CN106552606A - A kind of method that porous ion-exchange resin is prepared based on click chemistry reaction - Google Patents
A kind of method that porous ion-exchange resin is prepared based on click chemistry reaction Download PDFInfo
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- CN106552606A CN106552606A CN201611094940.7A CN201611094940A CN106552606A CN 106552606 A CN106552606 A CN 106552606A CN 201611094940 A CN201611094940 A CN 201611094940A CN 106552606 A CN106552606 A CN 106552606A
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- 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
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
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Abstract
The invention discloses a kind of method that click chemistry reaction based in High Internal Phase Emulsion prepares porous ion-exchange resin.The mixed solvent that invention is constituted using dimethylformamide and water constitutes the High Internal Phase Emulsion of oil-in-water type as water phase, by water phase in the nitrine alkynes click chemistry reaction that occurs of two kinds of monomers for containing azido and alkynyl respectively prepare polymer porous material.Step is as follows：Mixed solvent using the dimethylformamide dissolved with two kinds of monomers for containing azido group and alkynyl respectively and water composition is used as water phase, then adds proper catalyst and polysorbate60 toward water phase, is eventually adding oil phase；Gained water oil mixture is clipped to emulsify the High Internal Phase Emulsion for preparing oil-in-water type.After gained High Internal Phase Emulsion reacts certain hour in a water bath, extrct removes oil phase, dimethylformamide and catalyst, and eliminating water is gone in freeze-drying, obtains polymer porous material.The preparation method novel and unique of the present invention, is widely used, and resulting polymers aperture of porous material is between 2 ~ 10 microns, and can use as strongly acidic cation exchanger, and the cupric ion adsorption of every gram of material is up to 50 milligrams.
Description
Technical field
The present invention relates in a kind of High Internal Phase Emulsion based on oil-in-water type click chemistry reaction prepare with heavy metal from
The method of the polymer porous material of sub- switching performance, and in particular to the mixed solvent constituted using dimethylformamide and water as
Water phase, monomer, catalyst dissolution with polysorbate60 as stabilizer, prepare the High Internal Phase Emulsion of oil-in-water type, by breast in water phase
Liquid template prepares polymer porous material, and the heavy metal ion in water is adsorbed, and purifies sewage.
Background technology
Polymer porous material has high porosity, low-density, bigger serface and good material conveying capacity etc. excellent
Point, has very high application the aspects such as tissue cultures support, ion exchange resin, catalyst carrier and environmental science are prepared
Value, has been obtained for numerous applications；
Preparing polymer porous material has various methods, such as:Supercritical fluid, air-blowing, colloid template assembling, polybenzazole precursor mould
Plate method and High Internal Phase Emulsion template etc..There are many advantages using polymer porous material obtained in High Internal Phase Emulsion template,
Such as:Macropore diameter and pore-size distribution are adjustable, and pore volume is big, and products appearance pattern can have certain according to mould random molding
Mechanical stability and its surface can be according to different use environment functionalization etc..These advantages are obtained High Internal Phase Emulsion template
The research and preparing of polymer porous material scientific research and production practices are had great significance.So far, high interior phase
Polymer porous material prepared by emulsion template method is in such as bioengineered scaffolds, catalyst carrier, ion exchange resin and electricity
The multiple fields such as chemical sensor illustrate wide application prospect to people；
High Internal Phase Emulsion is emulsion of the disperse phase volume percentage more than or equal to 74. 05%.This emulsion is since twentieth century six
Since 10 years reported firsts, opening polymer material is prepared as template, there are numerous document reports, such as Dow Chemical is public
Take charge of United States Patent (USP) (US Pat 6,147,131) and Ka Meilong in application in 2000, polymer is equal to than Si Mai and Zhang Shengmiao
Series of articles delivered on magazine etc..However, as emulsion environment easily draws to the restriction of polymerizing condition and other materials
