CN110090561A - A kind of preparation method containing modified boehmite multifunctional membrane - Google Patents
A kind of preparation method containing modified boehmite multifunctional membrane Download PDFInfo
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- CN110090561A CN110090561A CN201910366665.7A CN201910366665A CN110090561A CN 110090561 A CN110090561 A CN 110090561A CN 201910366665 A CN201910366665 A CN 201910366665A CN 110090561 A CN110090561 A CN 110090561A
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- boehmite
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- esterification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/14—Membrane materials having negatively charged functional groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention provides a kind of preparation methods containing modified boehmite multifunctional membrane, belong to field of compound material.The preparation method obtains double bond containing esterification boehmite the following steps are included: be first esterified with organic acid containing double bonds to boehmite；Then esterification boehmite, polymer, pore-foaming agent and solvent are matched into preparation liquid, is film-made using phase inversion；Finally by film be immersed in containing initiator, monomer, a small amount of crosslinking agent water in, be graft-polymerized under nitrogen protection, obtain the multifunctional membrane containing modified boehmite；The film has the characteristics that good hydrophilic property, permeation flux are big, stain resistance is good, the pore size of pH value adjusting film can be passed through, anion, anionic surfactant and the anionic dye etc. in trap water can also can be acted on by electrical charge rejection and size exclusion by metal cation, cationic surfactant or the dye of positive ion etc. in ion exchange or complexing quick adsorption water body.
Description
Technical field
The present invention relates to field of compound material, and in particular to a kind of preparation side containing modified boehmite multifunctional membrane
Method.
Background technique
Boehmite (γ-Al00H) contains a large amount of hydroxyl, and good hydrophilic property has certain adsorption capacity, is used directly for
Prepare the modification of film and film.Such as with boehmite can prepare microfiltration membranes (patent: a kind of preparation method of composite ceramics microfiltration membranes,
A kind of preparation method etc. of environment-friendly ceramic microfiltration membranes)；As polyvinylidene fluoride (PVDF) ultrafiltration membrane is put into the vigorous nurse of nanofiber by Sun Feiyun
It is impregnated in stone solution, obtains the modification PVDF ultrafiltration membrane (patent: a kind of modification that hydrophily is strong, membrane flux is high, contamination resistance is strong
Ultrafiltration membrane and preparation method thereof)；It for another example records and only prepares adsorbed film with boehmite.
The esterification of boehmite can be used for the modification of material, as beam space passes through 5- amido-1,3,4-thiadiazoles -2- sulphur
The activity and chloroacetate reaction of sulfydryl in alcohol, prepare the corrosion inhibiter that end group is carboxylic acid group, then pass through esterification for inhibition
Agent is bonded with the hydroxyl in boehmite, is grafted to the surface of boehmite, and pH sensitivity release type inhibition antirust filler is made；Such as Chen Wei
Dimension is prepared for methacrylic acid (MAA) in-situ modified rubber (SBR)/boehmite (BM) nano combined material by direct blending
Material, MAA can be grafted to the surface BM by esterification and complexation reaction during processing, and be reacted by Diene-addition
It is grafted to above SBR strand, improves dispersion of the BM in rubber SBR, enhance the strong interaction between SBR and BM, thus
Greatly improve the mechanical property and interface cohesion of composite material.
It can be used for film containing carboxyl and sulfonic polymer such as polyacrylic acid (sodium), kayexalate good hydrophilic property
Hydrophilic modifying has and prepares Modified Membrane using Graft Method, if Yuan Gaoming is using asymmetric aluminium oxide as supporter, aluminate coupling agent,
Grafted polyacrylic acid (PAA) prepares hydrophily PAA-Al2O3Composite membrane；Flat Zheng Hua etc. is with Al2O3For bottom, using positive silicic acid
Ethyl ester (TEOS) vapour deposition process introduces activity SiO2Layer, then using silane coupling agent as transition zone, grafted polyacrylic acid (PAA)
Mode prepare hydrophilic macromolecule-ceramic composite membrane, for separating water-alcohol mixture；Also have and changed using construction from part preparation
Property ultrafiltration membrane (CN101053779A, a kind of method for preparing hydrophilic low catching molecular composite ultrafiltering membrane)；Containing carboxyl and sulfonic acid
The polymer of base can be used for preparing adsorbed film, such as using blending method prepare adsorbed film (patent, 201610941576.7, one
Adsorption ultrafiltrate film of the kind containing kayexalate).When preparing film using blending and construction from part, it polymerize containing carboxyl with sulfonic
Object is because water-soluble strong, and there is be dissolved in water without the risk lost that stops in use.
