Preparation of rosin-based trihydroxamic acids (salts) and use thereof
By using renewable rosin to prepare rosin-based ternary isohydroxamic acid (salt), the problems of environmental unfriendliness and low efficiency of existing hydroxamic acid compounds are solved, and the effect of efficient adsorption and recovery of heavy metal ions is achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGXI UNIV FOR NATITIES
- Filing Date
- 2024-11-27
- Publication Date
- 2026-07-24
AI Technical Summary
The raw materials for the preparation of existing hydroxamic acid compounds mainly come from petrochemical derivatives, which is not environmentally friendly. In addition, the number of monohydroxamic acid functional groups is limited, resulting in low efficiency and high cost.
Using renewable rosin as raw material, a DA addition reaction is carried out with unsaturated dicarboxylic acid to prepare a tricarboxylic acid, which is then reacted with hydroxylamine to generate rosin-based tricarboxylic acid (salt), increasing the number of hydroxamic acid groups and improving chelation ability.
The prepared rosin-based ternary hydroxamic acid (salt) has multiple hydroxamic acid groups, which can efficiently adsorb and recover heavy metal ions, reduce production costs, and is environmentally friendly.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic compound preparation, specifically relating to a method for preparing a ternary hydroxamic acid or hydroxamic acid salt. Background Technology
[0002] Hydroxime acids exist in two tautomers: isohydroxime and hydroxamic acid. These two isomers coexist, but isohydroxime is dominant, with the general structural formula RC(OH)=NOH. This structure features closely spaced oxygen and nitrogen atoms, each possessing a lone pair of electrons. Due to its efficient chelating effect, it has wide applications in flotation, metallurgy, and pharmaceuticals. In flotation and metallurgy, hydroxamic acids can chelate with metal ions (Sn2+, Pb2+, Cu2+, Co2+, Ni2+, Cd2+, etc.) on mineral surfaces and in industrial wastewater, forming stable multi-ring metal chelates. This makes hydroxamic acids and their hydroxamic acid salts widely used in the flotation of metal minerals and wastewater treatment. In the pharmaceutical field, isohydroxamic acid, when used in combination with other drugs or protein deacetylase inhibitors, has a wide range of pharmacological effects in the treatment of cancer, cardiovascular diseases, HIV, Alzheimer's disease, malaria, and allergic diseases.
[0003] Traditional hydroxamic acids typically have only one hydroxamic acid functional group. Their preparation generally involves reacting hydroxylamine salts and organic acid esters in an alkaline solvent, commonly water or methanol. For example, patent CN101519365A discloses a method for producing salicylic acid hydroxamic acid, where a strong alkaline aqueous solution is used to maintain the pH of the reaction system at approximately 12.0. Measuring amounts of hydroxylamine aqueous solution and methyl salicylate are mixed and reacted for a certain time, then the pH is adjusted to 4.0–5.0 with acid to obtain salicylic acid hydroxamic acid. Patent CN102513218A discloses a method for preparing a collector for bauxite flotation, which involves reacting hydroxylamine salts and organic acid esters in an alkaline solvent. Hydroxyxamate products are obtained by reacting aqueous amine solution, methyl benzoate and sodium hydroxide solution in a certain proportion; products with two or more hydroxyxamic acid functional groups are rare. For example, Sun Xin et al. prepared phthalic acid (synthesis of novel hydroxyxamic acid collector and its collection mechanism of malachite [J]. Mineral Resources Conservation and Utilization, 2022, 42(1): 9). The reaction was carried out by reacting dimethyl phthalate, hydroxylamine hydrochloride and sodium hydroxide in a molar ratio of 1:2.1:8.4 in a three-necked flask at 50°C for 4 h, and then acidified with hydrochloric acid to pH 4-5 to obtain phthalic acid with dihydroxyxamic acid groups.
[0004] Currently, commonly used hydroxamic acids such as benzyl hydroxamic acid and salicylic acid used in industrial applications have the following problems: ① The raw materials for preparing hydroxamic acid compounds are mostly derived from petrochemical derivatives such as styrene, which is not conducive to green environmental protection and sustainable development; ② Most existing isohydroxamic acid molecules have only one hydroxamic acid functional group, which can only chelate with one metal ion, resulting in low efficiency and excessive use of hydroxamic acid, thereby increasing the cost in actual production. To solve these problems, research is proposed to be carried out in the following aspects: ① Using renewable resources as raw materials for hydroxamic acid to replace petrochemical derivatives; ② Increasing the number of chelating functional groups in the hydroxamic acid molecule to improve the adsorption and collection efficiency of hydroxamic acid, thereby reducing the amount of hydroxamic acid used in production and thus reducing production costs.
