CN110339727A - A kind of preparation method and application of lead (II) ion trace composite membrane - Google Patents
A kind of preparation method and application of lead (II) ion trace composite membrane Download PDFInfo
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- CN110339727A CN110339727A CN201910589870.XA CN201910589870A CN110339727A CN 110339727 A CN110339727 A CN 110339727A CN 201910589870 A CN201910589870 A CN 201910589870A CN 110339727 A CN110339727 A CN 110339727A
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- 239000012528 membrane Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 210000004379 membrane Anatomy 0.000 claims abstract description 44
- 150000002500 ions Chemical class 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 8
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- -1 acryloyl Amine Chemical class 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 238000007872 degassing Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 150000003235 pyrrolidines Chemical class 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 6
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002607 hemopoietic effect Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention discloses a kind of preparation method and application of lead (II) ion trace composite membrane, belongs to absorption and separation function technical field of polymer materials.The method of the invention is using lead (II) ion as template ion, using compound N-ethyl (1- benzene)-N- ethyl (2- diphenylphosphine) -2- acrylamide of autonomous Design synthesis as function monomer, ethylene glycol dimethacrylate is crosslinking agent, azodiisobutyronitrile is initiator, commercial membranes are basement membrane, the mixed solution of organic solvent and water is pore-foaming agent, using surface grafting blotting, by hot initiation method in support membrane surface imprinted polymer thin layer.The compound membrane preparation method of lead (II) ion blotting provided by the invention is easy to operate, and economic cost is low, and obtained lead (II) ion blotting composite membrane can adsorb with high selectivity and remove the lead in aqueous solution (II) ion.
Description
Technical field
The present invention relates to a kind of preparation method and applications of lead (II) ion trace composite membrane, belong to absorption and separation function
Technical field of polymer materials.
Background technique
An important development direction of the metal ion engram technology as molecular imprinting technology, to environment, life and material
The fields such as science all have important science and application value.Ionic imprinting technique be using ion as template, by electrostatic interaction,
Coordination etc. forms chelate in conjunction with monomer, is eluted template ion with acid reagent etc. after polymerization, and final be made has
The imprinted material of three-dimensional cavity structure corresponding with target metal ions.
Membrane separation technique refer on a molecular scale, the mixture of different-grain diameter molecule when passing through semi-permeable membrane, realize choosing
The technology for selecting separation can be divided into microfiltration membranes (MF), ultrafiltration membrane (UF), nanofiltration membrane (NF) and reverse osmosis membrane according to pore size
(RO) etc., common organic fluoride-containing product film mainly has polytetrafluoroethylene (PTFE) (PTFE) and Kynoar (PVDF).And current
Product film cannot achieve the Selective Separation to single material, and metal ion engram technology is specific objective ion from its structure
It is separated in the mixture of analog and provides feasible effective solution approach.
Therefore, metal ion engram technology is combined with membrane separation technique, is mentioned for efficient and single-minded identification metal ion
Practical technique is supplied.Nowadays heavy metal pollution not only causes serious destruction to environment, but also causes seriously to human health
Threat.Wherein lead is that one kind is more toxic, and property is stable, is difficult to the heavy metal contaminants being degraded.Lead is in human body
Accumulation, can damage respiratory system, nervous system and hemopoietic system etc., therefore how effectively to solve the problems, such as that lead contamination is that the mankind are current
The vital task faced.
Summary of the invention
The present invention provides a kind of preparation method of lead (II) ion trace composite membrane, it is by ionic imprinting technique and membrane technology
It effectively combines, synthesizes lead (II) ion blotting composite membrane, operating process is easy, mild condition；Use the method for the invention
Lead (II) the ion blotting composite membrane being prepared can be simple and quick, carries out identification suction to lead (II) ion with high selectivity
It is attached, there is very high application value.
