CN109942735A - A kind of preparation method of the polymer microballoon for Rare Earth Separation - Google Patents
A kind of preparation method of the polymer microballoon for Rare Earth Separation Download PDFInfo
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Abstract
The technique that the present invention proposes a kind of polymer microballoon for Rare Earth Separation.Step is that 1 part of DGA monomer, 0.5-2 parts of styrene, 0.01-0.05 parts of divinylbenzenes, 0.01-0.02 parts of initiators, 0.1-0.2 parts of polyvinylpyrrolidone, 5-10 parts of stirring solvents are uniform, it is heated to 50-70 DEG C of reaction 3-6 hours under nitrogen atmosphere, obtains final products.The mode that absorption or Solid Phase Extraction can be used in the polymer microballoon of preparation carries out the separation of rare earth element；And polymer microballoon not phosphorus element-containing, after discarding can completely burned, be a kind of green adsorption and separation material.
Description
Technical field
The present invention is the synthesis technology of the polymer microballoon for Rare Earth Separation, in particular to a kind of amide containing pod ether gathers
Close the synthesis technology of object microballoon.
Background technique
With rare earth resources consumption and its exploitation application process in bring pollution, rare earth resources recycle and
The analysis detection of rare earth seems more important in environmental samples, thus during this essential rare earth separation, enrichment
Technology has been to be concerned by more and more people.Amido podand group (DGA) is that one kind has fine configurational energy for trivalent rare earth ions
The functional group of power, has been applied to extractant.Since it is without P elements common in conventional extraction agent, can burn completely
It burns, is a kind of green extractant (Chemical reviews. 2012,112,1751).Its modification for being used for adsorbent is also gradually
Attract attention (RSC Adv., 2015,5,103782).
In recent years, polymer microballoon has obtained extensively micrograde polymer microsphere in Solid Phase Extraction, the fields such as chromatographic isolation
Should gather.Dispersin polymerization is considered as the effective ways for preparing micrograde polymer microsphere.By the acyl for synthesizing carbon-carbon double bonds
Amine pod ether monomer, monomer, which is used for dispersin polymerization, can prepare the polymer microballoon rich in DGA group, and this polymer microballoon has
Hoping becomes a kind of efficient Rare Earth Separation material.
Summary of the invention
The present invention leads to styrene and the dispersion copolymerization of DGA function monomer is prepared for a kind of micron order that can be used for Rare Earth Separation
Polymer microballoon.The technical scheme is that
A kind of preparation method of micrograde polymer microsphere, its step are as follows:
(1) by 1 part of DGA monomer (vinyl compound containing amido podand functional group), 0.5-2 parts of styrene, 0.01-
0.05 part of divinylbenzene, 0.01-0.02 parts of initiators, 0.1-0.2 parts of polyvinylpyrrolidone, 5-10 parts of stirring solvents are equal
It is even；
(2) it is heated to 50-70 DEG C of reaction under nitrogen atmosphere and obtains final products within 3-6 hours.
Centrifugation, polymer beads ethanol washing after reaction, obtain final products.
Aforementioned proportion is mass ratio.
Wherein initiator be azodiisobutyronitrile (AIBN) or benzoyl peroxide (BPO), solvent be 100% methanol or
The mixed solvent of ethanol/water=4/1.
The DGA monomer the preparation method is as follows:
(1) after mixing 1 part of two sweet acid acid anhydrides and 4-10 parts of methylene chloride, 2.2 part of two positive fourth is slowly added dropwise at room temperature
Amine, heating, flow back 2h, obtains white solid M1；
(2) 1 part of M1,1 part of HOBT, 5 parts of THF are mixed, are slowly added to containing 1 part of DCC, 1 part Boc-EDA and 5 part
The solution of THF；Reaction obtains product M2；
(3) solution use is saturated NaHCO after 1 part of M2 and excessive hydrochloric acid to be stirred to 10h at 20 DEG C3It is washed till neutrality, is produced
Object M3；
(4) 1 part of M3,1 part of triethylamine and 2-10 parts of methylene chloride are stirred, are slowly added dropwise and are mixed with 1 part of acryloyl chloride
With the solution of 2-10 parts of methylene chloride；Reaction obtains DGA monomer.
