Hydroxamate-phosphonate / phosphinic acid compound and preparation method and application thereof

Abstract

The present invention provides hydroxamic acid-phosphonate / phosphinic acid compounds and preparation methods and applications thereof. A halogenated hydroxamic acid and a trialkyl phosphite are subjected to a substitution reaction to generate a hydroxamic acid-phosphonate compound, and the hydroxamic acid-phosphonate compound is then subjected to hydrolysis and saponification to generate a hydroxamic acid-phosphinic acid compound. The nitrogen atoms and oxygen atoms on the hydroxamic acid group in the molecular structure of this type of collector can chelate with metal ions on the surface of the ore to form a five-membered ring, and the phosphonate or phosphinic acid group forms a P-M (metal) or P-O-M bond partially or completely to adsorb on the metal active sites on the surface of the ore, and the two functional groups are connected by a hydrocarbon chain, which weakens the repulsion between the ligands and the repulsion between the surrounding hydration layers, effectively increases the hydrophobicity of the ore surface, and can significantly improve its ore flotation recovery performance.

Description

Technical Field

[0001] The invention relates to the technical field of ore flotation, and in particular to a hydroxamic acid-phosphonate / phosphinic acid compound and a preparation method and application thereof. Background Art

[0002] Flotation is one of the most important technical means to recover metal minerals from ores. Froth flotation uses collectors to regulate the hydrophobicity of the mineral surface, so that the target minerals gather on the surface of the slurry along with the bubbles, thereby selectively separating them from the gangue minerals. Therefore, collectors are the fundamental reason for achieving the selective separation of target minerals from gangue minerals.

[0003] Currently, non-ferrous metal ore collectors have problems such as weak collection capacity, large collector dosage or the need to add additional metal ions for post-activation flotation. For example, adding Pb 2+ In order to effectively improve the flotation recovery of cassiterite by salicylic acid hydroxamic acid; the recovery rate of cassiterite flotation by using benzohydroxamic acid as a collector is only about 30%. 3+ After activation, the recovery rate of cassiterite is significantly improved to 80%; when α-hydroxyoctylphosphinic acid is used for the flotation of malachite, the flotation recovery rate of malachite can reach more than 90% when the collector dosage reaches 400 mg / L. Therefore, developing a collector with strong collection ability, small dosage and no need to add other activators is an urgent problem for scientific researchers to solve. Summary of the invention

[0004] The object of the present invention is to provide a hydroxamic acid-phosphonate / phosphinic acid compound and a preparation method and application thereof in view of the above-mentioned deficiencies in the prior art.

[0005] To achieve the above object, the present invention adopts the following technical solution:

[0006] The first object of the present invention is to provide a hydroxamic acid group-phosphonate / phosphinic acid compound, the chemical structure of which is shown in formula (I) or (II):

[0007]

[0008] in,

[0009] R1 represents C1-C 16 Alkyl, C6-C 10 The aromatic and C7-C 16 any one of the aralkyl groups; R2 represents a C1-C3 hydrocarbon group.

[0010] Further, the R1 is selected from any one of ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, phenyl, p-tolyl, n-octyl, isooctyl, sec-octyl, 2-ethylhexyl, n-decyl and isodecyl.

[0011] Furthermore, the R2 is selected from methylene or 1,2-ethylene.

[0012] When R2 is methylene and R1 is ethyl, formula (I) is diethyl (2-(hydroxyamino)-2-oxoethyl)phosphonate, and formula (II) is ethyl (2-(hydroxyamino)-2-oxoethyl)phosphonate;

[0013] When R2 is a methylene group and R1 is a propyl group, formula (I) is (2-(hydroxyamino)-2-oxoethyl) dipropyl phosphonate, and formula (II) is (2-(hydroxyamino)-2-oxoethyl) hydrogen propyl phosphonate;

[0014] When R2 is methylene and R1 is isopropyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diisopropyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen isopropyl ester;

