CN114920906A - Polyurethane containing imidazole thione unit as well as preparation method and application thereof - Google Patents
Polyurethane containing imidazole thione unit as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses polyurethane containing imidazolethione units and a preparation method and application thereof. The structural formula of the polyurethane containing the imidazolethione unit is as follows:
in the formula, R 1 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -or
R 2 Is composed of
Or
n is an integer of 23-47. The polyurethane containing the imidazolethione unit can quickly, efficiently and selectively adsorb Au in a solution 3+ The method can be used for recovering gold elements from electronic industrial wastewater, and is simple in preparation process, low in raw material cost and suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of gold ion adsorbents, and particularly relates to polyurethane containing imidazolethione units, and a preparation method and application thereof.
Background
Gold is a metal element, has excellent conductivity, good ductility and excellent inherent inertia, is widely applied to the fields of electronic equipment, chemical catalysts, biomedicine and the like, and plays an irreplaceable role. It is known that the discarded electrical and electronic devices contain gold elements and have high recycling value, but it is still difficult to recover gold from the electronic waste with high selectivity due to the presence of a large amount of interfering metal elements such as copper and nickel.
Hydrometallurgy has the advantages of accuracy, predictability, easy control and the like, and is the method for recovering gold from electronic waste with the greatest application prospect. Hydrometallurgy requires leaching gold from solid materials with acids or bases and then separating and purifying the gold in the leachate by adsorption, photocatalytic, ion exchange, extraction or flotation. The adsorption method has the advantages of environmental protection, high efficiency, low cost, easy treatment and the like, and is considered to recover Au from the solution 3+ The most efficient method. At present, the adsorbents commonly used in the adsorption method mainly comprise activated carbon, resin, mesoporous adsorbent, natural biological adsorbent, COF and the like, and most of the adsorbents have the effect of adsorbing Au 3+ The adsorption capacity is weak, the selectivity is poor, the production cost is high, environmental pollution is easy to cause and the like, and the requirements of practical application are difficult to completely meet.
Therefore, a method capable of rapidly, efficiently and selectively adsorbing Au in a solution is developed 3+ The adsorbent has very important significance.
Disclosure of Invention
The invention aims to provide polyurethane containing imidazole thione units, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a polyurethane containing imidazolethione units, which has the structural formula:
in the formula, R 1 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -or
R 2 Is composed of
n is an integer of 23 to 47.
Preferably, the number average molecular weight of the polyurethane containing the imidazolethione unit is 15000g/mol to 30000g/mol, and the functionality is 23 to 47.
The preparation method of the polyurethane containing the imidazolethione unit comprises the following steps:
1) carrying out a reaction of a compound containing an imidazole unit and 11-bromo-1-undecanol to obtain a bifunctional imidazolium salt;
2) carrying out a reaction of bifunctionality imidazolium salt and sulfur to obtain imidazolethione;
3) and (3) carrying out reaction of the imidazolethione and isocyanate to obtain the polyurethane containing imidazolethione units.
Preferably, the preparation method of the polyurethane containing the imidazolethione unit comprises the following steps:
1) dispersing a compound containing an imidazole unit, 11-bromo-1-undecanol and sodium carbonate in a solvent for reaction, and separating and purifying a reaction product to obtain bifunctional imidazolium salt;
2) dispersing bifunctionality imidazolium salt, sulfur and potassium carbonate in a solvent, reacting in a protective atmosphere, and separating and purifying a reaction product to obtain imidazolethione;
3) dispersing imidazolethione, isocyanate and an initiator in a solvent for reaction, and then separating and drying a reaction product to obtain polyurethane containing imidazolethione units.
Preferably, the compound containing imidazole unit in the step 1) is imidazole, benzimidazole,
To (3) is provided.
Preferably, the molar ratio of the compound containing imidazole units in the step 1) to the 11-bromo-1-undecanol is 1: 3-4.
Preferably, the molar ratio of the compound containing imidazole units in the step 1) to sodium carbonate is 1: 3-4.