Boehmite is weak to cation adsorbing capabilities, not soluble in water；And containing carboxyl, sulfonic polymer such as polyacrylic acid,
Polyphenyl sodium sulfonate etc. has very strong adsorption capacity to ionic dye cationic in water body, cation surface activating and metal ion,
But their good hydrophilic properties are dissolved in water.It is prepared by the shortcomings that in order to overcome the two, the method for passing through the esterification of boehmite, blending, grafting
Containing the filter membrane with a large amount of carboxyls, sulfonic polymer modification boehmite particulate, not only anti-fouling performance is good for this film, film
Pore size it is adjustable using pH value, and in the case where strainability is constant, there are also suction-operated, can go to remove water
Negatively charged removal anionic part can also be used in deleterious cations substance in body.
Summary of the invention
The purpose of the present invention is a kind of modified boehmite multifunctional membranes aiming at the problem that background technique proposes, designed
Preparation method, this method obtain boehmite and organic acid reaction containing double bond to be esterified boehmite containing double bond, then will be esterified vigorous nurse
Stone, polymer, pore-foaming agent and solvent match preparation liquid, are film-made using phase inversion；Finally by film be immersed in containing initiator, monomer,
It in the water of a small amount of crosslinking agent, is graft-polymerized under nitrogen protection, obtains the multifunctional membrane containing modified boehmite；The film has
The feature that good hydrophilic property, permeation flux are big, stain resistance is good can pass through the pore size of pH value adjusting film, can be handed over by ion
Change or complexing quick adsorption water body in metal cation, cationic surfactant or the dye of positive ion etc., can also be with
Anion, anionic surfactant and the anionic dye etc. in trap water are acted on by electrical charge rejection and size exclusion.
Inventor passes through a large number of experiments and unremitting effort, is finally obtained following scheme:
A kind of preparation method containing modified boehmite multifunctional membrane, method includes the following steps:
(1) boehmite be first added to the water or the water containing a certain amount of hydroquinone in or be added dimethylbenzene in carry out at dispersion
Then reason is added double bond containing organic acid and carries out esterification, obtains double bond containing esterification boehmite, esterification condition
Are as follows: at 70-100 DEG C of temperature aqueous solution be stirred to react 10-72 hours or in dimethylbenzene, 138-145 DEG C reflux 10-72 hours；
The molar ratio of the boehmite and the organic acid containing double bond is 1:1-1:4；
The double bond containing organic acid is acrylic acid, methacrylic acid, butene dioic acid, styrene sulfonic acid, trans--benzene second
Any one of alkene acetic acid, 4- phenyl -3-butenoic acid；
Concentration of the boehmite in water or in the water containing a certain amount of hydroquinone or in dimethylbenzene is 1-8wt%；
(2) polymer, double bond containing esterification boehmite, solvent, pore-foaming agent are mixed, it is small in 50-70 DEG C of constant temperature stirring 24
Shi Peicheng film making solution, is film-made using immersion precipitation phase inversion process, and the film of preparation, which is placed in pure water, to be impregnated 24 hours or more, wherein
Polymer content is 16-24wt% in film making solution, esterification boehmite is 0.5-5wt%, pore-foaming agent 1-8wt%, and solvent is
63-82.5wt%；
The polymer is any one of polysulfones, polyether sulfone, polyacrylonitrile, polyvinyl chloride, Kynoar；
The solvent is any one of dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, N-Methyl pyrrolidone
Or it is a variety of；
The pore-foaming agent is any one of polyethylene glycol, polyvinylpyrrolidone, lithium chloride；
(3) film prepared by step (2) is put into monomer containing 3wt%, the initiator of 0.015wt% and 0.5wt%
It is impregnated in the aqueous solution of crosslinking agent, is passed through nitrogen, be heated to 65-75 DEG C and react 4 hours, take out washing, obtained containing modified vigorous nurse
Stone multifunctional membrane；
The monomer is acrylic acid, in sodium acrylate, methacrylic acid, Sodium methacrylate, sodium p styrene sulfonate
It is any one or more；
The initiator is any one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate；
The crosslinking agent is any one of ethylene glycol and diethylenetriamine.
Preferably, a kind of preparation method containing modified boehmite multifunctional membrane as described above, it is single in the step (3)
Body, initiator, crosslinking agent concentration be each substance aqueous solution mass concentration.
The present invention is as follows using the principle of boehmite and the organic acid reaction containing double bond: contain great amount of hydroxy group on boehmite, with
Carboxyl in organic acid containing double bond reacts, and dehydration obtains double bond containing ester.