Unstable, the polymerisation in High Internal Phase Emulsion of emulsion system is played, reported work is all adopted based on free radical initiation
Vinyl monomer polymerization；
Cycloaddition reaction (CuAAC) of " click chemistry ", particularly Cu (I) the compound for catalysis end with nitrine/ethynylene group, tool
There are gentle reaction condition, high conversion rate, low cost, high selectivity, preferable functional group tolerance.In recent years, point
Hit chemistry new approach is provided for design macromolecular compound of the synthesis with labyrinth and function.In chemistry, biological doctor
The fields such as medicine, Polymer Synthesizing, material all receive significant attention；
Containing sulfonic polymer, can use as highly acidic cation agent, after its dissociation, the negative electricity group contained by body
SO3-, can adsorb other cations in binding soln.Which can dissociate in acid or alkaline solution and produce ion exchange
Effect；
The polymer porous material that the present invention is obtained using High Internal Phase Emulsion template, is reacted by click chemistry --- Cu
(I) cycloaddition reaction of the compound for catalysis end with nitrine/ethynylene group）It is obtained, breaches High Internal Phase Emulsion template and only limit
The limitation of the vinyl monomer polymerization synthesis based on causing in free radical, realizes its basic material variation；For promotion clickization
Learn reaction the development of this crossing domain and High Internal Phase Emulsion template are prepared in High Internal Phase Emulsion template polymer porous material
The expansion of method polymer porous material performance is with important science and practice significance.Such as in the present invention, prepared polymerization
Thing porous material carries sulfonic acid group, therefore which can be used as highly acidic cation agent, and because its porous and hydrophily,
The heavy metal ion such as copper ion etc. exchanged in the aqueous solution can efficiently be adsorbed.
The content of the invention
The technical problem to be solved in the invention is that open one kind prepares polymer porous material by click chemistry reaction
Method, to give polymer porous material functionalization, widen the range of application of polymer porous material.System of the present invention
The method of standby polymer porous material, comprises the steps:Mixed solvent using dimethylformamide and water composition is used as water
Phase, the two kinds of monomers, catalyst dissolution respectively containing azido and alkynyl are also dissolved in water by stabilizer of polysorbate60 in water phase
Phase, is eventually adding oil phase, disperses 2 minutes in 14000 rpms of speed down cuts, prepares mutually newborn in the height of oil-in-water type
Liquid.After water-bath certain hour, extrct removes oil phase, dimethylformamide and catalyst, liquid to obtained High Internal Phase Emulsion
Chilled nitrogen, and eliminating water is gone in freeze-drying, and polymer porous material is obtained.When using as strongly acidic cation exchanger, take
A certain amount of polymer porous material, is placed in copper-bath, and the copper ion in water is adsorbed；
The described monomer containing azido is 4,4-two nitrine talan-2,2-sodium disulfonate tetrahydrate, and which accounts for water phase
Mass fraction is 22% ~ 30%；
The described monomer containing alkynyl is three propargyl amine, and which accounts for water phase mass fraction for 3.5% ~ 5%；
Described catalyst is cupric sulfate pentahydrate and sodium ascorbate, and mass fraction of the cupric sulfate pentahydrate in water phase is 1%, is resisted
Mass fraction of the bad hematic acid sodium in water phase is 7% ~ 15%；
Mass fraction of the polysorbate60 in water phase is 5% ~ 20%；
The volume fraction of water phase is 10% ~ 25%；
Described oil phase is paraffin oil, and the volume fraction of oil phase is 90% ~ 75%；
Described water-bath, temperature are 70 to 85 degrees Celsius；
Polymer porous material of the described a certain amount of polymer porous material for 12mg；
Copper sulfate solution of the described copper-bath for 40ml volume 0.5mmol/L concentration；
The pattern of ordered structure polymer porous material is observed using ESEM (SEM) S-3400 (Japanese JEOL companies), and
Determine its pitch of holes and aperture；Using inductive coupling plasma emission spectrograph Agilent 725-ES（U.S.'s Agilent is public
Department）Determine copper ion concentration in solution；
Preparation method of the present invention is easy to operate, and the polymer porous material aperture for obtaining, and can be used as strong between 2 ~ 10 microns
Acid cation-exchanger is used, copper ion that can efficiently in adsorption aqueous solution, the Copper Ion Exchange adsorbance of every gram of material
Up to 50 milligrams.
