CN109438619A - It is a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer - Google Patents
It is a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer Download PDFInfo
- Publication number
- CN109438619A CN109438619A CN201811138065.7A CN201811138065A CN109438619A CN 109438619 A CN109438619 A CN 109438619A CN 201811138065 A CN201811138065 A CN 201811138065A CN 109438619 A CN109438619 A CN 109438619A
- Authority
- CN
- China
- Prior art keywords
- hexavalent chromium
- composite membrane
- methacrylic acid
- function monomer
- trace composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 71
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000000178 monomer Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 14
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 13
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000011651 chromium Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- DGPGGSRBDAZGPP-UHFFFAOYSA-N ethane-1,2-diol;2-methylbut-2-ene Chemical group OCCO.CC=C(C)C DGPGGSRBDAZGPP-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0442—Elimination of an inorganic solid phase the inorganic phase being a metal, its oxide or hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or 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, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer, belongs to heavy metal ion adsorbed separation technology field.Using α-methacrylic acid as the preparation method of the hexavalent chromium trace composite membrane of function monomer, its step includes: to use hexavalent chromium for template ion, α-methacrylic acid is function monomer, ethylene glycol dimethacrylate is crosslinking agent, azodiisobutyronitrile is initiator, it is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, hexavalent chromium trace composite membrane is prepared by surface grafting method.This method is combined with ionic imprinting technique with membrane separation technique; without the complex operations such as grind or be sieved; specific recognition site can be protected; and stability is high; strong environmental adaptability; it can be used in extreme solution environmental, can be used for the adsorbing separation containing hexavalent chromium in Cr(VI) solution.
Description
Technical field
The present invention relates to a kind of using α-methacrylic acid as the preparation side of the hexavalent chromium trace composite membrane of function monomer
Method and application belong to heavy metal ion adsorbed separation technology field.
Background technique
Containing to biology toxic pollutant harmful with environment in industrial wastewater, in these pollutants, heavy metal is recognized
To be most dangerous one of pollutant, and hexavalent chromium passes through plating, metal watch as important one of heavy metal contaminants
The industries such as surface treatment, leather tanning, paint, pigment, weaving and steel and iron manufacturing are discharged into environment extensively, to the mankind and environment
It causes to seriously threaten.Currently, many methods have been used for processing hexavalent chromium, including it is reverse osmosis, reduction and precipitating, ultrafiltration, from
Son exchange and UF membrane etc..Though these methods have obtained certain effect, there are still many drawbacks, the researchers such as Li Hangbin are utilized
The barium salt precipitation method handle the Cr VI in electroplating wastewater, to the rate of recovery of Cr VI up to 65%, but the medicine of this method
Agent higher cost is relatively suitable for the plating such as professional chromium plating factory garden.Mankind's bring is seriously affected in view of hexavalent chromium, is needed
Seek more reasonable processing method.
Metal ion engram technology has many advantages, such as high efficiency, low cost and easy to operate, is widely used to a huge sum of money at present
Belong to ionic adsorption separation field.Patent application is 107446086 A of CN is with hexavalent chromium using metal ion engram technology
Template is prepared for a kind of imprinted polymer, and achieves preferable effect, but the preparation process of imprinted polymer needs to grind,
Destruction is easily caused to specific recognition site, is unfavorable for being selectively adsorbing and separating for hexavalent chromium.
Summary of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides one kind using α-methacrylic acid as function list
The preparation method and application of the hexavalent chromium trace composite membrane of body.This method is mutually tied with ionic imprinting technique and membrane separation technique
It closes, without the complex operations such as grinding or sieving, specific recognition site can be protected, and stability is high, environment adapts to energy
Power is strong, can use in extreme solution environmental, can be used for the adsorbing separation containing hexavalent chromium in Cr(VI) solution.