Preferably, the solvent in step 1) is at least one of acetonitrile, N-Dimethylformamide (DMF) and toluene.
Preferably, the reaction in the step 1) is carried out at 75-90 ℃, and the reaction time is 18-24 h.
Preferably, the molar ratio of the bifunctional imidazolium salt to the sulfur in the step 2) is 1: 2-4.
Preferably, the molar ratio of the bifunctional imidazolium salt and the potassium carbonate in the step 2) is 1: 2-4.
Preferably, the solvent in step 2) is methanol.
Preferably, the protective atmosphere in step 2) is a nitrogen atmosphere or an argon atmosphere.
Preferably, the reaction in the step 2) is carried out at 70-80 ℃, and the reaction time is 12-24 h.
Preferably, the isocyanate in step 3) is one of 1, 6-hexamethylene diisocyanate and 2, 4-toluene diisocyanate.
Preferably, the molar ratio of the imidazolethione to the isocyanate in the step 3) is 1: 1-2.
Preferably, the initiator in step 3) is an organotin catalyst.
Further preferably, the initiator in step 3) is at least one of dibutyltin dilaurate and stannous isooctanoate.
Preferably, the solvent in step 3) is at least one of Dichloromethane (DCM) and Tetrahydrofuran (THF).
Preferably, the reaction in the step 3) is carried out at 70-75 ℃, and the reaction time is 10-16 h.
A method for selectively recovering gold from gold-containing wastewater comprises the following steps: and adjusting the pH value of the gold-containing wastewater to 1-7, adding the polyurethane containing the imidazolethione unit, stirring, and centrifuging and filtering.
The polyurethane containing the imidazolethione unit adsorbs Au 3+ The action principle of (1): according to the theory of soft and hard acid-base, the sulfur donor atom in polyurethane containing imidazole thione unit is used as soft base, which has strong coordination capacity to gold atom as soft acid, and Au can be realized 3+ High selective adsorption of (2).
The beneficial effects of the invention are: the polyurethane containing the imidazolethione unit can quickly, efficiently and selectively adsorb Au in a solution 3+ The method can be used for recovering gold elements from electronic industrial wastewater, and is simple in preparation process, low in raw material cost and suitable for large-scale popularization and application.
Drawings
FIG. 1 shows the NMR hydrogen spectra of HO-Im-OH, HO-ImS-OH and ImS-HDI of example 1.
FIG. 2 is a NMR carbon spectrum of HO-ImS-OH of example 1.
FIG. 3 is an electrospray mass spectrum of HO-ImS-OH of example 1.
FIG. 4 shows Au adsorption of polyurethane containing imidazolethione units according to the present invention 3+ Schematic diagram of (a).
FIG. 5 shows the polyurethane pair Au containing imidazolethione units in examples 1 to 5 3+ The adsorption efficiency test result chart of (1).
FIG. 6 is a graph of ImS-HDI vs. Au at various doses 3+ The adsorption efficiency test result chart of (1).
FIG. 7 is a graph showing the results of ImS-HDI adsorption efficiency tests on different metal ions in electronic wastewater.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a polyurethane containing imidazolethione units is prepared by the following steps:
1) dispersing 2.2g of imidazole, 20g of 11-bromo-1-undecanol and 8.4g of sodium carbonate in 250mL of acetonitrile, refluxing at 85 ℃ for 24h, cooling to room temperature, filtering, evaporating the solvent from the filtrate under reduced pressure, washing with ethyl acetate, and drying to obtain a bifunctional imidazolium salt (designated as HO-Im-OH);
2) dispersing 2.08g of bifunctional imidazolium salt in 200mL of methanol, adding 320mg of sulfur powder and 1.37g of anhydrous potassium carbonate under the protection of nitrogen, carrying out reflux reaction at 75 ℃ for 24 hours, cooling to room temperature, filtering, evaporating a solvent from a filtrate under a reduced pressure condition to obtain a crude product, purifying the crude product by a silica gel chromatographic column, wherein an eluent consists of Petroleum Ether (PE) and Ethyl Acetate (EA) according to a volume ratio of 10:1 to obtain imidazolethione (light yellow transparent granular, which is recorded as HO-ImS-OH);
3) dispersing 440mg of imidazolethione and 168.2mg of 1, 6-hexamethylene diisocyanate in 5mL of ultra-dry dichloromethane, then dropwise adding 10 mu L of dibutyltin dilaurate, reacting at 70 ℃ for 12h, cooling to room temperature, dropwise adding the reaction liquid into 500mL of methanol to obtain yellow precipitate, centrifuging, and drying the solid obtained by centrifuging to obtain polyurethane containing imidazolethione units (recorded as ImS-HDI).