The method of the invention specifically includes the following steps:
(1) template ion Pb (II): being dissolved in porogenic solvents by the preparation of pre-polymer solution in the ratio of 0.005~0.01g/L,
Function monomer N- ethyl (1- benzene)-N- ethyl (2- diphenylphosphine) -2- acrylamide is added, vibrates 2~3h at room temperature, most
After sequentially add crosslinking agent ethylene glycol dimethacrylate, initiator azodiisobutyronitrile, ultrasonic degassing handles 5~10min,
Form pre-polymer solution.
(2) preparation of lead (II) ion blotting composite membrane: basement membrane is placed in the pre-polymer solution in above-mentioned steps (1), often
Temperature is lower to impregnate 3~60min, then heats to 24~48h of reaction at 60~70 DEG C, obtains lead (II) ion blotting composite membrane,
Template ion finally is removed with methanol and the elution of acetic acid mixed solution, it is multiple to obtain lead (II) ion blotting with three-dimensional hole
Close film.
Preferably, template ion, function monomer and crosslinking agent molar ratio described in step (1) of the present invention are 1:(4~10):
The quality molar ratio of (20~50), initiator and function monomer is 1:(10~15).
Preferably, pore-foaming agent of the present invention is the mixed solution of organic solvent and water, the volume ratio of organic solvent and water
For (1:3)~(3:1), wherein organic solvent is one of methanol, ethyl alcohol, acetonitrile, n,N-Dimethylformamide, isopropanol.
Preferably, function monomer N- ethyl (1- benzene)-N- ethyl (2- diphenylphosphine) -2- acrylamide of the present invention
The preparation method is as follows:
(1) 10~20mmol compound N-hydroxyethyl hydroxyethyl is weighed in reaction vessel, and is dissolved with 50~70mL HCl, instead
1- (2- vinyl chloride) pyrrolidines should be generated, 2~5h is heated to reflux, it is cooling with ice-water bath later, then by 5~10mmol acryloyl
Amine is added in above-mentioned reaction, continues heating stirring and reacts 5~10h, after fully reacting, is cooled to room temperature, by 10~30ml propylene
Acyl chlorides is added dropwise in above-mentioned mixed liquor after cooling, is dripped off and is removed ice-water bath, and room temperature reaction 12~for 24 hours；
(2) it post-processes: after completion of the reaction, first filtering, filtrate is extracted with chloroform, washing PH to neutrality, after anhydrous sodium sulfate is dry
It filters, after vacuum concentration, residue carries out column chromatography, petroleum ether and ethyl acetate with the mixed solution of petroleum ether and ethyl acetate
Volume ratio be (20~30): (1~5), isolated pale yellow oily liquid.
Preferably, the volume ratio of methanol and acetic acid is (1~9) in methanol and acetic acid mixed solution in step (2) of the present invention:
1。
Preferably, step (2) the of the present invention basement membrane is polytetrafluoroethylene (PTFE) miillpore filter (PTFE), Kynoar micropore
One of filter membrane (PVDF), nylon-6 miillpore filter (Nylon-6), the basement membrane are commercial product.
Lead (II) the ion blotting composite membrane being prepared another object of the present invention is to provide the method is for inhaling
Lead (II) ion in Fufen exsolution liquid.
The beneficial effects of the present invention are:
(1) the method for the invention uses surface grafting engram technology, the compound N-ethyl (1- benzene)-synthesized with autonomous Design
N- ethyl (2- diphenylphosphine) -2- acrylamide overcomes existing divalent using business miillpore filter as support membrane for function monomer
The disadvantages of preparation of lead ion adsorbent material is difficult, complicated for operation.
(2) the ion blotting composite membrane of the method for the invention preparation, which makes recognition site be exposed to film surface, to improve
Its singleness identity, and its adsorbance to lead (II) ion can also be improved.
Specific embodiment
Invention is further described in detail combined with specific embodiments below, but protection scope of the present invention is not limited to
The content.