Aforementioned proportion is molar ratio.
The more specific technical solution of the present invention is as follows:
(1) by 1 part of DGA monomer, 0.5-2 parts of styrene, 0.01-0.05 parts of divinylbenzenes, 0.01-0.02 parts of initiations
Agent, 0.1-0.2 parts of polyvinylpyrrolidone, 5-10 parts of solvents are added in schlenk bottles, are stirred evenly.
(2) it is heated to 50-70 DEG C of reaction 3-6 hours under nitrogen atmosphere.Centrifugation, polymer beads second after reaction
Alcohol washing, obtains final products.
Wherein initiator be azodiisobutyronitrile (AIBN) or benzoyl peroxide (BPO), solvent be 100% methanol or
The mixed solvent of ethanol/water=4/1.
Number described above is mass fraction.
Compared with existing product, the beneficial effects of the present invention are:
The mode that absorption or Solid Phase Extraction can be used in polymer microballoon prepared by the present invention carries out the separation of rare earth element；And
And polymer microballoon not phosphorus element-containing, after discarding can completely burned, be a kind of green adsorption and separation material.
Detailed description of the invention
Fig. 1 is the route map of monomer synthesis；
Fig. 2 is the nuclear magnetic spectrogram of monomer prepared by the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of 1 polymer microballoon of embodiment；
Fig. 4 is the infrared spectrum of 1 polymer microballoon of embodiment；
Fig. 5 is that polymer microballoon tries hard to the adsorption energy of each rare earth ion in embodiment 3.
Specific embodiment
Present invention is further described in detail With reference to embodiment:
The following examples can make the professional technician of this profession that the present invention be more fully understood, but not with any side
The formula limitation present invention.
It is referred to as follows for the reagent in embodiment:
Tetrahydrofuran: THF；Dimethyl sulfoxide: DMSO；N,N-dimethylformamide: DMF；I-hydroxybenzotriazole:
HOBT；Dicyclohexylcarbodiimide: DCC；N- tertbutyloxycarbonyl ethylenediamine: Boc-EDA；3-aminopropyltriethoxysilane:
APTES；2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline: EEDQ.
Embodiment 1
The preparation of monomer
(1) bis- sweet acid acid anhydride of 30g and 300mL methylene chloride are added to middle stirring after 1000mL round-bottomed flask.Delay at room temperature
Slow that 33g di-n-butylamine is added dropwise, heating, flow back 2h.Crude product recrystallization, obtains white solid and is denoted as M1.
(2) 24.5g M1,13.5g HOBT, 100mLTHF (100mL) are added in round-bottomed flask and are stirred, be slowly added to
Dissolved with the 150mLTHF solution of 20.6g DCC and 16g Boc-EDA.Room temperature continues to stir 10h.Reaction terminates filtering, and filtrate is dense
Degree.Crude product is purified with column chromatography method, and product is denoted as M2.
(3) solution use is saturated NaHCO after 20g M2 and 10mL hydrochloric acid to be stirred to 10h at 20 DEG C3It is washed till neutrality, solution is dense
Column chromatographic purifying is used after contracting, product is denoted as M3.
(4) 28.7g M3,10g triethylamine and 50mL methylene chloride are added sequentially to round-bottomed flask, stirred, ice bath is cold
But.The 20mL dichloromethane solution dissolved with 9.05g acryloyl chloride is slowly added dropwise.It is warming up to room temperature, continues to stir 3h.Reaction terminates
Filtering, filtrate concentration, obtains monomer with column chromatographic purifying.
The preparation of polymer microballoon
(1) by 10g function monomer, 10g styrene, 0.5g divinylbenzene, 0.2g AIBN, 3g polyvinylpyrrolidone
Ketone, 100g methanol are added in schlenk bottles, are stirred evenly.
(2) 55 DEG C are heated under nitrogen atmosphere to react 6 hours.Centrifugation, polymer beads are washed with ethyl alcohol after reaction
It washs, obtains final products.