The present invention uses hexavalent chromium for template ion, and α-methacrylic acid is function monomer, ethylene glycol dimethyl third
Olefin(e) acid ester is crosslinking agent, and azodiisobutyronitrile is initiator, and commercially available commercial membranes are support membrane, molten with the mixing of You machine Rong Ji ∕ water
Liquid is porogenic solvents, and hexavalent chromium trace composite membrane is prepared on support membrane by surface grafting method.Described in this method
Support membrane can generate the olefin(e) acid class function monomer of chelation in the presence of porogenic solvents, in its area load with metal ion,
Under the action of crosslinking agent and initiator, ion blotting composite membrane is formed in film surface cross-linked polymeric, elution removes template ion
Afterwards, film surface forms the hole for having specific recognition to template ion, to obtain having high absorption point to hexavalent chromium
Trace composite membrane from ability.
It is a kind of using α-methacrylic acid as the preparation method of the hexavalent chromium trace composite membrane of function monomer, step packet
It includes: using hexavalent chromium for template ion, α-methacrylic acid is function monomer, and ethylene glycol dimethacrylate is crosslinking
Agent, azodiisobutyronitrile are initiator, are the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, pass through
Hexavalent chromium trace composite membrane is prepared in surface grafting method.
Specific step is as follows:
Step 1, by K2Cr2O7It is dissolved in the organic solvent and water mixed solution porogenic solvents that volume ratio is 1:1, adds α-first
Base functional acrylic monomer, isothermal vibration reacts 2~3 h at room temperature, and ethylene glycol dimethacrylate and azo two is added
Isobutyronitrile is dissolved and is shaken up, and forms pre-polymerization liquid；
Support membrane is placed in the pre-polymerization liquid in step 1 by step 2, is impregnated 3~60 min at normal temperature, is then heated to 60~80
12~24 h are reacted at DEG C, the methanol for being finally 9:1 with volume ratio and the elution of acetic acid mixed solution remove template ion, are prepared into
To hexavalent chromium trace composite membrane.
K in the step 12Cr2O7, α-methacrylic acid and ethylene glycol dimethacrylate molar ratio be 1:2~8:10
~50.
Organic solvent is methanol, ethyl alcohol, acetonitrile, N-N- dimethylformamide or isopropanol in the step 1.
Support membrane is polytetrafluoroethylene (PTFE) miillpore filter in the step 2.Above-mentioned support membrane is commercially available commercial membranes.
A kind of hexavalent chromium trace composite membrane applies the adsorbing separation of hexavalent chromium in the solution.
The beneficial effects of the present invention are:
(1) certain chelating can be generated between olefin(e) acid class organic compound of the method for the present invention based on hexavalent chromium and containing oxygen atom
The principle of effect uses commercially available commercial membranes for support membrane, overcomes existing hexavalent chromium imprinted polymer preparation difficulty, method
The disadvantages of cumbersome.
(2) trace composite membrane prepared by can hexavalent chromium effectively in adsorbent solution, imprinting effect is good.
(3) the trace composite membrane is using α-methacrylic acid as function monomer, has stability good, and it is excellent that preparation method is simple etc.
Point can be used for the adsorbing separation containing hexavalent chromium in Cr (VI) solution.
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
, using α-methacrylic acid as the preparation method of the hexavalent chromium trace composite membrane of function monomer, step includes: to adopt for this
It is template ion with hexavalent chromium, α-methacrylic acid is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, even
Nitrogen bis-isobutyronitrile is initiator, is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is connect by surface
Hexavalent chromium trace composite membrane is prepared in branch method.
Specific step is as follows:
Step 1, by 0.1mmolK2Cr2O7It is dissolved in the organic solvent (methanol) and water mixed solution pore that 10 mL volume ratios are 1:1
In solvent, α-methacrylic acid function monomer is added, isothermal vibration reacts 2 h at room temperature, and ethylene glycol dimethyl third is added
Olefin(e) acid ester and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid；Wherein K2Cr2O7, α-methacrylic acid and ethylene glycol two
Methacrylate molar ratio is 1:2:10, K2Cr2O7It is 1:0.6 with azodiisobutyronitrile molar ratio；
Support membrane (support membrane is polytetrafluoroethylene (PTFE) miillpore filter) is placed in the pre-polymerization liquid in step 1 by step 2, is soaked at normal temperature
3 min are steeped, then heats at 60 DEG C and reacts 12 h, the methanol and acetic acid mixed solution for being finally 9:1 with 150 mL volume ratios
Elution removes template ion, and hexavalent chromium trace composite membrane is prepared.