ImS-HDI was synthesized as follows:
and (4) performance testing:
1) the hydrogen nuclear magnetic resonance spectrum of HO-Im-OH, HO-ImS-OH and ImS-HDI in the present example is shown in FIG. 1.
Performing spectrum analysis:
HO-Im-OH： 1 H NMR(400MHz,Chloroform-d)δ6.67(s,2H),4.08-3.99(m,4H),3.64(t,J＝6.6Hz,4H),1.81-1.72(m,4H),1.55(dt,J＝8.0,6.5Hz,5H),1.39-1.18(m,30H)。
HO-ImS-OH： 1 HNMR(400MHz,Chloroform-d)：δ6.67(s,2H),4.08-3.99(m,4H),3.64(t,J＝6.6Hz,4H),1.81-1.72(m,4H),1.55(dt,J＝8.0,6.5Hz,4H),1.36-1.22(m,28H)。
ImS-HDI： 1 H NMR(500MHz,Chloroform-d)：δ8.02(s,2H),4.02(t,J＝7.5Hz,4H),3.12(d,J＝27.7Hz,4H),2.96(s,6H),2.89(s,6H),1.59(s,8H),1.29(d,J＝31.4Hz,20H),0.86(dt,J＝17.0,6.1Hz,2H)。
2) the NMR spectrum of HO-ImS-OH in this example is shown in FIG. 2.
Performing spectrum analysis:
13 C NMR(101MHz,Chloroform-d)：δ161.45,116.53,77.25,63.04,47.88,32.79,29.52,29.42,29.37,29.17,28.93,26.57,25.72。
3) the electrospray mass spectrum of HO-ImS-OH in this example is shown in FIG. 3.
Performing spectrum analysis:
MS(ESI-MS，m/z)：Calc.for HO-ImS-OH：440，Found：463.3341(M+Na) + 。
the number average molecular weight of polyurethane containing imidazolethione units (ImS-HDI) in the example was 245634 g/mol (n in the structural formula is 38), and the functionality was 38.
Example 2:
the preparation method of polyurethane containing imidazolethione units comprises the following steps:
440mg of imidazolethione (prepared in example 1) and 174mg of 2, 4-toluene diisocyanate are dispersed in 5mL of ultra-dry dichloromethane, 10 mu L of dibutyltin dilaurate is dropwise added, the reaction is carried out at 70 ℃ for 12 hours, the reaction is cooled to room temperature, the reaction solution is dropwise added into 500mL of methanol to obtain yellow precipitate, the yellow precipitate is centrifuged, and the solid obtained by the centrifugation is dried to obtain polyurethane containing imidazolethione units (recorded as ImS-TDI).