[0015] When R2 is methylene and R1 is butyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl) dibutyl phosphonate, and formula (II) is (2-(hydroxyamino)-2-oxoethyl) hydrogen butyl phosphonate;

[0016] When R2 is methylene and R1 is isobutyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diisobutyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen isobutyl ester;

[0017] When R2 is methylene and R1 is sec-butyl, formula (I) is di-sec-butyl (2-(hydroxyamino)-2-oxoethyl)phosphonate, and formula (II) is sec-butyl (2-(hydroxyamino)-2-oxoethyl)phosphonate;

[0018] When R2 is a methylene group and R1 is a pentyl group, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid dipentyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen pentyl ester;

[0019] When R2 is methylene and R1 is isopentyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diisopentyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen isopentyl ester;

[0020] When R2 is methylene and R1 is neopentyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid dineopentyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen neopentyl ester;

[0021] When R2 is methylene and R1 is n-hexyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-n-hexyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen n-hexyl ester;

[0022] When R2 is methylene and R1 is isohexyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diisohexyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen isohexyl ester;

[0023] When R2 is methylene and R1 is phenyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl) diphenyl phosphonate, and formula (II) is (2-(hydroxyamino)-2-oxoethyl) phenyl hydrogen phosphonate;

[0024] When R2 is methylene and R1 is p-tolyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-p-tolyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen p-tolyl ester;

[0025] When R2 is methylene and R1 is n-octyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-n-octyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen n-octyl ester;

[0026] When R2 is methylene and R1 is isooctyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diisooctyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen isooctyl ester;

[0027] When R2 is methylene and R1 is sec-octyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-sec-octyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen sec-octyl ester;

[0028] When R2 is methylene and R1 is 2-ethylhexyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid bis(2-ethylhexyl) ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen 2-ethylhexyl ester;

[0029] When R2 is methylene and R1 is n-decyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-n-decyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen n-decyl ester;

[0030] When R2 is methylene and R1 is isodecyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diisodecyl ester, and formula (II) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid hydrogen isodecyl ester;

[0031] When R2 is 1,2-ethylene and R1 is ethyl, formula (I) is diethyl (3-(hydroxyamino)-3-oxopropyl)phosphonate, and formula (II) is ethyl (3-(hydroxyamino)-3-oxopropyl)phosphonate;

[0032] When R2 is 1,2-ethylene and R1 is propyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl) dipropyl phosphonate, and formula (II) is (3-(hydroxyamino)-3-oxopropyl) hydrogen propyl phosphonate;

[0033] When R2 is 1,2-ethylene and R1 is isopropyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisopropyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen isopropyl ester;

[0034] When R2 is 1,2-ethylene and R1 is butyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl) dibutyl phosphonate, and formula (II) is (3-(hydroxyamino)-3-oxopropyl) hydrogen butyl phosphonate;

[0035] When R2 is 1,2-ethylene and R1 is isobutyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisobutyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen isobutyl ester;

[0036] When R2 is 1,2-ethylene and R1 is sec-butyl, formula (I) is di-sec-butyl (3-(hydroxyamino)-3-oxopropyl)phosphonate, and formula (II) is sec-butyl (3-(hydroxyamino)-3-oxopropyl)phosphonate;

[0037] When R2 is 1,2-ethylene and R1 is pentyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid dipentyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen pentyl ester;

[0038] When R2 is 1,2-ethylene and R1 is isopentyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisopentyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen isopentyl ester;

[0039] When R2 is 1,2-ethylene and R1 is neopentyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid dineopentyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen neopentyl ester;

[0040] When R2 is 1,2-ethylene and R1 is n-hexyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-n-hexyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen n-hexyl ester;

[0041] When R2 is 1,2-ethylene and R1 is isohexyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisohexyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen isohexyl ester;

[0042] When R2 is 1,2-ethylene and R1 is phenyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl) diphenyl phosphonate, and formula (II) is (3-(hydroxyamino)-3-oxopropyl) phenyl hydrogen phosphonate;

[0043] When R2 is 1,2-ethylene and R1 is p-tolyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-p-tolyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen p-tolyl ester;

