CN114920906B - Polyurethane containing imidazolethione unit and preparation method and application thereof - Google Patents
Polyurethane containing imidazolethione unit and 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 to 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.
The hydrometallurgy has the advantages of accuracy, predictability, easy control and the like, and is the most promising for recovering gold from electronic wasteThe method of (1). Hydrometallurgy requires leaching gold from solid materials with acids or bases, followed by separation and purification of the gold in the leachate by adsorption, photocatalysis, 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 imidazolethione 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 a structural formula 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
n is an integer of 23 to 47.
Preferably, the imidazole thione unit-containing polyurethane has a number average molecular weight of 15000g/mol to 30000g/mol and a functionality of 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 imidazolethione and isocyanate to obtain 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,
One kind of (1).
Preferably, the molar ratio of the compound containing an imidazole unit in the step 1) to 11-bromo-1-undecanol is 1.
Preferably, the molar ratio of the imidazole unit-containing compound in step 1) to sodium carbonate is 1.
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 ℃ for 18-24 h.
Preferably, the molar ratio of the bifunctional imidazolium salt to the sulfur in step 2) is 1.
Preferably, the molar ratio of the bifunctional imidazolium salt to the potassium carbonate in the step 2) is 1.
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.
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: adjusting the pH value of the gold-containing wastewater to 1-7, adding the polyurethane containing the imidazolethione unit, stirring, 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 invention has the beneficial effects that: the polyurethane containing the imidazolethione unit can quickly, efficiently and selectively adsorb a solutionIn (5) Au 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 in example 1.
FIG. 2 is a NMR carbon spectrum of HO-ImS-OH in 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 invention 3+ Schematic diagram of (1).
FIG. 5 shows the polyurethane pair Au containing imidazolethione units of examples 1 to 5 3+ The adsorption efficiency test result chart of (1).
FIG. 6 is ImS-HDI vs Au at different doses 3+ The adsorption efficiency test result chart of (1).
FIG. 7 is a graph showing the result of ImS-HDI adsorption efficiency test 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 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, and obtaining imidazolethione (light yellow transparent granular, which is recorded as HO-ImS-OH);
3) 440mg 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 the centrifugation is dried to obtain polyurethane containing imidazolethione units (recorded as ImS-HDI).
The synthesis reaction of ImS-HDI is as follows:
and (3) performance testing:
1) The NMR spectra of HO-Im-OH, HO-ImS-OH and ImS-HDI in this example are 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 the polyurethane containing imidazolethione units (ImS-HDI) in this example was determined to be 245634 g/mol (where n in the structural formula is 38) and the functionality was 38.
Example 2:
a polyurethane containing imidazolethione units is prepared by 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 centrifugation is dried to obtain polyurethane containing imidazolethione units (recorded as ImS-TDI).
The synthesis reaction of ImS-TDI is 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, and obtaining 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 added dropwise, the reaction is carried out at 70 ℃ for 12 hours, the reaction is cooled to room temperature, the reaction solution is added dropwise 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 48 hours, 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 the liquid, collecting the organic phase, and adding Na to the organic phase 2 SO 4 Drying, filtering, heating the filtrate to evaporateSolvent 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 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 through a silica gel chromatographic column, wherein an eluent is composed of Petroleum Ether (PE) and Ethyl Acetate (EA) according to a volume ratio of 10, and thus obtaining imidazolethione (a light yellow transparent granular shape, 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 is dispersed in 120mL of hydrochloric acid solution with the mass fraction of 5% to prepare Au 3+ 10mL of the standard solution (concentration: 105.13 mg/L) was put into a glass bottle containing a magnetic stirrer, and 10mg of the solution containing the same as in examples 1 to 5 was addedPolyurethane of imidazolethione unit (polyurethane containing imidazolethione unit adsorbs Au 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 x 100%, wherein C 0 And C e Respectively Au in solution 3+ The initial concentration and the residual concentration of (2) in mg/L.
Polyurethane containing imidazolethione units to Au in examples 1 to 5 3+ The results of the adsorption efficiency test of (a) are shown in fig. 5 and table 1.
TABLE 1 polyurethane containing imidazolethione units of examples 1 to 5 vs Au 3+ Adsorption efficiency test results of
As can be seen from fig. 5 and table 1:
a) The gold extraction efficiencies of the imidazolethione unit-containing polyurethanes of examples 1 to 5 were 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 benzimidazole thione, so that the extraction rate of ImS-TDI is far higher than that of BnImS-TDI;
d) Polyurethane containing imidazolethione units of example 1 (starting from imidazolethione and 1, 6-hexamethylene diisocyanate) to Au 3+ The extraction efficiency 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+ A glass bottle containing the standard solution (same as in application example 1, concentration: 101.95 mg/L) was charged with 3.24mg, 6.48mg, 9.71mg, 12.95mg and 16.19mg of ImS-HDI of example 1, respectively, 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 doses of ImS-HDI vs Au 3+ Adsorption efficiency test results of
As can be seen from fig. 6 and table 2: when imidazolethione and Au are mixed 3+ 1, the efficiency of ImS-HDI extraction is only 82% due to the imidazole thione and Au 3+ Is coordinated in a manner of 2 3+ Two imidazolethiones are prepared, and one part of imidazolethiones is combined with only one imidazolethione, so that the adsorption efficiency of ImS-HDI is reduced; when imidazolethione and Au are mixed 3+ When the stoichiometric ratio of (a) to (b) is greater than or equal to 2, the adsorption efficiency of ImS-HDI reaches 99.3% or more, which indicates that the polyurethane containing 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 was directly added to 10mL of Au 3+ 、Na + 、Fe 3+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Mn 2+ 、Zn 2+ Stirring in ion water solution at room temperature for 1h, centrifuging at 4500r/min for 10min, filtering with filter membrane with pore diameter of 0.22 μm, measuring the concentration of residual metal ions in the filtrate by atomic absorption spectrophotometry, and calculating the polymer containing imidazolethione unitThe adsorption rate of the urethane, the test results are shown in fig. 7 and table 3:
table 3 test results of adsorption efficiency of ImS-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 can reach more than 99 percent, and the adsorption rate to the rest metal ions is lower than 10 percent, so the ImS-HDI can quickly, 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 modifications 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
And n is an integer of 23 to 47.
2. The imidazolethione unit containing polyurethane according to claim 1, wherein: 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.
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 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 imidazolethione and isocyanate to obtain 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 as claimed in 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.
6. The method for producing imidazolethione unit-containing polyurethane as claimed in claim 3, wherein: step 2) the molar ratio of the bifunctional imidazolium salt to sulfur is 1 to 2-4.
7. The method for producing imidazolethione unit-containing polyurethane according to claim 3, wherein: and 3) the isocyanate in the step 3) is one of 1, 6-hexamethylene diisocyanate and 2, 4-toluene diisocyanate.
8. The method for producing imidazolethione unit-containing polyurethane according to claim 3 or 7, characterized in that: the molar ratio of the imidazolethione to the isocyanate in the step 3) is 1-2.
9. The method for producing imidazolethione unit-containing polyurethane according to any one of claims 3, 4, 6 and 7, characterized in that: 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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