Compared with prior art, advantages of the present invention are as follows:
1, by the esterification of boehmite and the organic acid containing double bond, double bond containing active monomer is secured by covalent bond
Ground is incorporated on boehmite, and then can easily carry out subsequent graft modification, to overcome the profit of hydrophobic adsorbent
The problems such as wet problem or the water solubility of hydrophilic adsorbent.
2, what is be prepared contains a large amount of carboxyl or sulfonic group containing modified boehmite multifunctional membrane, with the following functions:
The good hydrophilic property of film has the characteristics that stain resistance is strong, permeation flux is big；The pore size of film is adjustable by pH value, in acid
The aperture of property condition lower film becomes smaller, and aperture becomes larger under alkaline condition；Ion exchange or complexing quick adsorption water body can be passed through
In metal cation, cationic surfactant or the dye of positive ion etc., have the characteristics that large amount of adsorption, the rate of adsorption are fast；
The surface of film is negatively charged, can pass through anion, the anion table in electrical charge rejection and size exclusion effect effect retention water body
Face activating agent and anionic dye etc.；It is grafted on boehmite not soluble in water containing carboxyl or sulfonic water-soluble polymer,
It is wrapped by and is fixed in film, avoid the loss by dissolution problem of water-soluble polymer；Film temperature in grafting process is higher, membrane aperture
The film for becoming smaller and reaching stable, prepared can be shunk and belong to ultrafiltration membrane and nanofiltration membrane scope.
Detailed description of the invention
Fig. 1 is the schematic diagram that boehmite is reacted with acrylic acid.
Specific embodiment
Below in conjunction with attached drawing, embodiments of the present invention is further illustrated, to make the purpose of the present invention, technical solution and excellent
Point is clearer, below technical solution in the present invention be clearly and completely described, it is clear that described embodiment is this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation method containing modified boehmite multifunctional membrane, method includes the following steps:
(1) 50 gram of boehmite (0.83mol), which is added in 800 milliliters of distilled water, disperses, and is ultrasonically treated, 5 minutes
3 grams of hydroquinones are added afterwards；Then be slowly added to methacrylic acid (154g, 1.8mol) at room temperature, 70 DEG C stirring under into
Row reaction in 20 hours, solid matter with deionized water washing, finally in a vacuum 50 DEG C drying 20 hours i.e. obtain esterification suddenly
Nurse stone.
(2) it is mixed with 20g polyether sulfone, 1g esterification boehmite, 1g polyvinylpyrrolidone and 78g dimethyl acetamide,
60 DEG C of stirrings, 24 hours wiring solution-formings are film-made by gel media of water, and evaporation time is 30 seconds, and it is small that film puts immersion 24 in water
When.
(3) second of the acrylic acid with 500 milliliters of aqueous solutions preparations containing 3wt%, the potassium peroxydisulfate of 0.015wt%, 0.5wt%
Two alcohol solutions are poured into the container of dress film, lead to nitrogen, are heated to 72 DEG C, are reacted 4 hours, are then washed, containing modified vigorous nurse
The performance of stone multifunctional membrane, film is shown in Table 1.
Embodiment 2
A kind of preparation method containing modified boehmite multifunctional membrane, method includes the following steps:
(1) it disperses 10.0g boehmite in 250mL dimethylbenzene, adds 48g acrylic acid, mixture 138- in dimethylbenzene
145 DEG C are flowed back 72 hours, and vacuum distillation removal dimethylbenzene washs solid removal impurity with ether, obtain white esterification after dry
Boehmite powder.
(2) it is mixed with 24g polyvinyl chloride, 5g esterification boehmite, 8g polyethylene glycol and 73g N-Methyl pyrrolidone, 60
DEG C stirring 24 hours wiring solution-formings, using water be gel media be film-made, evaporation time be 10 seconds, film put in water immersion 26 hours.
(3) the ethylene glycol water of sodium p styrene sulfonate containing 3wt%, the ammonium persulfate of 0.015wt%, 0.5wt% are prepared
It 800 milliliters of solution, is poured into the container of dress film, leads to nitrogen, be heated to 65-70 DEG C, react 4 hours, then wash, containing modification
Boehmite multifunctional membrane.
Embodiment 3
A kind of preparation method containing modified boehmite multifunctional membrane, method includes the following steps:
(1) 50 gram of boehmite (0.83mol), which is added in 800 milliliters of distilled water, disperses, and is ultrasonically treated, 5 minutes
3 grams of hydroquinones are added afterwards；Then be slowly added to methacrylic acid (154g, 1.8mol) at room temperature, 70 DEG C stirring under into
Row reaction in 20 hours, solid matter with deionized water washing, finally in a vacuum 50 DEG C drying 20 hours i.e. obtain esterification suddenly
Nurse stone.