Embodiment 1
A kind of preparation method of lead (II) ion trace composite membrane, specifically includes the following steps:
(1) it prepares function monomer: weighing 10mmol compound N-hydroxyethyl hydroxyethyl and dissolved in there-necked flask, and with 50mLHCl,
Reaction generates 1- (2- vinyl chloride) pyrrolidines, is heated to reflux 2h, cooling with ice-water bath later, then 5mmol acrylamide is added
Enter in above-mentioned reaction, continues heating stirring and react 6h, after fully reacting, be cooled to room temperature, 12ml acryloyl chloride is added dropwise to
It in above-mentioned mixed liquor after cooling, drips off and removes ice-water bath, react at room temperature 12h.After completion of the reaction, it first filters, filtrate chloroform
Extraction, washing PH to neutrality, anhydrous sodium sulfate filters after drying, and after vacuum concentration, residue is with petroleum ether and ethyl acetate
The volume ratio of mixed solution progress column chromatography, petroleum ether and ethyl acetate is 20:1, isolated pale yellow oily liquid.
(2) by 0.1mmolPb (NO3)2Being added to volume ratio is in the methanol and water mixed solution pore-foaming agent of 1:1, to whole
0.4mmol function monomer N- ethyl (1- benzene)-N- ethyl (2- diphenylphosphine) -2- acrylamide, room temperature oscillation is added in dissolution
3h is uniformly mixed it, and 2mmol crosslinking agent ethylene glycol dimethacrylate and two isobutyl of 15mg initiator azo is then added
Nitrile shakes up, and ultrasonic degassing handles 10min to get prepolymerization liquid is arrived.
(3) polyvinylidene fluoride microporous filtering film is placed in the prepolymerization liquid that step (1) obtains, soak at room temperature 3min, then
Thermal booster reaction is for 24 hours at 60 DEG C.
(4) methanol and acetic acid mixed solution eluted template ion for being 9:1 with volume ratio, reuses methanol and washs into
Property to get to and template ion shape, size match and there is lead (II) the ion blotting composite membrane in three-dimensional hole.
20.00mg lead (II) ion blotting composite membrane that the present embodiment is prepared is applied and is in lead (II) concentration
Isothermal adsorption is carried out in 18mg/mL solution；As the result is shown: the adsorbance of lead (II) ion blotting composite membrane is 990.49 μm of ol/
G, imprinting factor 1.78.
Embodiment 2
A kind of preparation method of lead (II) ion trace composite membrane, specifically includes the following steps:
(1) it prepares function monomer: weighing 17mmol compound N-hydroxyethyl hydroxyethyl and dissolved in there-necked flask, and with 72mLHCl,
Reaction generates 1- (2- vinyl chloride) pyrrolidines, is heated to reflux 3h, cooling with ice-water bath later, then 10mmol acrylamide is added
Enter in above-mentioned reaction, continues heating stirring and react 7h, after fully reacting, be cooled to room temperature, 13ml acryloyl chloride is added dropwise to
It in above-mentioned mixed liquor after cooling, drips off and removes ice-water bath, react at room temperature 14h.After completion of the reaction, it first filters, filtrate chloroform
Extraction, washing PH to neutrality, anhydrous sodium sulfate filters after drying, and after vacuum concentration, residue is with petroleum ether and ethyl acetate
The volume ratio of mixed solution progress column chromatography, petroleum ether and ethyl acetate is 30:5, isolated pale yellow oily liquid.
(2) by 0.1mmolPb (NO3)2Being added to volume ratio is in the ethyl alcohol and water mixed solution pore-foaming agent of 1:1, to whole
0.6mmol function monomer N- ethyl (1- benzene)-N- ethyl (2- diphenylphosphine) -2- acrylamide, room temperature oscillation is added in dissolution
3h is uniformly mixed it, and 3mmol crosslinking agent ethylene glycol dimethacrylate and two isobutyl of 15mg initiator azo is then added
Nitrile shakes up, and ultrasonic degassing handles 10min to get prepolymerization liquid is arrived.