The 1.80g hexavalent chromium trace composite membrane that the present embodiment is prepared is applied and is in hexavalent chromium concentration
In 0.24 mmol/L solution, adsorbance is 29.91 μm of ol/g, imprinting factor 1.11.
Embodiment 2
, using α-methacrylic acid as the preparation method of the hexavalent chromium trace composite membrane of function monomer, step includes: to adopt for this
It is template ion with hexavalent chromium, α-methacrylic acid is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, even
Nitrogen bis-isobutyronitrile is initiator, is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is connect by surface
Hexavalent chromium trace composite membrane is prepared in branch method.
Specific step is as follows:
Step 1, by 0.1mmolK2Cr2O7It is dissolved in the organic solvent (ethyl alcohol) and water mixed solution pore that 10 mL volume ratios are 1:1
In solvent, α-methacrylic acid function monomer is added, isothermal vibration reacts 3h at room temperature, and ethylene glycol dimethyl propylene is added
Acid esters and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid；Wherein K2Cr2O7, α-methacrylic acid and glycol dinitrate
Base acrylate molar ratio is 1:4:20, K2Cr2O7It is 1:0.9 with azodiisobutyronitrile molar ratio；
Support membrane (support membrane is polytetrafluoroethylene (PTFE) miillpore filter) is placed in the pre-polymerization liquid in step 1 by step 2, is soaked at normal temperature
3min is steeped, then heats at 60 DEG C and reacts 24 h, the methanol and acetic acid mixed solution for being finally 9:1 with 150 mL volume ratios are washed
Template ion is removed in removing, and hexavalent chromium trace composite membrane is prepared.
The 1.85 g hexavalent chromium trace composite membranes that the present embodiment is prepared are applied is in hexavalent chromium concentration
In 0.24 mmol/L solution, adsorbance is 35.28 μm of ol/g, imprinting factor 1.25.
Embodiment 3
, using α-methacrylic acid as the preparation method of the hexavalent chromium trace composite membrane of function monomer, step includes: to adopt for this
It is template ion with hexavalent chromium, α-methacrylic acid is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, even
Nitrogen bis-isobutyronitrile is initiator, is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is connect by surface
Hexavalent chromium trace composite membrane is prepared in branch method.
Specific step is as follows:
Step 1, by 0.1mmolK2Cr2O7It is dissolved in the organic solvent (acetonitrile) and water mixed solution pore that 10 mL volume ratios are 1:1
In solvent, α-methacrylic acid function monomer is added, isothermal vibration reacts 3 h at room temperature, and ethylene glycol dimethyl third is added
Olefin(e) acid ester and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid；Wherein K2Cr2O7, α-methacrylic acid and ethylene glycol two
Methacrylate molar ratio is 1:4:30, K2Cr2O7It is 1:1 with azodiisobutyronitrile molar ratio；
Support membrane (support membrane is polytetrafluoroethylene (PTFE) miillpore filter) is placed in the pre-polymerization liquid in step 1 by step 2, is soaked at normal temperature
3 min are steeped, then heats at 60 DEG C and reacts 24 h, the methanol and acetic acid mixed solution for being finally 9:1 with 150 mL volume ratios
Elution removes template ion, and hexavalent chromium trace composite membrane is prepared.
The 1.82g hexavalent chromium trace composite membrane that the present embodiment is prepared is applied and is in hexavalent chromium concentration
In 0.24 mmol/L solution, adsorbance is 29.76 μm of ol/g, imprinting factor 1.19.
Embodiment 4
, using α-methacrylic acid as the preparation method of the hexavalent chromium trace composite membrane of function monomer, step includes: to adopt for this
It is template ion with hexavalent chromium, α-methacrylic acid is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, even
Nitrogen bis-isobutyronitrile is initiator, is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is connect by surface
Hexavalent chromium trace composite membrane is prepared in branch method.
