take a certain amount of chitosan (CS) and be dissolved in 2% acetic acid solution, add a certain amount of silicon-dioxide (SiO
2) as pore-creating agent, this solution is tiled on sheet glass, dry rear with sodium hydroxide solution immersion 10 h, remove SiO
2, make porous-film;
(2) the porous-film drying that makes is weighed, and take a certain amount of
N-N-isopropylacrylamide and vinylformic acid, and benzoyl peroxide are placed in autoclave;
(3) make the autoclave sealing, put into ice-water bath, then the air with in carbonic acid gas eliminating reactor is filled with a certain amount of carbonic acid gas;
The reactor that (4) will be filled with carbonic acid gas is put into water-bath, and 30
oC preheating 3 h fully mix raw material in precritical carbonic acid gas, then slowly be warming up to 80
oC reaches predetermined pressure, reaction 10 h;
(5) after reaction finishes, make reactor naturally cool to room temperature, emit carbonic acid gas in still, open the film after reactor can obtain grafting.
2. described how empty film graft-modification method according to claim 1, is characterized in that take supercritical co as solvent.
3. the method for reacting in supercritical co according to claim 1 is characterized in that utilizing easily pressure, the thermoregulation process of changing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101137350A CN103172901A (en) | 2013-04-03 | 2013-04-03 | New method for preparing intelligent polymeric membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101137350A CN103172901A (en) | 2013-04-03 | 2013-04-03 | New method for preparing intelligent polymeric membrane |
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| CN103172901A true CN103172901A (en) | 2013-06-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106395802A (en) * | 2016-09-08 | 2017-02-15 | 山东理工大学 | Method for preparing graphene porous membrane |
-
2013
- 2013-04-03 CN CN2013101137350A patent/CN103172901A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106395802A (en) * | 2016-09-08 | 2017-02-15 | 山东理工大学 | Method for preparing graphene porous membrane |
| CN106395802B (en) * | 2016-09-08 | 2020-08-11 | 山东理工大学 | Preparation method of graphene porous membrane |
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Application publication date: 20130626 |