Embodiment 1
By 0.032 gram of three propargyl amine, 0.20 gram of 4,4-two nitrine talan-2,2-sodium disulfonate tetrahydrate,
0.006 gram of cupric sulfate pentahydrate, 0.042 gram of sodium ascorbate and 0.03 gram of polysorbate60 be added to 0.20 gram of dimethylformamide with
In the mixed solvent of 0.40 gram of water composition, ultrasonic disperse is subsequently added 1.8g paraffin oils as oil phase, difference uniformly as water phase
Two kinds of monomers containing azido and alkynyl, catalyst dissolution disperse 2 in 14000 rpms of speed down cuts in water phase
Minute, it is prepared into the High Internal Phase Emulsion of oil-in-water type.Obtained High Internal Phase Emulsion is taken out after 70 C water baths react 60 hours
Removing oil phase paraffin oil, dimethylformamide and catalyst, liquid nitrogen frozen are carried, and eliminating water is gone in freeze-drying, polymer is obtained many
Porous materials；
About 3.5 microns of the aperture of resulting polymers porous material；
12 milligrams of polymer porous material is added in 40 milliliters 0.50 mM per liter of copper sulfate solution, every gram of material
About 50 milligrams of the cupric ion adsorption of material.
Embodiment 2
By 0.032 gram of three propargyl amine, 0.20 gram of 4,4-two nitrine talan-2,2-sodium disulfonate tetrahydrate,
0.006 gram of cupric sulfate pentahydrate, 0.06 gram of sodium ascorbate and 0.12 gram of polysorbate60 be added to 0.20 gram of dimethylformamide with
In the mixed solvent of 0.40 gram of water composition, ultrasonic disperse is subsequently added 2.4 grams of paraffin oils as oil phase uniformly as water phase, point
Not Han two kinds of monomers of azido and alkynyl, catalyst dissolution in water phase, disperse in 14000 rpms of speed down cuts
2 minutes, it is prepared into the High Internal Phase Emulsion of oil-in-water type.Obtained High Internal Phase Emulsion 80 C water baths react 24 hours after,
Extrct removes oil phase paraffin oil, dimethylformamide and catalyst, liquid nitrogen frozen, and eliminating water is gone in freeze-drying, and polymer is obtained
Porous material；
About 1.5 microns of the aperture of resulting polymers porous material；
12 milligrams of polymer porous material is added in 40 milliliters 0.50 mM per liter of copper sulfate solution, every gram of material
About 50 milligrams of the cupric ion adsorption of material.
Embodiment 3
By 0.057 gram of three propargyl amine, 0.34 gram of 4,4-two nitrine talan-2,2-sodium disulfonate tetrahydrate,
0.006 gram of cupric sulfate pentahydrate, 0.090 gram of sodium ascorbate and 0.075 gram of polysorbate60 be added to 0.20 gram of dimethylformamide with
In the mixed solvent of 0.40 gram of water composition, ultrasonic disperse is subsequently added 5.4 grams of paraffin oils as oil phase uniformly as water phase, point
Not Han two kinds of monomers of azido and alkynyl, catalyst dissolution in water phase, disperse in 14000 rpms of speed down cuts
2 minutes, it is prepared into the High Internal Phase Emulsion of oil-in-water type.Obtained High Internal Phase Emulsion 85 C water baths react 16 hours after,
Extrct removes oil phase paraffin oil, dimethylformamide and catalyst, liquid nitrogen frozen, and eliminating water is gone in freeze-drying, and polymer is obtained
Porous material；
About 2 microns of the aperture of resulting polymers porous material；
12 milligrams of polymer porous material is added in 40 milliliters 0.50 mM per liter of copper sulfate solution, every gram of material
About 50 milligrams of the cupric ion adsorption of material.
