CN109942735B - Preparation method of polymer microspheres for rare earth separation - Google Patents
Preparation method of polymer microspheres for rare earth separation Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 11
- 238000000926 separation method Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000012467 final product Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 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 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- PIYNUZCGMLCXKJ-UHFFFAOYSA-N 1,4-dioxane-2,6-dione Chemical compound O=C1COCC(=O)O1 PIYNUZCGMLCXKJ-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000003999 initiator Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- -1 rare earth ions Chemical class 0.000 description 7
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- GKQLYSROISKDLL-UHFFFAOYSA-N EEDQ Chemical compound C1=CC=C2N(C(=O)OCC)C(OCC)C=CC2=C1 GKQLYSROISKDLL-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- 241001495452 Podophyllum Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- YJGVMLPVUAXIQN-XVVDYKMHSA-N podophyllotoxin Chemical compound COC1=C(OC)C(OC)=CC([C@@H]2C3=CC=4OCOC=4C=C3[C@H](O)[C@@H]3[C@@H]2C(OC3)=O)=C1 YJGVMLPVUAXIQN-XVVDYKMHSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- AOCSUUGBCMTKJH-UHFFFAOYSA-N tert-butyl n-(2-aminoethyl)carbamate Chemical compound CC(C)(C)OC(=O)NCCN AOCSUUGBCMTKJH-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a process for preparing polymer microspheres for rare earth separation. Uniformly stirring 1 part of DGA monomer, 0.5-2 parts of styrene, 0.01-0.05 part of divinylbenzene, 0.01-0.02 part of initiator, 0.1-0.2 part of polyvinylpyrrolidone and 5-10 parts of solvent, and heating to 50-70 ℃ in a nitrogen atmosphere for reaction for 3-6 hours to obtain a final product. The prepared polymer microspheres can be used for separating rare earth elements by adopting an adsorption or solid-phase extraction mode; and the polymer microspheres do not contain phosphorus elements, can be completely combusted after being discarded, and are green adsorption separation materials.
Description
Technical Field
The invention relates to a synthesis process of polymer microspheres for rare earth separation, in particular to a synthesis process of polymer microspheres containing amide podophyllum ether.
Background
With the consumption of rare earth resources and pollution caused in the process of mining and application thereof, the recycling of the rare earth resources and the analysis and detection of rare earth in environmental samples become more and more important, so that the separation and enrichment technology of rare earth, which is essential in the process, is more and more concerned by people. Amide poda ether group (DGA) is a functional group with good coordination ability to trivalent rare earth ions, and has been applied to an extractant. It is a green extractant (Chemical reviews. 2012,112,1751) because it contains no phosphorus element common in common extractant and can be completely incinerated. Their use for the modification of adsorbents is also of increasing interest (RSC adv.,2015,5, 103782).
In recent years, the micron-sized polymer microspheres are widely polymerized in the fields of solid-phase extraction, chromatographic separation and the like. Dispersion polymerization is considered to be an effective method for preparing micron-sized polymeric microspheres. The polymer microsphere rich in DGA groups can be prepared by synthesizing amide podand ether monomers containing carbon-carbon double bonds and using the monomers for dispersion polymerization, and the polymer microsphere is expected to become a high-efficiency rare earth separation material.
Disclosure of Invention
The invention prepares a micron-sized polymer microsphere for rare earth separation by dispersing and copolymerizing styrene and DGA functional monomers. The technical scheme of the invention is as follows:
a preparation method of micron-sized polymer microspheres comprises the following steps:
(1) 1 part of DGA monomer (vinyl compound containing amide podand ether functional groups), 0.5-2 parts of styrene, 0.01-0.05 part of divinylbenzene, 0.01-0.02 part of initiator, 0.1-0.2 part of polyvinylpyrrolidone and 5-10 parts of solvent are stirred uniformly;
(2) heating to 50-70 ℃ in nitrogen atmosphere, and reacting for 3-6 hours to obtain the final product.
And after the reaction is finished, centrifuging, and washing the polymer particles by using ethanol to obtain the final product.
The above ratio is a mass ratio.
Wherein the initiator is Azobisisobutyronitrile (AIBN) or Benzoyl Peroxide (BPO), and the solvent is 100% methanol or ethanol/water 4/1 mixed solvent.