[0044] When R2 is 1,2-ethylene and R1 is n-octyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-n-octyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen n-octyl ester;

[0045] When R2 is 1,2-ethylene and R1 is isooctyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisooctyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen isooctyl ester;

[0046] When R2 is 1,2-ethylene and R1 is sec-octyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-sec-octyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen sec-octyl ester;

[0047] When R2 is 1,2-ethylene and R1 is 2-ethylhexyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid bis(2-ethylhexyl) ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid 2-ethylhexyl ester;

[0048] When R2 is 1,2-ethylene and R1 is n-decyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-n-decyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen n-decyl ester;

[0049] When R2 is 1,2-ethylene and R1 is isodecyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisodecyl ester, and formula (II) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid hydrogen isodecyl ester.

[0050] The second object of the present invention is to provide a method for preparing the above hydroxamic acid-phosphonate / phosphinic acid compound, wherein a halogenated hydroxamic acid and a trialkyl phosphite are subjected to a substitution reaction, the molar ratio of the halogenated hydroxamic acid to the trialkyl phosphite is 1:(0.8-2), the reaction temperature is 140-170° C., and the reaction time is 2-10 hours to generate a hydroxamic acid-phosphonate compound of formula I, and the hydroxamic acid-phosphonate compound of formula I is further hydrolyzed and saponified to generate a hydroxamic acid-phosphinic acid compound of formula II, wherein the structure of the halogenated hydroxamic acid is shown in formula (III), and the structure of the trialkyl phosphite is shown in formula (IV):

[0051]

[0052] The third object of the present invention is to provide the use of the above hydroxamic acid-phosphonate / phosphinic acid compound in the flotation of non-ferrous metal minerals.

[0053] Furthermore, the non-ferrous metal minerals include one or more of tungsten-containing ores, tin-containing ores, cerium-containing ores, gold-containing ores and silver-containing ores.

[0054] Furthermore, the method for using the hydroxamic acid-phosphonate / phosphinic acid compound as a flotation collector for non-ferrous metal ores is as follows: adding the non-ferrous metal flotation collector to the grinding and / or flotation process to prepare the slurry, and obtaining non-ferrous metals by froth flotation.

[0055] Furthermore, during the slurry adjustment process, the amount of the non-ferrous metal ore flotation collector used is (15-2700) g / t of ore, and the pH value of the slurry is 8-9.

[0056] Furthermore, the frother selected in the froth flotation method is MIBC, and the amount used is (16-4950) g / t of ore.

[0057] Furthermore, the particle size distribution of the ore is not higher than 200 mesh, and the particle size is not greater than 0.076 mm.

[0058] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0059] The invention provides a hydroxamic acid-phosphonate / phosphinic acid compound and a preparation method and application thereof. A halogenated hydroxamic acid and a trialkyl phosphite are subjected to a substitution reaction, wherein the molar ratio of the halogenated hydroxamic acid to the trialkyl phosphite is 1:(0.8-2), the reaction temperature is 140-170°C, and the reaction time is 2-10 hours to generate a hydroxamic acid-phosphonate compound. The hydroxamic acid-phosphonate compound is then hydrolyzed and saponified to generate a hydroxamic acid-phosphinic acid compound. For the first time, a class of hydroxamic acid-phosphonic acid compounds having both hydroxamic acid and trialkyl phosphite is obtained. The flotation collectors of the hydroxamic acid group and the phosphoryl group, the nitrogen and oxygen atoms on the hydroxamic acid group in the molecular structure of this type of collector can chelate with the metal ions on the surface of the ore to form a five-membered ring, and the phosphonate or phosphinate group forms a PM (metal) or POM bond partially or completely to adsorb on the metal active sites on the surface of the ore. The two functional groups are connected by a hydrocarbon chain, which weakens the repulsion between the ligands and the repulsion between the surrounding hydration layers, effectively increases the hydrophobicity of the ore surface, and can significantly improve its flotation recovery performance for the ore. It is expected to achieve effective flotation separation and recovery of non-ferrous metals and precious metals by using it as a collector for non-ferrous metal and precious metal ores in the flotation separation of non-ferrous metals and precious metal ores. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 The infrared spectrum of dibutyl (2-(hydroxyamino)-2-oxoethyl)phosphonate prepared in Example 1;