Claims (1)
1. a kind of method that click chemistry reaction based in High Internal Phase Emulsion prepares porous ion-exchange resin, it is characterised in that
Novel and unique, simple possible mainly comprise the steps：The mixed solvent constituted using dimethylformamide and water as water phase,
Two kinds of monomers, catalyst and polysorbate60s for being contained azido and alkynyl respectively are dissolved in water phase, are eventually adding oil phase, 14000
Rpm speed down cut disperse 2 minutes, be obtained oil-in-water type High Internal Phase Emulsion；
After water-bath certain hour, extrct removes oil phase, dimethylformamide and catalyst to obtained High Internal Phase Emulsion, and
Eliminating water is gone in freeze-drying, obtains polymer porous material；
The described monomer containing azido is 4,4-two nitrine talan-2,2-sodium disulfonate tetrahydrate, and which accounts for water phase
Mass fraction is 22% ~ 30%；
The described monomer containing alkynyl is three propargyl amine, and which accounts for water phase mass fraction for 3.5% ~ 5%；
Described catalyst is cupric sulfate pentahydrate and sodium ascorbate, and mass fraction of the cupric sulfate pentahydrate in water phase is 1%, is resisted
Mass fraction of the bad hematic acid sodium in water phase is 7% ~ 15%；
Mass fraction of the polysorbate60 in water phase is 5% ~ 20%；
The volume fraction of water phase is 10% ~ 25%；
Described oil phase is paraffin oil, and the volume fraction of oil phase is 90% ~ 75%；
Described water-bath, temperature are 70 to 85 degrees Celsius.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391416A (en) * | 2011-09-02 | 2012-03-28 | 华东理工大学 | Preparation method of porous material based on inorganic nanoparticles for stabilizing high internal phase emulsion |
| CN103539929A (en) * | 2013-10-10 | 2014-01-29 | 华东理工大学 | Method for preparing polymer porous material by using diene synthetic reaction in high internal phase emulsion |
| CN104741101A (en) * | 2013-12-26 | 2015-07-01 | 戴安公司 | Ion Exchange Foams To Remove Ions From Samples |
| CN105885082A (en) * | 2016-04-21 | 2016-08-24 | 同济大学 | Method for preparing surface glycosyl modified porous material by utilizing highly-introverted emulsion template method |
-
2016
- 2016-12-02 CN CN201611094940.7A patent/CN106552606B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391416A (en) * | 2011-09-02 | 2012-03-28 | 华东理工大学 | Preparation method of porous material based on inorganic nanoparticles for stabilizing high internal phase emulsion |
| CN103539929A (en) * | 2013-10-10 | 2014-01-29 | 华东理工大学 | Method for preparing polymer porous material by using diene synthetic reaction in high internal phase emulsion |
| CN104741101A (en) * | 2013-12-26 | 2015-07-01 | 戴安公司 | Ion Exchange Foams To Remove Ions From Samples |
| CN105885082A (en) * | 2016-04-21 | 2016-08-24 | 同济大学 | Method for preparing surface glycosyl modified porous material by utilizing highly-introverted emulsion template method |
Non-Patent Citations (3)
| Title |
|---|
| DAVID CUMMINS ET AL.: "Click chemistry as a means to functionalize macroporous PolyHIPE", 《SOFT MATTER》 * |
| VICTORIA D. BOCK ET AL.: "CuI-Catalyzed Alkyne–Azide "Click" Cycloadditions from a Mechanistic and", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| 贾雪等: "高内相乳液模板法多孔材料的研究进展", 《胶体与聚合物》 * |
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