The preparation method of the DGA monomer comprises the following steps:
(1) mixing 1 part of diglycolic anhydride and 4-10 parts of dichloromethane, slowly dropwise adding 2.2 parts of di-n-butylamine at room temperature, heating, and refluxing for 2 hours to obtain a white solid M1;
(2) mixing and stirring 1 part of M1, 1 part of HOBT and 5 parts of THF, and slowly adding a solution containing 1 part of DCC, 1 part of Boc-EDA and 5 parts of THF; the reaction is carried out to obtain a product M2;
(3) after 1 part of M2 and excess hydrochloric acid have been stirred for 10h at 20 ℃ the solution is saturated NaHCO3Washing to neutrality to obtain product M3;
(4) stirring and mixing 1 part of M3, 1 part of triethylamine and 2-10 parts of dichloromethane, and slowly dropwise adding a solution mixed with 1 part of acryloyl chloride and 2-10 parts of dichloromethane; the DGA monomer is obtained by reaction.
The above ratios are molar ratios.
The more specific technical scheme of the invention is as follows:
(1) adding 1 part of DGA monomer, 0.5-2 parts of styrene, 0.01-0.05 part of divinylbenzene, 0.01-0.02 part of initiator, 0.1-0.2 part of polyvinylpyrrolidone and 5-10 parts of solvent into a schlenk bottle, and uniformly stirring.
(2) Heating to 50-70 ℃ in nitrogen atmosphere for reaction for 3-6 hours. And after the reaction is finished, centrifuging, and washing the polymer particles by using ethanol to obtain the final product.
Wherein the initiator is Azobisisobutyronitrile (AIBN) or Benzoyl Peroxide (BPO), and the solvent is 100% methanol or ethanol/water 4/1 mixed solvent.
The parts are all parts by mass.
Compared with the existing product, the invention has the beneficial effects that:
the polymer microspheres prepared by the invention can be used for separating rare earth elements by adopting an adsorption or solid-phase extraction mode; and the polymer microspheres do not contain phosphorus elements, can be completely combusted after being discarded, and are green adsorption separation materials.
Drawings
FIG. 1 is a scheme of monomer synthesis;
FIG. 2 is a nuclear magnetic spectrum of a monomer prepared in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of polymeric microspheres of example 1;
FIG. 4 is an infrared spectrum of the polymeric microsphere of example 1;
FIG. 5 is a graph showing the adsorption capacity of the polymer microspheres of example 3 for each rare earth ion.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments below:
the following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The reagents used in the examples are abbreviated as follows:
tetrahydrofuran: THF; dimethyl sulfoxide: DMSO; n, N-dimethylformamide: DMF; 1-hydroxybenzotriazole: HOBT; dicyclohexylcarbodiimide: DCC; N-Boc-ethylenediamine: Boc-EDA; 3-aminopropyltriethoxysilane: APTES; 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline: EEDQ.
Example 1
Preparation of monomers
(1) 30g of diethylene glycol anhydride and 300mL of methylene chloride were added to a 1000mL round-bottom flask and stirred. 33g of di-n-butylamine are slowly added dropwise at room temperature, the temperature is raised, and the reflux is carried out for 2 h. The crude product was recrystallized to give a white solid noted M1.
(2) 24.5g M1, 13.5g HOBT, 100mL THF (100mL) were added to the round bottom flask and stirred, and a solution of 20.6g DCC and 16g Boc-EDA in 150mL THF was slowly added. Stirring was continued at room temperature for 10 h. After the reaction, the mixture was filtered to obtain a filtrate. The crude product was purified by column chromatography and the product was designated as M2.
(3) 20g M2 and 10mL hydrochloric acid were stirred at 20 ℃ for 10h and the solution was saturated NaHCO3The solution was washed to neutrality, concentrated and purified by column chromatography, and the product was designated as M3.
(4) 28.7g M3, 10g triethylamine and 50mL dichloromethane were added sequentially to the round bottom flask, stirred and cooled in an ice bath. A solution of 9.05g acryloyl chloride in 20mL methylene chloride was slowly added dropwise. The temperature is raised to room temperature, and stirring is continued for 3 h. Filtering after the reaction is finished, concentrating the filtrate, and purifying by column chromatography to obtain the monomer.
