CN112676045B

CN112676045B - Hydroxyl thiourethane compound, preparation method and application thereof, derivative thereof, preparation method and application thereof

Info

Publication number: CN112676045B
Application number: CN202011403885.1A
Authority: CN
Inventors: 钟宏; 林奇阳; 王帅; 马鑫
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2020-12-04
Filing date: 2020-12-04
Publication date: 2023-05-02
Anticipated expiration: 2040-12-04
Also published as: CN112676045A

Abstract

The invention provides a hydroxyl thiourethane compound and a preparation method and application thereof, and a derivative of the hydroxyl thiourethane compound and a preparation method and application thereof, wherein the structure of the hydroxyl thiourethane compound is as shown in a formula I:

the hydroxyl thiourethane compound derivative has a structure shown in a formula II or a formula III:

the hydroxyl thiourethane compound and the derivative thereof provided by the invention have good dispersion effect in the flotation process, and can act with the thiourethane group together with minerals to realize intramolecular synergy and improve the collection capacity and the selectivity to the minerals.

Description

Hydroxyl thiourethane compound, preparation method and application thereof, derivative thereof, preparation method and application thereof

Technical Field

The invention relates to the technical field of mineral collectors, in particular to a hydroxyl thiourethane compound, a preparation method and application thereof, a derivative of the hydroxyl thiourethane compound, and a preparation method and application of the derivative.

Background

The thiourethane is an excellent collecting agent for minerals such as copper sulfide, lead, zinc and the like, is widely applied due to high efficiency, no toxicity and good selectivity, and has the problems of poor water solubility, poor dispersing effect and weak collecting capacity. Xanthate is also an excellent sulfide ore collector, and has greatly pushed the progress of mineral separation technology since 1925 when it was introduced into the flotation field by Keller, but it has been the sulfide ore collector with the greatest dosage, but it still has the problem of poor selectivity, and in addition, the commercially available alkyl xanthate product has a pungent odor, causing serious pollution to the xanthate production plant and the environment of the mineral separation plant.

Chinese patent CN104056725a improves the dispersion effect of collectors and improves flotation efficiency and metal recovery by introducing ether groups into the thiourethane molecule. Chinese patent CN109225647a obtained a novel xanthate collector Liuji Sodium ethylxanthate (Xiaoping Huang, yun Jia, shi i Wang, xin Ma, zhan fang Cao, and Hong zhong. Novel Sodium O-Benzythioethyl Xanthate Surfactant: synthesis, DFT Calculation and Adsorption Mechanism on Chalcopyrite Surface [ J ], langmuir,2019, 35 (47): 15106-15113.) with less odor and high collecting capacity and selectivity by introducing tertiary butyl groups and ether linkages into the xanthate structure. Chinese patent CN1138031A takes methyl isobutyl carbinol as raw material, synthesizes 1, 3-dimethylbutyl xanthate and improves the grade of copper gold ores.

The existing industrial multi-thiourethane and xanthate products respectively have the problems of poor water solubility, poor dispersion effect, strong pungent smell or poor selectivity, and bring huge pressure to improving flotation indexes and treating surrounding environment, so that the development of the novel sulfide ore collector with better dispersion effect, smaller smell, stronger collecting capacity and better selectivity has important significance for effective flotation separation of minerals and improvement of economic benefit and social benefit.

Disclosure of Invention

Aiming at the problems of poor water solubility, poor dispersing effect and weak collecting capacity of a thiourethane collecting agent and the problems of pungent smell and poor selectivity of a xanthate collecting agent in the prior art, one of the purposes of the invention is to provide a hydroxythiourethane compound, which has a structure shown in a formula I:

wherein R is ¹ Is C ₁ ～C ₁₆ Alkyl or cycloalkyl, R ² Is alkylene, cycloalkylene or arylene;

or R is ¹ Is aryl, R ² Is alkylene or cycloalkylene and the cycloalkylene group does not include hexacycloalkylene;

the alkyl, aryl, cycloalkyl groups allow for the bearing of heteroatoms in the ring or chain, including at least one of oxygen, nitrogen, sulfur.