[0005] Based on the literature review, no research reports have been found to date on the preparation of polyhydroxyoximes using renewable rosin as a substitute for petrochemical products. With my country's increasing emphasis on environmental issues, the preparation and application of a rosin-based triisohydroxyoxime acid (salt) of this invention is of great significance for the research and development of efficient and environmentally friendly isohydroxyoxime acids and isohydroxyoxime salts, as well as the optimization of their preparation processes. Summary of the Invention
[0006] This invention mainly provides a rosin-based trihydroxyoxime acid (salt), its preparation method, and its applications. Using renewable rosin as the starting material, a DA addition reaction is performed with an unsaturated dicarboxylic acid to obtain a tricarboxylic acid. The activated tricarboxylic acid is then reacted with a hydroxylamine solution to obtain the rosin-based trihydroxyoxime acid (salt). The synthesized product has multiple hydroxamic acid groups, exhibits strong coordination ability with metal ores and metal ions, and can be used to remove toxic heavy metal cations from environmental water bodies. It can also be used to recover precious or rare metal ions from water, and can be used as a flotation collector for metal ores. The technical solution is as follows:
[0007] A method for preparing a triisohydroxamic acid is as follows: under stirring conditions, using hydroxylamine solution as a substrate, rosinyl triacyl chloride or rosinyl triester is added to synthesize rosinyl triisohydroxamic acid (salt) compounds, wherein the molar ratio of rosinyl triacyl chloride (or ester) to hydroxylamine is 1:4.5-8.
[0008] Preferably, the preparation method includes the following steps:
[0009] (1) The hydroxylamine solution is prepared from hydroxylamine salt, alkali, and solvent. Take the prescribed amounts of hydroxylamine salt, alkali, and solvent and stir at 5-35℃ for 0.5-1h to obtain the hydroxylamine solution.
[0010] (2) The acyl chloride is rosin-based triacyl chloride, and the ester is rosin-based triester. The precursors of both, fumarosin, are derived from the modification of renewable biomass rosin. The solution is prepared by taking the prescribed amount of acyl chloride (or ester) and solvent to prepare an acyl chloride (or ester) solution.
[0011] (3) At a temperature of -5℃ to 95℃, while stirring the hydroxylamine solution, add the acyl chloride (ester) solution dropwise and keep the reaction at this temperature for 2-6 hours; then separate and purify to obtain isohydroxamic acid solution.
[0012] The preparation method of its rosin-based triisohydroxamic acid salt is as follows: preferably, an alkaline ethanol solution is added to the isohydroxamic acid solution, centrifuged and dried to obtain the isohydroxamic acid salt.
[0013] Preferably, the hydroxylamine salt in step (1) is hydroxylamine hydrochloride or hydroxylamine sulfate, and the base is one or two of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, triethylamine, and pyridine; the molar ratio of the base to the hydroxylamine salt is 1:1-2.
[0014] Preferably, the concentration of the acyl chloride solution in step (2) is 5%-15%, and the concentration of the ester solution is 10%-20%.
[0015] Preferably, the alkaline ethanol solution used in the preparation of rosin-based triisohydroxamic acid salt is one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, and sodium carbonate.
[0016] Preferably, when treating wastewater containing metal ions, the formula amount of rosin-based triisohydroxamic acid is taken, and the sodium salt or its sodium salt is prepared into an aqueous solution and added to the wastewater. After the metal ions form a complex with it, a precipitate is produced. The purpose of recovering precious metal ions or removing toxic metal ions from the wastewater can be achieved by simple filtration.
[0017] By adopting the above solution, the present invention has the following advantages:
[0018] This invention uses renewable rosin as a starting material, reacting it with an unsaturated dicarboxylic acid via a diene addition reaction to obtain a tricarboxylic acid. The activated tricarboxylic acid then reacts with a hydroxylamine solution to yield rosin-based triisohydroxamic acid (salt). The synthesized product possesses multiple hydroxamic acid groups, exhibiting strong coordination ability with metal ores and metal ions. It can be used to remove toxic heavy metal cations from environmental water bodies, recover precious or rare metal ions from water, and serve as a flotation collector for metal ores. Post-processing is simple, convenient, and environmentally friendly. Attached Figure Description
[0019] Figure 1 Infrared spectra of rosin-based tricarboxylic acid and rosin-based triisohydroxyoxime acid prepared in Example 1 of this invention.