Preparation of polymeric microspheres
(1) 10g of functional monomer, 10g of styrene, 0.5g of divinylbenzene, 0.2g of AIBN, 3g of polyvinylpyrrolidone and 100g of methanol were put into a schlenk bottle and stirred uniformly.
(2) The reaction was heated to 55 ℃ for 6 hours under nitrogen atmosphere. And after the reaction is finished, centrifuging, and washing the polymer particles by using ethanol to obtain the final product.
Example 2
Preparation of monomers as in example 1
Preparation of polymeric microspheres
(1) 10g of functional monomer, 5g of styrene, 0.5g of divinylbenzene, 0.2g of BPO, 3g of polyvinylpyrrolidone and 75g of ethanol/water (4/1) mixed solvent were put into a schlenk bottle and stirred uniformly.
(2) The reaction was heated to 70 ℃ for 3 hours under nitrogen atmosphere. And after the reaction is finished, centrifuging, and washing the polymer particles by using ethanol to obtain the final product.
Example 3
Adsorption Performance test
The preparation concentration is 200mg L-1Taking 10mL of rare earth ion solution, adding 10mg of the polymer microsphere prepared in example 1, ultrasonically shaking for 10 minutes, and standing for 5 hours.
According to the formula Q ═ C0-Ce) V/W the adsorption capacity was calculated, where Q (mg g)-1) To adsorption capacity, C0And Ce(mg L-1) is the concentration of the rare earth ions in the solution before and after adsorption, V (mL) is the volume of the solution, and W (mg) is the mass of the polymer microspheres. The adsorption capacity of the polymer microspheres to each rare earth ion is shown in figure 5.
Claims (1)
1. A preparation method of polymer microspheres for rare earth separation is characterized by comprising the following preparation steps:
1) preparation of monomers
(1) Adding 30g of diglycolic anhydride and 300mL of dichloromethane into a 1000mL round-bottom flask, and stirring; slowly dropwise adding 33g of di-n-butylamine at room temperature, heating and refluxing for 2 h; recrystallizing the crude product to obtain a white solid which is recorded as M1;
(2) 24.5g M1, 13.5g HOBT, 100ml THF were added to the round bottom flask and stirred, and a solution of 20.6g DCC and 16g Boc-EDA in 150ml THF was slowly added; continuously stirring for 10 hours at room temperature; filtering after the reaction is finished, concentrating the filtrate, and purifying a crude product by using a column chromatography method, wherein the product is marked as M2;
(3) 20g M2 and 10mL hydrochloric acid were stirred at 20 ℃ for 10h and the solution was saturated NaHCO3Washing to neutrality, concentrating the solution, and purifying by column chromatography to obtain product M3;
(4) adding 28.7g M3, 10g triethylamine and 50mL dichloromethane into a round-bottom flask in sequence, stirring, and cooling in an ice bath; slowly dripping 20mL of dichloromethane solution dissolved with 9.05g of acryloyl chloride; heating to room temperature, and continuously stirring for 3 h; filtering after the reaction is finished, concentrating the filtrate, and purifying by column chromatography to obtain a monomer;
2) preparation of polymeric microspheres
(1) Adding 10g of the monomer prepared in the step 1), 10g of styrene, 0.5g of divinylbenzene, 0.2g of AIBN, 3g of polyvinylpyrrolidone and 100g of methanol into a schlenk bottle, and uniformly stirring;
(2) heating to 55 ℃ in nitrogen atmosphere to react for 6 hours; and after the reaction is finished, centrifuging, and washing the polymer particles by using ethanol to obtain the final product.
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| CN101139418A (en) * | 2007-07-19 | 2008-03-12 | 四川大学 | Extraction resin with amide compound as extraction agent and preparation method thereof |
| 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 |
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|---|---|---|---|---|
| JP6493868B2 (en) * | 2014-09-24 | 2019-04-03 | 日東電工株式会社 | Vinyl monomer having diglycolamide acid type ligand |
| US10344355B2 (en) * | 2016-08-22 | 2019-07-09 | Uchicago Argonne, Llc | Process for the separation and purification of scandium medical isotopes |
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|---|---|---|---|---|
| CN101139418A (en) * | 2007-07-19 | 2008-03-12 | 四川大学 | Extraction resin with amide compound as extraction agent and preparation method thereof |
| 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 |
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