Preferably, said R ¹ One selected from ethyl, isopropyl, n-butyl, isobutyl, isopentyl, hexyl, benzyl or alkoxyalkyl; r is R ² One selected from 1, 2-ethylene, 1, 2-isopropylidene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, and 1, 4-phenylene.

The second object of the present invention is to provide a method for preparing the above-mentioned hydroxythiourethane, which comprises the following steps:

s1, preparing xanthate: carrying out substitution reaction on xanthate with a structure of formula IV and sodium chloroacetate to obtain sodium xanthate with a structure of formula V;

s2, preparing hydroxyl thiourethane: carrying out ammonolysis reaction on the sodium xanthate prepared in the step S1 and alcohol amine with a structure of a formula VI to obtain the hydroxyl thiourethane compound with a structure of a formula I;

wherein, formula IV structure is:

the structure of formula V is:

the structure of formula VI is:

HO-R ² -NH ₂ ；

wherein M is Na or K; r is R ¹ Is C ₁ ～C ₁₆ Alkyl or cycloalkyl, R ² Is alkylene, cycloalkylene or arylene;

or:

R ¹ is aryl, R ² Is alkylene or cycloalkylene and the cycloalkylene group does not include hexacycloalkylene;

the alkyl, aryl, cycloalkyl groups allow for the bearing of heteroatoms in the ring or chain, including at least one of oxygen, nitrogen, sulfur;

in the preparation method, the synthesis reaction equation of the step S1 and the step S2 is as follows:

step S1: preparation of xanthate:

step S2: preparation of the hydroxythiourethane compound:

wherein M is K or Na.

In some embodiments, in the step S1, the xanthate and the sodium chloroacetate are dissolved in water, and then heated to perform substitution reaction; wherein the molar ratio of the xanthate to the sodium chloroacetate is 1:0.8-1.5; the concentration of the sodium chloroacetate is 2-20mol/L; in the step S2, the molar ratio of the xanthate to the alcohol amine is 1:1-1.5.

Preferably, in the step S1, the reaction temperature is 20-100 ℃ and the reaction time is 0.5-8 h; in the step S2, the reaction temperature is 20-100 ℃ and the reaction time is 0.5-5 h.

It is still another object of the present invention to provide a derivative of a hydroxythiourethane compound having a structure represented by formula II or formula III:

wherein m=1 to 6, n=2 to 6, and m is Na or K; r is R ¹ Is alkyl or cycloalkyl; r is R ² Is alkylene, cycloalkylene or arylene;

or:

R ¹ is aryl; r is R ² Is alkylene or cycloalkylene and the cycloalkylene group does not include hexacycloalkylene.

Preferably, said R ¹ One selected from ethyl, isopropyl, n-butyl, isobutyl, isopentyl, hexyl, benzyl or alkoxyalkyl; the R is ² One selected from 1, 2-ethylene, 1, 2-isopropylidene, 1, 3-propylene, 1, 4-butylene or 1, 5-pentylene, 1, 4-phenylene.

The fourth object of the present invention is to provide a process for producing a hydroxythiourethane derivative, which comprises the steps of:

step 1, preparation of xanthate: carrying out substitution reaction on xanthate with the structure of the formula IV and sodium chloroacetate to obtain sodium xanthate with the structure of the formula V;

step 2, preparing hydroxyl thiourethane: carrying out ammonolysis reaction on the sodium xanthate prepared in the step 1 and alcohol amine with the structure of the formula VI to obtain the hydroxythiourethane compound with the structure of the formula I;

step 3, preparing thiourethane xanthate: mixing the hydroxyl thiourethane compound with the structure shown in the formula I prepared in the step 2 with caustic alkali and carbon disulfide in a solvent to perform xanthation reaction to obtain thiourethane xanthate derivative of hydroxyl thiourethane with the structure shown in the formula II, wherein m=1;