Specific step is as follows:
Step 1, by 0.1mmolK2Cr2O7It is dissolved in the organic solvent (N-N- dimethylformamide) and water that 10 mL volume ratios are 1:1
In mixed solution porogenic solvents, α-methacrylic acid function monomer is added, isothermal vibration reacts 3 h at room temperature, and second is added
Diol dimethacrylate and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid；Wherein K2Cr2O7, Alpha-Methyl propylene
Acid and ethylene glycol dimethacrylate molar ratio are 1:6:40, K2Cr2O7It is 1:1.2 with azodiisobutyronitrile molar ratio；
Support membrane (support membrane is polytetrafluoroethylene (PTFE) miillpore filter) is placed in the pre-polymerization liquid in step 1 by step 2, is soaked at normal temperature
60 min are steeped, then heats at 80 DEG C and reacts 36 h, the methanol and acetic acid for being finally 9:1 with 150 mL volume ratios mix molten
Liquid elution removes template ion, and hexavalent chromium trace composite membrane is prepared.
The 1.85 g hexavalent chromium trace composite membranes that the present embodiment is prepared are applied is in hexavalent chromium concentration
In 0.24 mmol/L solution, adsorbance is 38.84 μm of ol/g, imprinting factor 1.14.
Embodiment 5
, using α-methacrylic acid as the preparation method of the hexavalent chromium trace composite membrane of function monomer, step includes: to adopt for this
It is template ion with hexavalent chromium, α-methacrylic acid is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, even
Nitrogen bis-isobutyronitrile is initiator, is the organic solvent of 1:1 and the mixed solution of water as porogenic solvents using volume ratio, is connect by surface
Hexavalent chromium trace composite membrane is prepared in branch method.
Specific step is as follows:
Step 1, by 0.1mmolK2Cr2O7It is dissolved in the organic solvent (isopropanol) and water mixed solution cause that 10mL volume ratio is 1:1
In the solvent of hole, α-methacrylic acid function monomer is added, isothermal vibration reacts 2.5 h at room temperature, and glycol dinitrate is added
Base acrylate and azodiisobutyronitrile are dissolved and are shaken up, and form pre-polymerization liquid；Wherein K2Cr2O7, α-methacrylic acid and second two
Alcohol dimethylacrylate molar ratio is 1:8:50, K2Cr2O7It is 1:1.2 with azodiisobutyronitrile molar ratio；
Support membrane (support membrane is polytetrafluoroethylene (PTFE) miillpore filter) is placed in the pre-polymerization liquid in step 1 by step 2, is soaked at normal temperature
30 min are steeped, then heats at 70 DEG C and reacts 24 h, the methanol and acetic acid for being finally 9:1 with 150 mL volume ratios mix molten
Liquid elution removes template ion, and hexavalent chromium trace composite membrane is prepared.
The 1.82g hexavalent chromium trace composite membrane that the present embodiment is prepared is applied and is in hexavalent chromium concentration
In 0.24 mmol/L solution, adsorbance is 28.88 μm of ol/g, imprinting factor 1.21.
The reagent that concentration is not involved in above-described embodiment is analytical reagents.
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 (6)
1. a kind of using α-methacrylic acid as the preparation method of the hexavalent chromium trace composite membrane of function monomer, it is characterised in that
Step includes: to use hexavalent chromium for template ion, and α-methacrylic acid is function monomer, ethylene glycol dimethacrylate
For crosslinking agent, azodiisobutyronitrile is initiator, molten as pore for the organic solvent of 1:1 and the mixed solution of water using volume ratio
Hexavalent chromium trace composite membrane is prepared by surface grafting method in agent.