Embodiment 2
The preparation of monomer is the same as embodiment 1
The preparation of polymer microballoon
(1) by 10g function monomer, 5g styrene, 0.5g divinylbenzene, 0.2g BPO, 3g polyvinylpyrrolidone,
75g ethanol/water (4/1) mixed solvent is added in schlenk bottles, is stirred evenly.
(2) 70 DEG C are heated under nitrogen atmosphere to react 3 hours.Centrifugation, polymer beads are washed with ethyl alcohol after reaction
It washs, obtains final products.
Embodiment 3
Absorption property test
Compound concentration is 200mg L-1Single rare earth solion, take rare-earth ion solution 10mL, embodiment 1 be added and makes
Standby polymer microballoon 10mg, ultrasonic vibration stand 5 hours after ten minutes.
According to formula Q=(C0-Ce) V/W calculates adsorption capacity, wherein Q (mg g-1) it is adsorption capacity, C0And Ce(mg L-
It 1) is respectively the concentration for adsorbing rare earth ion in forward and backward solution, V (mL) is the volume of solution, and W (mg) is polymer microballoon
Quality.Polymer microballoon is shown in attached drawing 5 to the adsorption capacity of each rare earth ion.
Claims (6)
1. a kind of preparation method of polymer microballoon, which is characterized in that steps are as follows:
1) vinyl compound by 1 part containing amido podand functional group (DGA monomer), 0.5-2 parts of styrene, 0.01-0.05
Part divinylbenzene, 0.01-0.02 parts of initiators, 0.1-0.2 parts of polyvinylpyrrolidone, 5-10 parts of stirring solvents are uniform；
2) it is heated to 50-70 DEG C of reaction under nitrogen atmosphere and obtains final products within 3-6 hours；
Number described above is mass fraction.
2. preparation method according to claim 1, which is characterized in that the initiator be azodiisobutyronitrile (AIBN) or
Benzoyl peroxide (BPO).
3. preparation method according to claim 1, which is characterized in that the methanol or ethanol/water that the solvent is 100%=
4/1 mixed solvent.
4. preparation method according to claim 1, which is characterized in that described to contain the vinylated of amido podand functional group
Close object the preparation method is as follows:
(1) after mixing 1 part of two sweet acid acid anhydrides and 4-10 parts of methylene chloride, 2.2 parts of di-n-butylamines are slowly added dropwise at room temperature, rise
Temperature, flow back 2h, obtains white solid M1；
(2) 1 part of M1,1 part of HOBT, 5 parts of THF are mixed, be slowly added to containing 1 part of DCC, 1 part of Boc-EDA and 5 part of THF it is molten
Liquid；Reaction obtains product M2；
(3) solution use is saturated NaHCO after 1 part of M2 and excessive hydrochloric acid to be stirred to 10h at 20 DEG C3It is washed till neutrality, obtains product M3；
(4) 1 part of M3,1 part of triethylamine and 2-10 parts of methylene chloride are stirred, are slowly added dropwise and are mixed with 1 part of acryloyl chloride and 2-
The solution of 10 parts of methylene chloride；Reaction obtains DGA monomer.
5. a kind of polymer microballoon of the described in any item preparation method preparations of claim 1-4.
6. polymer microballoon purposes described in claim 5, which is characterized in that be used for Rare Earth Separation.
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| CN107001513A (en) * | 2014-09-24 | 2017-08-01 | 日东电工株式会社 | Vinyl monomer with diethylene glycol (DEG) acid amides acid type part |
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2019
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| CN102993042A (en) * | 2012-11-19 | 2013-03-27 | 四川大学 | Method for synthesizing diamide podand extraction agent |
| CN103553958A (en) * | 2013-11-08 | 2014-02-05 | 四川大学 | Column [5] aromatic derivative modified by amido podand as well as preparation method and application thereof |
| CN107001513A (en) * | 2014-09-24 | 2017-08-01 | 日东电工株式会社 | Vinyl monomer with diethylene glycol (DEG) acid amides acid type part |
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