step 4, preparation of a hydroxythiourethane compound derivative: repeating the steps 1 and 2 by taking the thiourethane xanthate prepared in the step 3 as a raw material to obtain the polythiourethane derivative with the structure shown in the formula III and n=2 polythiourethane groups; the method comprises the following steps: taking thiourethane xanthate prepared in the step 3 as a raw material, carrying out substitution reaction with sodium chloroacetate (repeating the step 1), and carrying out ammonolysis reaction with alcohol amine with a structure shown in a formula VI (repeating the step 2) on the obtained product with the structure shown in the formula V to obtain a polythiourethane-based hydroxyl thiourethane compound derivative with n=2 shown in a formula III;

step 5, continuously repeating the step 3 by taking the product with the structure shown in the formula III obtained in the step 4 as a raw material to obtain the m & gt 1 hydroxyl-thiourethane compound derivative with the structure shown in the formula II; continuously repeating the step 3 and the step 4 by taking the product with the structure shown in the formula III obtained in the step 4 as a raw material to obtain the hydroxyl thiourethane compound derivative with the structure shown in the formula III, wherein n is more than 2;

wherein M is Na or K; r is R ¹ Is alkyl or cycloalkyl; r is R ² Is alkylene, cycloalkylene or arylene;

or:

R ¹ is aryl; r is R ² Is alkylene or cycloalkylene; and the cycloalkylene group does not include hexacycloalkylene.

In the preparation method, the synthesis reaction equation of the step 1-4 is as follows:

step 1, preparation of xanthate:

step 2, preparation of a hydroxythiourethane compound:

step 3, preparing thiourethane xanthate:

preferably, said R ¹ One selected from ethyl, isopropyl, n-butyl, isobutyl, isopentyl, hexyl, benzyl or alkoxyalkyl; the R is ² One selected from 1, 2-ethylene, 1, 2-isopropylidene, 1, 3-propylene, 1, 4-butylene or 1, 5-pentylene, 1, 4-phenylene. In some embodiments, in the step 1, the xanthate and the sodium chloroacetate are dissolved in water, and then heated to perform substitution reaction; wherein the molar ratio of the xanthate to the sodium chloroacetate is 1:0.8-1.5; the concentration of the sodium chloroacetate is 2-20mol/L; in the step 2, the molar ratio of the xanthate to the alcohol amine is 1:1-1.5; in the step 3, the molar ratio of the hydroxyl thiourethane, caustic alkali and carbon disulfide is 1:0.8-1.5:1-8; the solvent is at least one of water, carbon disulfide, methylene dichloride and tetrahydrofuran.

Preferably, in the step 1, the reaction temperature is 20-100 ℃ and the reaction time is 0.5-8 h; in the step 2, the reaction temperature is 20-100 ℃ and the reaction time is 0.5-5 h; in the step 3, the xanthation reaction temperature is 0-40 ℃ and the reaction time is 0.5-8 h.

The fifth object of the present invention is to provide an application of the hydroxythiourethane according to any one of the above embodiments or the hydroxythiourethane prepared by the preparation method according to any one of the above embodiments in mineral flotation; in particular to the application in the mineral flotation of copper sulfide ores, lead zinc sulfide ores, nickel sulfide ores, copper molybdenum sulfide ores and the like.

The sixth object of the present invention is to provide an application of the hydroxythiourethane derivative according to any one of the above embodiments or the hydroxythiourethane derivative produced by the production method according to any one of the above embodiments in mineral flotation; in particular to the application in the mineral flotation of copper sulfide ores, lead zinc sulfide ores, nickel sulfide ores, copper molybdenum sulfide ores and the like.

The seventh object of the present invention is to provide a mineral flotation collector comprising a hydroxythiourethane and/or a hydroxythiourethane derivative, wherein the hydroxythiourethane is the hydroxythiourethane compound according to any one of the above embodiments or the hydroxythiourethane compound produced by the production method according to any one of the above embodiments; the hydroxythiourethane derivative is a derivative of the hydroxythiourethane compound of any one of the above embodiments or a derivative of the hydroxythiourethane compound produced by the production method of any one of the above embodiments; preferably, the mineral flotation collector is at least one of copper sulfide ore, lead zinc sulfide ore, nickel sulfide ore and copper molybdenum sulfide ore.