ImS-TDI was synthesized as follows:
example 3:
a polyurethane containing imidazolethione units is prepared by the following steps:
1) 3.8g of benzimidazole, 20g of 11-bromo-1-undecanol and 8.4g of sodium carbonate were dispersed in 250mL of acetonitrile, refluxed at 85 ℃ for 24h, cooled to room temperature, filtered, the filtrate was evaporated under reduced pressure, washed with ethyl acetate and dried to obtain a bifunctional imidazolium salt (designated as HO-BnIm-OH);
2) dispersing 2.29g of bifunctional imidazolium salt in 200mL of methanol, adding 320mg of sulfur powder and 1.37g of anhydrous potassium carbonate under the protection of nitrogen, carrying out reflux reaction at 75 ℃ for 24h, cooling to room temperature, filtering, evaporating a solvent from a filtrate under a reduced pressure condition to obtain a crude product, purifying the crude product by a silica gel chromatographic column, wherein an eluent consists of Petroleum Ether (PE) and Ethyl Acetate (EA) according to a volume ratio of 10:1 to obtain imidazolethione (light yellow transparent granular, which is recorded as HO-BnImS-OH);
3) 490mg of imidazolethione and 168.2mg of 1, 6-hexamethylene diisocyanate are dispersed in 5mL of ultra-dry dichloromethane, 10 mu L of dibutyltin dilaurate is dropwise added, the reaction is carried out at 70 ℃ for 12h, the reaction is cooled to room temperature, the reaction solution is dropwise added into 500mL of methanol to obtain yellow precipitate, the yellow precipitate is centrifuged, and the solid obtained by centrifugation is dried to obtain polyurethane containing imidazolethione units (recorded as BnImS-HDI).
The synthesis reaction of BnImS-HDI is as follows:
example 4:
a polyurethane containing imidazolethione units is prepared by the following steps:
490mg of imidazolethione (prepared in example 3) and 174mg of 2, 4-toluene diisocyanate are dispersed in 5mL of ultra-dry dichloromethane, 10 mu L of dibutyltin dilaurate is dropwise added, the reaction is carried out at 70 ℃ for 12 hours, the reaction is cooled to room temperature, the reaction solution is dropwise added into 500mL of methanol to obtain yellow precipitate, the yellow precipitate is centrifuged, and the solid obtained by centrifugation is dried to obtain polyurethane containing imidazolethione units (recorded as BnImS-TDI).
The synthesis reaction of BnImS-TDI is as follows:
example 5:
a polyurethane containing imidazolethione units is prepared by the following steps:
1) dispersing 1.32g of 1, 3-dibromobenzene, 0.68g of imidazole, 0.04g of cuprous iodide, 0.11g of salicylaldoxime and 3.91g of cesium carbonate in 5mL of acetonitrile, reacting at 80 ℃ for 48h, filtering, washing the filtered solid with 30mL of dichloromethane for 2 times, combining the washed liquid with the filtrate, washing the filtrate with 30mL of water for 2 times, separating, collecting the organic phase, and adding Na to the organic phase 2 SO 4 Drying, filtering, heating the filtrate to evaporate the solvent to obtain
(yellow solid, noted DisMiz-Bn);
2) 679mg of
Dispersing 2g of 11-bromo-1-undecanol and 840mg of sodium carbonate in 25mL of acetonitrile, refluxing at 85 ℃ for 24h, cooling to room temperature, filtering, evaporating the solvent from the filtrate under reduced pressure, washing with ethyl acetate, and drying to obtain a bifunctional imidazolium salt (described as HO-Diim-OH);
3) dispersing 2.08g of bifunctional imidazolium salt in 200mL of methanol, adding 640mg of sulfur powder and 2.74g of anhydrous potassium carbonate under the protection of nitrogen, carrying out reflux reaction at 75 ℃ for 24 hours, cooling to room temperature, filtering, evaporating a solvent from a filtrate under a reduced pressure condition to obtain a crude product, purifying the crude product by a silica gel chromatographic column, wherein an eluent consists of Petroleum Ether (PE) and Ethyl Acetate (EA) according to a volume ratio of 10:1 to obtain imidazolethione (light yellow transparent granular, which is recorded as HO-DiImS-OH);
4) 614mg of imidazolethione and 168.2mg of 1, 6-hexamethylene diisocyanate are dispersed in 5mL of ultra-dry dichloromethane, 10 mu L of dibutyltin dilaurate is dropwise added, the reaction is carried out at 70 ℃ for 12 hours, the reaction is cooled to room temperature, the reaction solution is dropwise added into 500mL of methanol to obtain yellow precipitate, the yellow precipitate is centrifuged, and the solid obtained by centrifugation is dried to obtain polyurethane containing imidazolethione units (recorded as DiImS-HDI).