[0061] Figure 2 The infrared spectrum of diphenyl (2-(hydroxyamino)-2-oxoethyl)phosphonate prepared in Example 2;

[0062] Figure 3 This is the infrared spectrum of 8-methylnonyl hydrogen (2-(hydroxyamino)-2-oxoethyl)phosphonate prepared in Example 3. DETAILED DESCRIPTION

[0063] In order to make the purpose, technical scheme and advantages of the present invention clearer, the specific embodiments of the present invention are further described in detail below in conjunction with specific examples and drawings. If no specific technology or conditions are specified in the examples, the technology or conditions described in the literature in this field or the product instructions are used. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be obtained commercially.

[0064] Example 1

[0065] Preparation of dibutyl (2-(hydroxyamino)-2-oxoethyl)phosphonate

[0066] 10.96 parts of methyl chloroacetate were added to 25.03 parts of tributyl phosphite solution at 160°C under stirring, and stirred at 160°C for 3 hours. The reactants were then added to a mixed solution of 7.64 parts of hydroxylamine hydrochloride, 8 parts of sodium hydroxide, and 40 parts of methanol, and reacted for 2 hours under ice bath conditions, with the temperature not exceeding 10°C, and the pH value adjusted to about 6, filtered, and the filtrate was washed with reduced pressure distilled water and dried to obtain a colorless, transparent, oily liquid, namely (2-(hydroxyamino)-2-oxoethyl)phosphonic acid dibutyl ester, whose infrared spectrum is as follows: Figure 1 The yield was 96%.

[0067] Example 2

[0068] Preparation of diphenyl (2-(hydroxyamino)-2-oxoethyl)phosphonate

[0069] 5.48 parts of methyl chloroacetate were added to 15.83 parts of triphenyl phosphite solution at 160°C under stirring, and stirred at 160°C for 3 hours. The reactants were then added to a mixed solution of 3.83 parts of hydroxylamine hydrochloride, 4.4 parts of sodium hydroxide, and 25 parts of methanol, and reacted for 2 hours under ice bath conditions, with the temperature not exceeding 10°C and the pH value adjusted to about 6. The filtrate was filtered, and the filtrate was washed with reduced pressure distilled water and dried to obtain a red oily liquid, namely (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diphenyl ester, whose infrared spectrum is as follows: Figure 2 The yield was 95%.

[0070] Example 3

[0071] Preparation of 8-methylnonylhydrogen(2-(hydroxyamino)-2-oxoethyl)phosphonate

[0072] 5.48 parts of methyl chloroacetate were added to 26.46 parts of tributyl phosphite solution at 160°C under stirring, and stirred at 160°C for 3 hours after the addition. The reactants were then added to a mixed solution of 3.83 parts of hydroxylamine hydrochloride, 4.4 parts of sodium hydroxide, and 25 parts of methanol, and reacted for 2 hours under ice bath conditions at a temperature not exceeding 10°C. The filtrate was filtered, and the filtrate was washed with water and dried under reduced pressure distillation to obtain a light yellow transparent oily liquid, which was then saponified and hydrolyzed with sodium hydroxide solution in 1,4-dioxane, acidified to a pH of about 6, extracted, and distilled under reduced pressure to obtain a colorless transparent oily liquid, which is 8-methylnonyl hydrogen (2-(hydroxyamino)-2-oxoethyl) phosphonate, and its infrared spectrum is as follows: Figure 3 The yield was 95%.

[0073] Examples 4 to 6 use the flotation collectors having the hydroxamic acid group-phosphonate / phosphinic acid structure prepared in Examples 1 to 3 for the flotation collection of non-ferrous metals and precious metal minerals.