In some embodiments, the mineral flotation collector further comprises at least one of xanthates, thiourethanes, and azothionates.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the hydroxyl thiourethane compound provided by the invention, the hydroxyl is introduced at the terminal position, so that on one hand, the compound can form a hydrogen bond with water more easily due to the existence of the hydroxyl, the solvation energy of the compound in an aqueous solution is reduced, the water solubility of the compound is improved, the dispersion effect of thiourethane medicament molecules in a flotation process is improved, on the other hand, the charge population in the thiourethane molecules can be changed due to the introduction of the hydroxyl, the hydroxyl and the thiourethane groups can be combined with minerals, and as the thiourethane functional groups and the hydroxyl functional groups are both used as the hydrophilic groups, the hydroxyl functional groups can be combined with metal ions on the surfaces of the minerals to realize intramolecular coordination, so that the capture capacity and selectivity of the hydroxythiourethane compound are improved.

2. The hydroxyl thiourethane derivative-thiourethane xanthate provided by the invention has the hydrophilic functional groups of the thiourethane and the thiourethane, wherein the selectivity of the thiourethane group is better than that of the xanthate, and the selectivity of the thiourethane derivative can be improved, so that the hydroxyl thiourethane derivative can better and selectively act with the surface of a mineral, thereby having stronger collecting capacity and better selectivity, and the use amount is less in the use process, and the method is particularly suitable for the flotation of sulfide minerals such as copper sulfide ore, nickel sulfide ore, copper molybdenum ore, lead zinc ore and the like. In addition, in the mineral flotation process, the thiourethane xanthate can be combined with collectors such as xanthate, thiourethane, and thioazote, so that better flotation indexes can be obtained, and a new development direction is provided for mineral flotation.

3. Compared with the existing alkyl xanthate collector, the existence of the thiourethane group introduces sulfur and nitrogen atoms, so that the intramolecular or intermolecular interaction is enhanced, and the smell of the collector is reduced, therefore, the thiourethane-based xanthate product has no peculiar smell, the influence of the pungent smell of the conventional xanthate collector on the environment is avoided, and the working environment of the production and use processes of the medicament can be improved.

4. All the raw materials adopted by the invention have the characteristics of wide sources and large yield, are not easy to limit, can form a compound medicament with thiourethane xanthate even if the hydroxyl thiourethane is excessive or incompletely reacted in the process of producing the xanthate, improve the selectivity, do not need to purify the product, and are simple to operate. The preparation method provided by the invention adopts the conventional production process of the medicament, can be directly carried out on the existing production equipment of a medicament factory, does not need to reform the equipment according to production, and can reduce the production cost.

5. Compared with the traditional synthesis process of the thiourethane, the preparation method provided by the invention does not need to use hazardous chemicals such as methylamine, ethylamine and the like for synthesizing the hydroxythiourethane compound, so that the production safety is better ensured.

6. According to the preparation method provided by the invention, the alcohol amine compound with a higher boiling point is used instead of ethylamine, so that the amine can be directly added for aminolysis after esterification is finished, the connection of the two steps is smoother, the amine is not required to be firstly cooled and added and then heated for aminolysis in the production process, the investment of public engineering is reduced, and the production time is shortened.