2. according to claim 1 using α-methacrylic acid as the preparation of the hexavalent chromium trace composite membrane of function monomer
Method, it is characterised in that specific step is as follows:
Step 1, by K2Cr2O7It is dissolved in the organic solvent and water mixed solution porogenic solvents that volume ratio is 1:1, adds α-first
Base functional acrylic monomer, isothermal vibration reacts 2~3 h at room temperature, and ethylene glycol dimethacrylate and azo two is added
Isobutyronitrile is dissolved and is shaken up, and forms pre-polymerization liquid；
Support membrane is placed in the pre-polymerization liquid in step 1 by step 2, is impregnated 3~60 min at normal temperature, is then heated to 60~80
12~36 h are reacted at DEG C, the methanol for being finally 9:1 with volume ratio and the elution of acetic acid mixed solution remove template ion, are prepared into
To hexavalent chromium trace composite membrane.
3. according to claim 2 using α-methacrylic acid as the preparation of the hexavalent chromium trace composite membrane of function monomer
Method, it is characterised in that: K in the step 12Cr2O7, α-methacrylic acid and ethylene glycol dimethacrylate molar ratio be
1:2~8:10~50.
4. according to claim 2 using α-methacrylic acid as the preparation of the hexavalent chromium trace composite membrane of function monomer
Method, it is characterised in that: organic solvent is methanol, ethyl alcohol, acetonitrile, N-N- dimethylformamide or isopropanol in the step 1.
5. according to claim 2 using α-methacrylic acid as the preparation of the hexavalent chromium trace composite membrane of function monomer
Method, it is characterised in that: support membrane is polytetrafluoroethylene (PTFE) miillpore filter in the step 2.
6. a kind of according to claim 1 to hexavalent chromium trace composite membrane described in 5 any one using sexavalence in the solution
The adsorbing separation of chromium ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811138065.7A CN109438619A (en) | 2018-09-28 | 2018-09-28 | It is a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811138065.7A CN109438619A (en) | 2018-09-28 | 2018-09-28 | It is a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109438619A true CN109438619A (en) | 2019-03-08 |
Family
ID=65545957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811138065.7A Pending CN109438619A (en) | 2018-09-28 | 2018-09-28 | It is a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109438619A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110339727A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and application of lead (II) ion trace composite membrane |
| CN110339728A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | One kind being based on the preparation method and application of new function monomer lead (II) ion blotting composite membrane |
| CN110339731A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and applications of chromium (VI) ion blotting composite membrane |
| CN110339730A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and application of trivalent chromic ion trace composite membrane |
| CN117089020A (en) * | 2023-08-30 | 2023-11-21 | 昆明理工大学 | Based on nanometer TiO 2 Preparation method of Co (II) ion imprinting adsorption material |
| CN117089020B (en) * | 2023-08-30 | 2024-06-07 | 昆明理工大学 | Based on nanometer TiO2Preparation method of Co (II) ion imprinting adsorption material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106256839A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of method that ion blotting composite membrane is prepared in surface heat polymerization |
| CN107376655A (en) * | 2017-07-07 | 2017-11-24 | 江苏大学 | A kind of preparation method and use of lithium ion trace nano composite membrane |
| CN108339529A (en) * | 2018-01-24 | 2018-07-31 | 江苏大学 | A kind of preparation method and application of ion blotting composite membrane for Selective Separation palladium ion |
| CN109351347A (en) * | 2018-09-28 | 2019-02-19 | 昆明理工大学 | It is a kind of using acrylamide as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
-
2018
- 2018-09-28 CN CN201811138065.7A patent/CN109438619A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106256839A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of method that ion blotting composite membrane is prepared in surface heat polymerization |
| CN107376655A (en) * | 2017-07-07 | 2017-11-24 | 江苏大学 | A kind of preparation method and use of lithium ion trace nano composite membrane |
| CN108339529A (en) * | 2018-01-24 | 2018-07-31 | 江苏大学 | A kind of preparation method and application of ion blotting composite membrane for Selective Separation palladium ion |