[0020] Figure 2 Infrared spectra of rosin-based triisohydroxamic acid and sodium rosin-based triisohydroxamic acid prepared in Example 1 of this invention.
[0021] Figure 3The infrared spectra of sodium rosin-based triisohydroxamic acid after adsorbing metal ions are shown in Examples 3, 4, 5, and 6 of this invention. Detailed Implementation
[0022] The present invention is further illustrated by the following embodiments. Unless otherwise specified, all methods are conventional, and the experimental reagents and materials involved are conventional biochemical reagents and materials unless otherwise specified.
[0023] Example 1
[0024] This embodiment uses hydroxylamine hydrochloride as a raw material to react with rosinyl triacyl chloride to prepare rosinyl triisohydroxamic acid and its sodium salt. The specific synthesis process is as follows:
[0025] 3.00 g of triethylamine, 2.60 g of hydroxylamine hydrochloride, and dichloromethane were reacted at 25 °C for 1 h to obtain a hydroxylamine solution. 2.00 g of rosinyl triacyl chloride and a certain amount of dichloromethane were used to prepare a 10% acyl chloride solution. The acyl chloride solution was added dropwise to the hydroxylamine solution while stirring at 5 °C. After the addition was complete, the reaction was maintained at this temperature for 2 h. The reaction product was filtered to obtain a rosinyl triisohydroxyxamic acid solution, which was dried to obtain a solid rosinyl triisohydroxyxamic acid. Its infrared spectrum is shown in [insert infrared spectrum here]. Figure 1 Add sodium hydroxide ethanol solution to a rosinyl triisohydroxamic acid solution, centrifuge, and dry to obtain sodium rosinyl triisohydroxamic acid salt, the infrared spectrum of which is shown in [insert infrared spectrum here]. Figure 2 .
[0026] Example 2
[0027] This embodiment uses hydroxylamine hydrochloride as a raw material to prepare rosin-based triisohydroxamic acid and its sodium salt with rosin-based triester. The specific synthesis process is as follows:
[0028] 2.42 g of sodium hydroxide, 1.21 g of hydroxylamine hydrochloride, and water were stirred at 25 °C for 1 h to obtain a hydroxylamine solution. 2.00 g of rosinyl triester and a certain amount of ethyl acetate were used to prepare a 10% ester solution. The hydroxylamine solution and the ester solution were added to a three-necked flask and reacted at 45 °C for 4 h. The reaction product was filtered to obtain a rosinyl triisohydroxamic acid solution. Sodium hydroxide aqueous solution was added to the rosinyl triisohydroxamic acid solution, and the mixture was centrifuged and dried to obtain sodium rosinyl triisohydroxamic acid.
[0029] Example 3
[0030] This embodiment uses synthesized sodium rosin-based triisohydroxamic acid as raw material to treat simulated industrial wastewater containing Cu2+ ions with an initial Cu2+ concentration of 20 mg / L and pH = 5.0. The specific process is as follows:
[0031] A 25 mL standard solution with an initial Cu2+ concentration of 20 mg / L and pH = 5.0 was prepared, and 25 mg of sodium rosinyl triisohydroxamic acid was added. Static adsorption was performed at 25 °C for 24 h. 96.06% of the Cu2+ ions in the simulated industrial wastewater were adsorbed and recovered by the sodium rosinyl triisohydroxamic acid, demonstrating good performance. After simple filtration, the chelate of Cu2+ ions and rosinyl triisohydroxamic acid was obtained; its infrared spectrum is shown below. Figure 3 .
[0032] Example 4
[0033] This embodiment uses synthesized sodium rosin-based triisohydroxamic acid as raw material to treat simulated wastewater containing Cd2+ ions with an initial Cd2+ concentration of 20 mg / L and pH = 5.0. The specific process is as follows:
[0034] A 25 mL standard solution with an initial Cd²⁺ concentration of 20 mg / L and pH = 5.0 was prepared, and 25 mg of sodium rosinyl triisohydroxamic acid was added. Static adsorption was performed at 25 °C for 24 h. 97.23% of the Cd²⁺ ions in the simulated industrial wastewater were removed by adsorption of sodium rosinyl triisohydroxamic acid, demonstrating good performance. After simple filtration, the chelate of Cd²⁺ ions and rosinyl triisohydroxamic acid was obtained; its infrared spectrum is shown in the figure. Figure 3 .