(3) polytetrafluoroethylene (PTFE) miillpore filter (PTFE) is placed in the prepolymerization liquid that step (1) obtains, soak at room temperature
10min, then thermal booster reaction is for 24 hours at 60 DEG C.
(4) methanol and acetic acid mixed solution eluted template ion for being 9:1 with volume ratio, reuses methanol and washs into
Property to get to and template ion shape, size match and there is lead (II) the ion blotting composite membrane in three-dimensional hole.
20.00 mg lead (II) ion blotting composite membranes that the present embodiment is prepared are applied is in lead (II) concentration
Isothermal adsorption is carried out in 18mg/mL solution；As the result is shown: the adsorbance of lead (II) ion blotting composite membrane is 1010.31 μm of ol/
G imprinting factor is 2.01.
Embodiment 3
A kind of preparation method of lead (II) ion trace composite membrane, specifically includes the following steps:
(1) it prepares function monomer: weighing 14mmol compound N-hydroxyethyl hydroxyethyl and dissolved in there-necked flask, and with 60mLHCl,
Reaction generates 1- (2- vinyl chloride) pyrrolidines, is heated to reflux 4h, cooling with ice-water bath later, then 8mmol acrylamide is added
Enter in above-mentioned reaction, continues heating stirring and react 7h, after fully reacting, be cooled to room temperature, 15ml acryloyl chloride is added dropwise to
It in above-mentioned mixed liquor after cooling, drips off and removes ice-water bath, react at room temperature 18h.After completion of the reaction, it first filters, filtrate chloroform
Extraction, washing PH to neutrality, anhydrous sodium sulfate filters after drying, and after vacuum concentration, residue is with petroleum ether and ethyl acetate
The volume ratio of mixed solution progress column chromatography, petroleum ether and ethyl acetate is 25:4, isolated pale yellow oily liquid.
(2) by 0.1mmol Pb (NO3)2Being added to volume ratio is in the acetonitrile and water mixed solution pore-foaming agent of 1:1, to complete
0.4mmol function monomer N- ethyl (1- benzene)-N- ethyl (2- diphenylphosphine) -2- acrylamide, room temperature oscillation is added in portion's dissolution
3h is uniformly mixed it, and 4mmol crosslinking agent ethylene glycol dimethacrylate and two isobutyl of 15mg initiator azo is then added
Nitrile shakes up, and ultrasonic degassing handles 10min to get prepolymerization liquid is arrived.
(3) nylon-6 miillpore filter (Nylon-6) is placed in the prepolymerization liquid that step (1) obtains, soak at room temperature
20min, then thermal booster reaction is for 24 hours at 60 DEG C.
(4) methanol and acetic acid mixed solution eluted template ion for being 9:1 with volume ratio, reuses methanol and washs into
Property to get to and template ion shape, size match and there is lead (II) the ion blotting composite membrane in three-dimensional hole.
20.00mg lead (II) ion blotting composite membrane that the present embodiment is prepared is applied and is in lead (II) concentration
Isothermal adsorption is carried out in 18mg/mL solution.As the result is shown: the adsorbance of lead (II) ion blotting composite membrane is 957.43 μm of ol/g
Imprinting factor is 1.60.
Embodiment 4
A kind of preparation method of lead (II) ion trace composite membrane, specifically includes the following steps:
(1) it prepares function monomer: weighing 15mmol compound N-hydroxyethyl hydroxyethyl and dissolved in there-necked flask, and with 65mLHCl,
Reaction generates 1- (2- vinyl chloride) pyrrolidines, is heated to reflux 5h, cooling with ice-water bath later, then 7mmol acrylamide is added
Enter in above-mentioned reaction, continues heating stirring and react 9h, after fully reacting, be cooled to room temperature, 11ml acryloyl chloride is added dropwise to
It in above-mentioned mixed liquor after cooling, drips off and removes ice-water bath, react at room temperature 20h.After completion of the reaction, it first filters, filtrate chloroform
Extraction, washing PH to neutrality, anhydrous sodium sulfate filters after drying, and after vacuum concentration, residue is with petroleum ether and ethyl acetate
The volume ratio of mixed solution progress column chromatography, petroleum ether and ethyl acetate is 28:3, isolated pale yellow oily liquid.