[0074] Example 4

[0075] Flotation of Scheelite by Dibutyl (2-(Hydroxyamino)-2-oxoethyl)phosphonate

[0076] In the case of dibutyl (2-(hydroxyamino)-2-oxoethyl)phosphonate, 5×10 -5 mol / L, the slurry pH is 8-9, the concentration of the frother (MIBC) is 45 mg / L, the N2 gas flow rate is 200 mL / min, the scheelite with a particle size of 0.076 mm to 0.038 mm is floated for 3 minutes, the amount of collector is 1500 g / t scheelite, the amount of frother is 4950 g / t scheelite, and the flotation recovery rate of the scheelite reaches 85.91%.

[0077] Example 5

[0078] Flotation of Wolframite by Diphenyl (2-(Hydroxyamino)-2-oxoethyl)phosphonate

[0079] When the concentration of (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diphenyl ester was 8×10 -5 mol / L, the slurry pH is 8-9, the concentration of the frother (MIBC) is 30 mg / L, the N2 gas flow rate is 200 mL / min, the wolframite with a particle size of 0.076 mm to 0.038 mm is floated for 3 minutes, the amount of collector is 2700 g / t wolframite, the amount of frother is 3300 g / t wolframite, and the flotation recovery rate of the wolframite is 80.97%.

[0080] Example 6

[0081] Flotation of cassiterite with 8-methylnonylhydrogen(2-(hydroxyamino)-2-oxoethyl)phosphonate

[0082] In the case of 8-methylnonyl hydro(2-(hydroxyamino)-2-oxoethyl)phosphonate, the concentration was 5×10 -5 mol / L, slurry pH is 8-9, the concentration of frother (MIBC) is 15 mg / L, N2 gas flow rate is 200 mL / min, cassiterite with a particle size of 0.038 mm is floated for 3 minutes, the amount of collector is 1600 g / t cassiterite, the amount of frother is 1650 g / t cassiterite, and the flotation recovery rate of cassiterite is 90.56%.

[0083] In the absence of conflict, the above embodiments and features in the embodiments may be combined with each other.