| CN109351347A (en) * | 2018-09-28 | 2019-02-19 | 昆明理工大学 | It is a kind of using acrylamide as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
Non-Patent Citations (1)
| Title |
|---|
| 李积升 等: ""六价铬离子印迹聚合物合成原理的研究"", 《化学工程师》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110339727A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and application of lead (II) ion trace composite membrane |
| CN110339728A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | One kind being based on the preparation method and application of new function monomer lead (II) ion blotting composite membrane |
| CN110339731A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and applications of chromium (VI) ion blotting composite membrane |
| CN110339730A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and application of trivalent chromic ion trace composite membrane |
| CN110339727B (en) * | 2019-07-02 | 2021-10-22 | 昆明理工大学 | Preparation method and application of divalent lead ion imprinting composite membrane |
| CN110339728B (en) * | 2019-07-02 | 2021-10-22 | 昆明理工大学 | Preparation method and application of lead (II) ion imprinting composite membrane based on new functional monomer |
| CN117089020A (en) * | 2023-08-30 | 2023-11-21 | 昆明理工大学 | Based on nanometer TiO 2 Preparation method of Co (II) ion imprinting adsorption material |
| CN117089020B (en) * | 2023-08-30 | 2024-06-07 | 昆明理工大学 | Based on nanometer TiO2Preparation method of Co (II) ion imprinting adsorption material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109438619A (en) | It is a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer | |
| Karimi et al. | Column study of Cr (VI) adsorption onto modified silica–polyacrylamide microspheres composite | |
| Bayramoğlu et al. | Ethylenediamine grafted poly (glycidylmethacrylate-co-methylmethacrylate) adsorbent for removal of chromate anions | |
| Yu et al. | Enhanced and selective adsorption of Pb2+ and Cu2+ by EDTAD-modified biomass of baker’s yeast | |
| CN109351348A (en) | It is a kind of using 4-vinylpridine as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer | |
| Weidman et al. | Nanoporous block polymer thin films functionalized with bio-inspired ligands for the efficient capture of heavy metal ions from water | |
| Zang et al. | Research on adsorption of Cr (Ⅵ) by Poly-epichlorohydrin-dimethylamine (EPIDMA) modified weakly basic anion exchange resin D301 | |
| CN103041791B (en) | Preparation method of novel lead removal agent | |
| Genç et al. | Procion Green H-4G immobilized poly (hydroxyethylmethacrylate/chitosan) composite membranes for heavy metal removal | |
| CN106621842B (en) | A kind of preparation method, regeneration method and application chelating microfiltration membranes | |
| Wang et al. | Preparation of novel composites based on hydrophilized and functionalized polyacrylonitrile membrane-immobilized NZVI for reductive transformation of metronidazole | |
| Cheng et al. | Development of a novel hollow fiber cation-exchange membrane from bromomethylated poly (2, 6-dimethyl-1, 4-phenylene oxide) for removal of heavy-metal ions | |
| CN109351347A (en) | It is a kind of using acrylamide as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer | |
| Malachowski et al. | Immobilized peptides/amino acids on solid supports for metal remediation | |
| CN109647232B (en) | Method for preparing cobalt (II) ion imprinting composite membrane by using N-methylpyrrolidine acrylamide | |
| CN108371938A (en) | Mesoporous magnetic Nano iron oxide material, preparation method and applications | |
| Hao et al. | UV pre-activation/thermal initiated grafting of caffeic acid on PVDF for preparation of adsorptive membranes for cesium | |
| Kim et al. | Removal of Pb (II) ions from aqueous solutions using functionalized cryogels | |
| Kim et al. | Separation of valuables from spent selective catalytic reduction catalyst leaching solution by fabricated anion extraction resins | |
| CN105944698A (en) | Adsorbent for heavy metal ions in industrial wastewater and preparation method of adsorbent | |
| Zhao et al. | Preparation and characterization of Co (II) ion-imprinted composite membrane based on a novel functional monomer | |
| CN109589799B (en) | Preparation method of cadmium (II) ion imprinting composite membrane | |
| JP2004188307A (en) | Method of synthesizing zirconium-deposited fibrous adsorbing material having phosphate group and method of removing arsenic by using the same | |
| CN109663581B (en) | Method for preparing cobalt (II) ion imprinting composite membrane by using N-pyrrolidinylacrylamide | |
| CN110256726B (en) | Preparation method and application of lead (II) ion imprinting composite membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190308 |
|
| RJ01 | Rejection of invention patent application after publication |