The synthesis reaction of DiImS-HDI is as follows:
application example 1:
18.468mg of chloroauric acid was dispersed in 120mL of a hydrochloric acid solution with a mass fraction of 5% to prepare Au 3+ 10mL of the standard solution (concentration: 105.13mg/L) was put into a glass bottle containing a magnetic stirrer, and 10mg of the imidazolethione unit-containing polyurethane of examples 1 to 5 (imidazolethione unit-containing polyurethane-adsorbed Au) was added 3+ The schematic diagram is shown in figure 4), stirring for 1h at room temperature, centrifuging for 10min at 4500r/min, filtering with a filter membrane with the pore diameter of 0.22 mu m, and measuring the residual Au in the filtrate by atomic absorption spectrophotometry 3+ And the adsorption rate (q) of the imidazolethione unit-containing polyurethane is calculated by the following formula:
q＝(C 0 -C e )/C 0 x100%, wherein C 0 And C e Respectively Au in solution 3+ The initial concentration and the residual concentration of (2) in mg/L.
Examples 1 to 5 polyurethane Pair Au containing Imidazothione Unit 3+ Fig. 5 and table 1 show the results of the adsorption efficiency test.
TABLE 1 polyurethane containing imidazolethione units to Au in examples 1 to 5 3+ Adsorption efficiency test results of
As can be seen from fig. 5 and table 1:
a) the gold extraction efficiency of the polyurethane containing imidazolethione units in examples 1-5 is 99.99% (ImS-HDI), 99.80% (ImS-TDI), 99.96% (BnImS-HDI), 46.04% (BnImS-TDI) and 99.91% (DiImS-HDI), respectively;
b) compared with the BnImS-TDI, the BnImS-HDI has better adsorption performance because the polymer chain of the BnImS-TDI has a benzene ring with stronger rigidity, and imidazole thione and Au are prevented to a certain extent 3+ The coordination between the two components reduces the adsorption efficiency;
c) since imidazolethione and Au 3+ The coordination capacity of the compound is higher than that of benzimidazolethione, so the extraction rate of ImS-TDI is much higher than that of BnImS-TDI;
d) polyurethane containing imidazolethione units (starting from imidazolethione and 1, 6-hexamethylene diisocyanate) versus Au as in example 1 3+ The extraction efficiency of (2) is highest;
in conclusion, the polyurethane containing the imidazolethione unit can quickly, efficiently and selectively adsorb gold elements from an acidic solution similar to electronic waste liquid.
Application example 2:
in 5 cells, 10mL of Au was contained 3+ 3.24mg, 6.48mg, 9.71mg, 12.95mg and 16.19mg of ImS-HDI of example 1 were added to a glass bottle containing a standard solution (same as in application example 1, concentration: 101.95mg/L), stirred at room temperature for 1 hour, centrifuged at 4500r/min for 10 minutes, filtered through a filter having a pore size of 0.22 μm, and the remaining Au content in the filtrate was measured by atomic absorption spectrophotometry 3+ And the adsorption rate of the polyurethane containing imidazolethione units is calculated, and the test results are shown in fig. 6 and table 2:
TABLE 2 different dosages of ImS-HDI vs. Au 3+ Adsorption efficiency test results of
As can be seen from fig. 6 and table 2: when imidazole sulfurKetones and Au 3+ The extraction efficiency of ImS-HDI was only 82% at a stoichiometric ratio of 1:1, due to the imidazole thione and Au 3+ Coordinated in a 2:1 manner resulting in a portion of Au being adsorbed during the adsorption process 3+ Two imidazolethiones are prepared, and a part of the imidazolethiones is combined with only one imidazolethione, so that the adsorption efficiency of ImS-HDI is reduced; when imidazolethione is reacted with Au 3+ The adsorption efficiency of ImS-HDI reaches more than 99.3% when the stoichiometric ratio of (1) is more than or equal to 2:1, which shows that the polyurethane containing the imidazolethione adsorbs Au in an acidic aqueous solution 3+ The efficiency and sensitivity of (a) is rather high.