(2) by 0.1mmol Pb (NO3)2It is added to the N,N-dimethylformamide and water mixed solution cause that volume ratio is 1:1
In the agent of hole, to whole dissolutions, 0.6mmol function monomer N- ethyl (1- benzene)-N- ethyl (2- diphenylphosphine) -2- acryloyl is added
Amine, room temperature vibrate 3h, are uniformly mixed it, and 5mmol crosslinking agent ethylene glycol dimethacrylate is then added and 15mg causes
Agent azodiisobutyronitrile, shakes up, and ultrasonic degassing handles 10min to get prepolymerization liquid is arrived；
(3) polyvinylidene fluoride microporous filtering film is placed in the prepolymerization liquid that step (1) obtains, soak at room temperature 30min, then 60
Thermal booster reaction is for 24 hours at DEG C；
(4) methanol and acetic acid mixed solution eluted template ion for being 9:1 with volume ratio reuses methanol and washs to neutrality, i.e.,
Obtain with and template ion shape, size match and there is lead (II) the ion blotting composite membrane in three-dimensional hole.
20.00 mg lead (II) ion blotting composite membranes that the present embodiment is prepared are applied is in lead (II) concentration
Isothermal adsorption is carried out in 18mg/mL solution.As the result is shown: the adsorbance of lead (II) ion blotting composite membrane is 960.76 μm of ol/g
Imprinting factor is 1.58.
Embodiment 5
A kind of preparation method of lead (II) ion trace composite membrane, specifically includes the following steps:
(1) it prepares function monomer: weighing 20mmol compound N-hydroxyethyl hydroxyethyl and dissolved in there-necked flask, and with 55mLHCl,
Reaction generates 1- (2- vinyl chloride) pyrrolidines, is heated to reflux 4h, cooling with ice-water bath later, then 7mmol acrylamide is added
Enter in above-mentioned reaction, continues heating stirring and react 10h, after fully reacting, be cooled to room temperature, 30ml acryloyl chloride is added dropwise to
It in above-mentioned mixed liquor after cooling, drips off and removes ice-water bath, room temperature reaction is for 24 hours.After completion of the reaction, it first filters, filtrate chloroform
Extraction, washing PH to neutrality, anhydrous sodium sulfate filters after drying, and after vacuum concentration, residue is with petroleum ether and ethyl acetate
The volume ratio of mixed solution progress column chromatography, petroleum ether and ethyl acetate is 25:5, isolated pale yellow oily liquid.
(2) by 0.1mmolPb (NO3)2Being added to volume ratio is in the isopropanol and water mixed solution pore-foaming agent of 1:1, to complete
0.4mmol function monomer N- ethyl (1- benzene)-N- ethyl (2- diphenylphosphine) -2- acrylamide, room temperature oscillation is added in portion's dissolution
3h is uniformly mixed it, and 2mmol crosslinking agent ethylene glycol dimethacrylate and two isobutyl of 15mg initiator azo is then added
Nitrile shakes up, and ultrasonic degassing handles 10min to get prepolymerization liquid is arrived.
(3) polyvinylidene fluoride microporous filtering film is placed in the prepolymerization liquid that step 1 obtains, soak at room temperature 60min, then
Thermal booster reaction is for 24 hours at 60 DEG C.
(4) methanol and acetic acid mixed solution eluted template ion for being 9:1 with volume ratio, reuses methanol and washs into
Property to get to and template ion shape, size match and there is lead (II) the ion blotting composite membrane in three-dimensional hole.