[0035] Example 5
[0036] This embodiment uses synthesized sodium rosin-based triisohydroxamic acid as raw material to treat simulated Fe2+ ion-containing wastewater with an initial Fe2+ concentration of 20 mg / L and pH = 5.0. The specific process is as follows:
[0037] A standard solution with an initial Fe2+ concentration of 20 mg / L and pH = 5.0 was prepared (25 mL). 25 mg of sodium rosinyl triisohydroxamic acid was added, and static adsorption was performed at 25 °C for 24 h. The removal rate of Fe2+ by sodium rosinyl triisohydroxamic acid reached 97.28%, demonstrating good performance. After simple filtration, the chelate of Fe2+ ions and rosinyl triisohydroxamic acid was obtained; its infrared spectrum is shown below. Figure 3 .
[0038] Example 6
[0039] This embodiment uses synthesized sodium rosin-based triisohydroxamic acid as raw material to treat simulated wastewater with an initial Ni2+ concentration of 40 mg / L and pH = 5.0. The specific process is as follows:
[0040] A standard solution of 25 mL with an initial Ni²⁺ concentration of 40 mg / L and pH = 5.0 was prepared, and 25 mg of sodium rosinyl triisohydroxamic acid was added. Static adsorption was performed at 25 °C for 24 h. The removal rate of Ni²⁺ by sodium rosinyl triisohydroxamic acid reached 69.26%. After simple filtration, the chelate of Ni²⁺ ions and rosinyl triisohydroxamic acid was obtained, and its infrared spectrum is shown in the figure. Figure 3 .
Claims
1. A rosin-based triisohydroxyoxime acid, characterized in that, The structure contains a rosinylphenanthrene ring and has corresponding tautomers, with the molecular formula being:
2. The method for preparing rosin-based triisohydroxamic acid according to claim 1, characterized in that, A rosin-based triisohydroxyoxime acid was synthesized by adding rosin-based triacyl chloride or rosin-based triester to a hydroxylamine solution as a substrate under stirring conditions; wherein the molar ratio of rosin-based triacyl chloride or rosin-based triester to hydroxylamine was 1:4.5-8.
3. The method for preparing rosin-based triisohydroxamic acid according to claim 2, characterized in that, The hydroxylamine solution is prepared from hydroxylamine salt, alkali, and solvent.
4. The method for preparing rosin-based triisohydroxamic acid according to claim 1, characterized in that, Includes the following steps: (1) Take the prescribed amounts of hydroxylamine salt, alkali, and solvent and stir at 5-35℃ for 0.5-1h to obtain a hydroxylamine solution; (2) Take the prescribed amount of rosin-based triacyl chloride or rosin-based triester and solvent to prepare an acyl chloride solution or ester solution; (3) At a temperature of -5℃ to 95℃, the hydroxylamine solution is stirred while the acyl chloride or ester solution is added dropwise, and the reaction is kept at this temperature for 2-6 hours. Then, the solution was separated and purified to obtain isohydroxamic acid solution.
5. The method for preparing rosin-based triisohydroxamic acid according to claim 4, characterized in that, The hydroxylamine salt mentioned in step (1) is hydroxylamine hydrochloride or hydroxylamine sulfate; the base is one or two of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, triethylamine, and pyridine; the solvent is water, dichloromethane, or ethyl acetate; and the molar ratio of the base to the hydroxylamine salt is 1:1-2.
6. The method for preparing rosin-based triisohydroxamic acid according to claim 4, characterized in that, The solvent mentioned in step (2) is one or more of dichloromethane, ethyl acetate, and tetrahydrofuran; the concentration of the acyl chloride solution is 5%-15%, and the concentration of the ester solution is 10%-20%.
7. A method for preparing a rosin-based triisohydroxamic acid salt, characterized in that, Add an alkaline ethanol solution to the isohydroxamic acid solution according to claim 4, centrifuge and dry to obtain isohydroxamic acid salt.
8. The method for preparing rosin-based triisohydroxyoxime salt according to claim 7, characterized in that, The alkaline ethanol solution is one or more of sodium hydroxide ethanol solution, potassium hydroxide ethanol solution, sodium bicarbonate ethanol solution, and sodium carbonate ethanol solution.
9. Rosin-based triisohydroxyoxime salt prepared by the method of claim 7 or 8.
10. The use of the rosinyl triisohydroxamic acid of claim 1 or the rosinyl triisohydroxamic acid salt of claim 9 in the treatment of wastewater containing metal ions.