Application example 3:
10mg of ImS-HDI solid powder were added directly to 10mL of Au 3+ 、Na + 、Fe 3+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Mn 2+ 、Zn 2+ Stirring the ionic water solution for 1h at room temperature, centrifuging the solution at 4500r/min for 10min, filtering the solution by using a filter membrane with the pore diameter of 0.22 mu m, measuring the concentration of the residual metal ions in the filtrate by using an atomic absorption spectrophotometry, and calculating the adsorption rate of polyurethane containing imidazolethione units, wherein the test results are shown in a figure 7 and a table 3:
table 3 ImS-results of testing the adsorption efficiency of HDI on different metal ions in electronic wastewater
As can be seen from fig. 7 and table 3: ImS-HDI is only for Au 3+ The adsorption efficiency of the gold-doped tin oxide can reach more than 99 percent, and the adsorption rate of the gold-doped tin oxide to the rest metal ions is lower than 10 percent, so ImS-HDI can rapidly, efficiently and selectively recover Au under the acidic condition 3+ This has a very broad prospect for recovering gold from electronic waste.
In summary, the invention provides a polyurethane material capable of selectively adsorbing gold ions, which can rapidly, efficiently and selectively adsorb gold elements from an acidic solution similar to electronic waste liquid.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A polyurethane containing imidazolethione units is characterized in that the structural formula is as follows:
in the formula, R 1 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -or
R 2 Is composed of
Or
n is an integer of 23-47.
2. The imidazolethione unit containing polyurethane as claimed in claim 1, wherein: the number average molecular weight of the polyurethane containing the imidazolethione unit is 15000 g/mol-30000 g/mol, and the functionality is 23-47.
3. The method for producing imidazolethione unit-containing polyurethane as claimed in claim 1 or 2, which comprises the steps of:
1) carrying out a reaction of a compound containing imidazole units and 11-bromo-1-undecanol to obtain a bifunctional imidazolium salt;
2) carrying out a reaction of bifunctionality imidazolium salt and sulfur to obtain imidazolethione;
3) and (3) carrying out reaction of the imidazolethione and isocyanate to obtain the polyurethane containing imidazolethione units.
4. The method for producing imidazolethione unit-containing polyurethane according to claim 3, wherein: the compound containing the imidazole unit in the step 1) is imidazole, benzimidazole,
One kind of (1).
5. The method for producing imidazolethione unit-containing polyurethane according to claim 3 or 4, wherein: the molar ratio of the compound containing the imidazole unit in the step 1) to the 11-bromo-1-undecanol is 1: 3-4.
6. The method for producing imidazolethione unit-containing polyurethane according to claim 3, wherein: the molar ratio of the bifunctionality imidazolium salt to sulfur in the step 2) is 1: 2-4.
7. The method for producing imidazolethione unit-containing polyurethane as claimed in claim 3, wherein: and in the step 3), the isocyanate is one of 1, 6-hexamethylene diisocyanate and 2, 4-toluene diisocyanate.
8. The method for producing imidazolethione unit-containing polyurethane as claimed in claim 3 or 7, wherein: the molar ratio of the imidazolethione to the isocyanate in the step 3) is 1: 1-2.
9. The method for producing imidazolethione unit-containing polyurethane as claimed in any one of claims 3, 4, 6 and 7, wherein: the reaction of the step 1) is carried out at 75-90 ℃ for 18-24 h; the reaction in the step 2) is carried out at 70-80 ℃, and the reaction time is 12-24 h; the reaction in the step 3) is carried out at 70-75 ℃, and the reaction time is 10-16 h.
10. Use of the polyurethane containing imidazolethione units according to claim 1 or 2 for the selective recovery of gold from gold-containing waste waters.
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