20.00 mg lead (II) ion blotting composite membranes that the present embodiment is prepared are applied is in lead (II) concentration
Isothermal adsorption is carried out in 18mg/mL solution.As the result is shown: the adsorbance of lead (II) ion blotting composite membrane is 1020.89 μm of ol/
G imprinting factor is 1.77.
Above the embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment party
Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art
Various change out.
Claims (7)
1. a kind of preparation method of lead (II) ion trace composite membrane, which is characterized in that specifically includes the following steps:
(1) template ion Pb (II): being dissolved in porogenic solvents by the preparation of pre-polymer solution in the ratio of 0.005~0.01g/L,
Function monomer N- ethyl (1- benzene)-N- ethyl (2- diphenylphosphine) -2- acrylamide is added, vibrates 2~3h at room temperature, most
After sequentially add crosslinking agent ethylene glycol dimethacrylate, initiator azodiisobutyronitrile, ultrasonic degassing handles 5~10min,
Form pre-polymer solution；
(2) preparation of lead (II) ion blotting composite membrane: basement membrane is placed in the pre-polymer solution in above-mentioned steps (1), under room temperature
3~60min is impregnated, 24~48h of reaction at 60~70 DEG C is then heated to, obtains lead (II) ion blotting composite membrane, finally
Template ion is removed with methanol and the elution of acetic acid mixed solution, it is compound to obtain lead (II) ion blotting with three-dimensional hole
Film.
2. method according to claim 1, which is characterized in that template ion, function monomer and crosslinking agent described in step (1)
Molar ratio is 1:(4~10): the quality molar ratio of (20~50), initiator and function monomer is 1:(10~15).
3. method according to claim 1, it is characterised in that: the pore-foaming agent is the mixed solution of organic solvent and water, is had
Solvent and the volume ratio of water are (1:3)~(3:1), and wherein organic solvent is methanol, ethyl alcohol, acetonitrile, N, N- dimethyl formyl
One of amine, isopropanol.
4. method according to claim 1, it is characterised in that: function monomer N- ethyl (1- benzene)-N- ethyl (2- diphenyl
Phosphorus) -2- acrylamide the preparation method is as follows:
(1) 10~20mmol compound N-hydroxyethyl hydroxyethyl is weighed in reaction vessel, and is dissolved with 50~70mL HCl, instead
1- (2- vinyl chloride) pyrrolidines should be generated, 2~5h is heated to reflux, it is cooling with ice-water bath later, then by 5~10mmol acryloyl
Amine is added in above-mentioned reaction, continues heating stirring and reacts 5~10h, after fully reacting, is cooled to room temperature, by 10~30ml propylene
Acyl chlorides is added dropwise in above-mentioned mixed liquor after cooling, is dripped off and is removed ice-water bath, and room temperature reaction 12~for 24 hours；
(2) it post-processes: after completion of the reaction, first filtering, filtrate is extracted with chloroform, washing PH to neutrality, after anhydrous sodium sulfate is dry
It filters, after vacuum concentration, residue carries out column chromatography, petroleum ether and ethyl acetate with the mixed solution of petroleum ether and ethyl acetate
Volume ratio be (20~30): (1~5), isolated pale yellow oily liquid.
5. method according to claim 1, which is characterized in that methanol and vinegar in methanol and acetic acid mixed solution in step (2)
The volume ratio of acid is (1~9): 1.
6. method according to claim 1, it is characterised in that: step (2) basement membrane is polytetrafluoroethylene (PTFE) miillpore filter
(PTFE), one of polyvinylidene fluoride microporous filtering film (PVDF), nylon-6 miillpore filter (Nylon-6).
7. lead (II) the ion blotting composite membrane that claim 1 ~ 5 any one the method is prepared is molten for adsorbing separation
Lead (II) ion in liquid.
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