[0084] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A hydroxamate-phosphonate compound, characterized in that: The chemical structure is shown in formula (I): (Ⅰ) wherein R1 is selected from any one of ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, phenyl, p-tolyl, n-octyl, isooctyl, sec-octyl, 2-ethylhexyl, n-decyl and isodecyl; R2 is selected from methylene or 1,2-ethylene; When R2 is methylene and R1 is ethyl, formula (I) is diethyl (2-(hydroxyamino)-2-oxyethyl)phosphonate; When R2 is a methylene group and R1 is a propyl group, the formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid dipropyl ester; When R2 is a methylene group and R1 is an isopropyl group, the formula (I) is (2-(hydroxyamino)-2-oxyethyl)phosphonic acid diisopropyl ester; When R2 is a methylene group and R1 is a butyl group, the formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid dibutyl ester; When R2 is a methylene group and R1 is an isobutyl group, the formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diisobutyl ester; When R2 is a methylene group and R1 is a sec-butyl group, the formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-sec-butyl ester; When R2 is a methylene group and R1 is a pentyl group, the formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid dipentyl ester; When R2 is methylene and R1 is isopentyl, the formula (I) is (2-(hydroxyamino)-2-oxyethyl)phosphonic acid diisopentyl ester; When R2 is methylene and R1 is neopentyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid dineopentyl ester; When R2 is methylene and R1 is n-hexyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-n-hexyl ester; When R2 is methylene and R1 is isohexyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid diisohexyl ester; When R2 is methylene and R1 is phenyl, the formula (I) is (2-(hydroxyamino)-2-oxoethyl) diphenyl phosphonate; When R2 is methylene and R1 is p-tolyl, the formula (I) is (2-(hydroxyamino)-2-oxyethyl)phosphonic acid di-p-tolyl ester; When R2 is methylene and R1 is n-octyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-n-octyl ester; When R2 is methylene and R1 is isooctyl, formula (I) is (2-(hydroxyamino)-2-oxyethyl)phosphonic acid diisooctyl ester; When R2 is methylene and R1 is sec-octyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-sec-octyl ester; When R2 is methylene and R1 is 2-ethylhexyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid bis(2-ethylhexyl) ester; When R2 is methylene and R1 is n-decyl, formula (I) is (2-(hydroxyamino)-2-oxoethyl)phosphonic acid di-n-decyl ester; When R2 is methylene and R1 is isodecyl, formula (I) is (2-(hydroxyamino)-2-oxyethyl)phosphonic acid diisodecyl ester; When R2 is 1,2-ethylene and R1 is ethyl, the formula (I) is diethyl (3-(hydroxyamino)-3-oxopropyl)phosphonate; When R2 is 1,2-ethylene and R1 is propyl, the formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid dipropyl ester; When R2 is 1,2-ethylene and R1 is isopropyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisopropyl ester; When R2 is 1,2-ethylene and R1 is butyl, the formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid dibutyl ester; When R2 is 1,2-ethylene and R1 is isobutyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisobutyl ester; When R2 is 1,2-ethylene and R1 is sec-butyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-sec-butyl ester; When R2 is 1,2-ethylene and R1 is pentyl, the formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid dipentyl ester; When R2 is 1,2-ethylene and R1 is isopentyl, the formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisopentyl ester; When R2 is 1,2-ethylene and R1 is neopentyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid dineopentyl ester; When R2 is 1,2-ethylene and R1 is n-hexyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-n-hexyl ester; When R2 is 1,2-ethylene and R1 is isohexyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisohexyl ester; When R2 is 1,2-ethylene and R1 is phenyl, the formula (I) is (3-(hydroxyamino)-3-oxopropyl) diphenyl phosphonate; When R2 is 1,2-ethylene and R1 is p-tolyl, the formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-p-tolyl ester; When R2 is 1,2-ethylene and R1 is n-octyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-n-octyl ester; When R2 is 1,2-ethylene and R1 is isooctyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisooctyl ester; When R2 is 1,2-ethylene and R1 is sec-octyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-sec-octyl ester; When R2 is 1,2-ethylene and R1 is 2-ethylhexyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid bis(2-ethylhexyl) ester; When R2 is 1,2-ethylene and R1 is n-decyl, formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid di-n-decyl ester; When R2 is 1,2-ethylene and R1 is isodecyl, the formula (I) is (3-(hydroxyamino)-3-oxopropyl)phosphonic acid diisodecyl ester.

2. The method for preparing a hydroxamate-phosphonate compound according to claim 1, wherein: The halogenated hydroxamic acid and trialkyl phosphite are subjected to substitution reaction, the molar ratio of the halogenated hydroxamic acid to the trialkyl phosphite is 1:(0.8-2), the reaction temperature is 140-170°C, and the reaction time is 2-10 hours to generate a hydroxamic acid-phosphonate compound of the structure of formula I.

3. Use of the hydroxamate-phosphonate compound as claimed in claim 1 in flotation of non-ferrous metal minerals.

4. The use according to claim 3, characterized in that The non-ferrous metal minerals It includes one or more of tungsten-containing ores, tin-containing ores, cerium-containing ores, gold-containing ores and silver-containing metals.

5. The use according to claim 4, characterized in that The hydroxamate-phosphonic acid The application method of the ester compound as a flotation collector for non-ferrous metal ores is as follows: the non-ferrous metal ores flotation collector is added to the grinding and / or flotation process to prepare the slurry, and the non-ferrous metal is obtained by froth flotation.

6. The use according to claim 5, characterized in that During the slurry preparation process, The dosage of the nonferrous metal ore flotation collector is (15-2700) g / t of ore, and the pH of the slurry is 8-9.

7. The use according to claim 6, characterized in that In the froth flotation method The selected frother is MIBC, and the dosage is (16-4950) g / t of ore.

8. The use according to claim 7, characterized in that The particle size of the ore The mesh size is not higher than 200 and the particle size is not larger than 0.076mm.

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