(2) it is mixed with 16g polyacrylonitrile, 0.5g esterification boehmite, 1g polyvinylpyrrolidone and 82.5g dimethyl sulfoxide,
It in 60 DEG C of stirrings, 24 hours wiring solution-formings, is film-made by gel media of water, evaporation time is 30 seconds, and film is put impregnates 24 in water
Hour.
(3) sodium peroxydisulfate, the 0.5wt% of the methacrylic acid with 500 milliliters of aqueous solutions preparations containing 3wt%, 0.015wt%
Glycol water, be poured into the container of dress film, lead to nitrogen, be heated to 72-75 DEG C, react 4 hours, then wash, contain
Modified boehmite multifunctional membrane.
The sample that we prepare embodiment 1, is determined its performance, is specifically shown in Table 1.
The performance of table 1, modified boehmite multifunctional membrane
Note: the pH value of 1. test fluids 0.01M sodium hydroxide solution and 0.01M aqueous hydrochloric acid solution are adjusted.
2. feeding liquid Pb2+、Cd2+, chromate concentration be 20ppm, 25 DEG C of temperature.
Claims (1)
1. a kind of preparation method containing modified boehmite multifunctional membrane, it is characterised in that: method includes the following steps:
(1) boehmite be first added to the water or the water containing a certain amount of hydroquinone in or be added dimethylbenzene in carry out decentralized processing, so
After double bond containing organic acid be added carry out esterification, obtain double bond containing esterification boehmite, esterification condition are as follows: temperature
Be stirred to react at 70-100 DEG C 10-72 hours or in dimethylbenzene, 138-145 DEG C reflux 10-72 hours；
The molar ratio of the boehmite and the organic acid containing double bond is 1:1-1:4；
The double bond containing organic acid is acrylic acid, methacrylic acid, butene dioic acid, styrene sulfonic acid, trans--styrene second
Any one of acid, 4- phenyl -3-butenoic acid；
Concentration of the boehmite in water or in the water containing a certain amount of hydroquinone or in dimethylbenzene is 1-8wt%；
(2) polymer, double bond containing esterification boehmite, solvent, pore-foaming agent are mixed, is stirred 24 hours under 50-70 DEG C of constant temperature
It is made into film making solution, is film-made using immersion precipitation phase inversion process, the film of preparation, which is placed in pure water, to be impregnated 24 hours or more, wherein making
Polymer content is 16-24wt% in coating solution, esterification boehmite is 0.5-5wt%, pore-foaming agent 1-8wt%, solvent 63-
82.5wt%；
The polymer is any one of polysulfones, polyether sulfone, polyacrylonitrile, polyvinyl chloride and Kynoar；
The solvent is dimethylformamide, in dimethyl acetamide, dimethyl sulfoxide, N-Methyl pyrrolidone
It is any one or more；
The pore-foaming agent is any one of polyethylene glycol, polyvinylpyrrolidone, lithium chloride；
(3) film prepared by step (2) is put into the crosslinking agent of monomer containing 3wt%, the initiator of 0.015wt% and 0.5wt%
It is impregnated in aqueous solution, is passed through nitrogen, be heated to 65-75 DEG C and react 4 hours, take out washing, obtained multi-functional containing modified boehmite
Film；
The monomer is acrylic acid, sodium acrylate, methacrylic acid, Sodium methacrylate, any in sodium p styrene sulfonate
Kind is a variety of；
The initiator is any one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate；
The crosslinking agent is any one of ethylene glycol and diethylenetriamine.
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| CN201811530190 | 2018-12-13 | ||
| CN2018115301902 | 2018-12-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112999896A (en) * | 2021-03-11 | 2021-06-22 | 上海洁晟环保科技有限公司 | Boehmite modified adsorption film and preparation method and application thereof |
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2019
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| CN1656161A (en) * | 2002-04-19 | 2005-08-17 | 圣戈本陶瓷及塑料股份有限公司 | Novel boehmite particles and polymer materials incorporating same |
| US20070098990A1 (en) * | 2002-06-12 | 2007-05-03 | Cook Ronald L | Nanoparticles modified with multiple organic acids |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112999896A (en) * | 2021-03-11 | 2021-06-22 | 上海洁晟环保科技有限公司 | Boehmite modified adsorption film and preparation method and application thereof |
| CN112999896B (en) * | 2021-03-11 | 2023-12-22 | 西西埃热能(南京)有限公司 | Boehmite modified adsorption film and preparation method and application thereof |
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Application publication date: 20190806 |