Drawings

FIG. 1 is a nuclear magnetic resonance spectrum of potassium 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate;

FIG. 2 is a nuclear magnetic carbon spectrum of potassium 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate;

FIG. 3 is a nuclear magnetic resonance spectrum of potassium 2- ((isobutoxymethyl) amino) ethyl xanthate;

FIG. 4 is a nuclear magnetic carbon spectrum of potassium 2- ((isobutoxymethyl) amino) ethyl xanthate;

FIG. 5 is an infrared spectrum of potassium O- (1, 6, 11-trimethyl-4, 9-dithiocarbonyl-5, 10-dioxa-3, 8-diazadecyl) xanthate;

FIG. 6 is an optimal configuration of isobutyl xanthogen at the level of B3LYP/6-311G+ (d);

FIG. 7 is an optimal configuration of 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate at a level of B3LYP/6-311G+ (d);

FIG. 8 shows the highest occupied molecular orbital HOMO and the lowest unoccupied molecular orbital LUMO of isobutylxanthate at the level of B3LYP/6-311G+ (d);

FIG. 9 is the highest occupied molecular orbital HOMO and the lowest unoccupied molecular orbital LUMO of 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate at a B3LYP/6-311G+ (d) level;

FIG. 10 is a molecular electrostatic potential of isobutyl xanthate at a level of B3LYP/6-311G+ (d);

FIG. 11 is a molecular electrostatic potential of 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate at a level of B3LYP/6-311G+ (d).

Detailed Description

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Example 1

Preparation of O-isopropyl-N-hydroxyethyl thiocarbamate

Adding 20.45 parts of sodium isopropyl xanthate with the purity of 85% into a reaction container, adding 30 parts of distilled water to completely dissolve the sodium isopropyl xanthate, adding 11.77 parts of sodium chloroacetate with the purity of 99%, heating to 80 ℃ for reaction for 2 hours, adding 6.17 parts of ethanolamine with the purity of 99% after the reaction is finished, preserving heat for 2 hours at 70 ℃, cooling to room temperature, separating liquid, washing an oil phase with 30ml of water for three times, and drying to obtain 14.84 parts of O-isopropyl-N-hydroxyethyl thiocarbamate product. The product purity was 96% and the yield based on ethanolamine was 87%.

Example 2

Preparation of O-isopropyl-N-hydroxyisopropyl thiocarbamate

Adding 20.45 parts of sodium isopropyl xanthate with the purity of 85% into a reaction vessel, adding 30 parts of distilled water to completely dissolve the sodium isopropyl xanthate, adding 11.77 parts of sodium chloroacetate with the purity of 99%, heating to 80 ℃ for reaction for 2 hours, adding 8.16 parts of isopropanolamine with the purity of 92% after the reaction is finished, preserving heat for 2 hours at 70 ℃, cooling to room temperature, separating liquid, washing an oil phase with 30ml of water for three times, and drying to obtain 17.18 parts of O-isopropyl-N-hydroxyisopropyl thiocarbamate product with the purity of 98% and the yield of 95% based on ethanolamine.

Example 3

Preparation of Potassium 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate

17.18 parts of O-isopropyl-N-hydroxyisopropyl thiocarbamate with the purity of 98% obtained in example 2 is transferred into a reaction vessel, 40 parts of carbon disulfide with the purity of 99% is added, the temperature of the mixture is kept below 30 ℃, 6.27 parts of potassium hydroxide is added in three times, the temperature is kept at 25 ℃ for 4 hours, the reaction is completed, and 30.88g of 2- ((isopropoxymethyl sulfonyl) amino) isopropyl potassium xanthate product is obtained after removing the solvent by rotary evaporation.

The nuclear magnetic hydrogen spectrum and the nuclear magnetic carbon spectrum of the 2- ((isopropoxymethyl sulfonyl) amino) isopropyl potassium xanthate prepared by the invention are shown in figures 1 and 2, and tables 2 and 3; the energy, front molecular orbital energy and ClogP are shown in Table 1.

TABLE 1 energy, front molecular orbital energy and CLogP of collector in aqueous solution at DFT/B3LYP6-311+G (d) level

As shown in table 1, the quantum chemical calculation result shows that the hydrophobic constant CLogP value of the 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate is 2.074, which is slightly higher than the CLogP value (1.946) of the current general collector isobutyl xanthate (potassium isobutyl xanthate) for sulphide ores, which makes the thiourethane-based xanthate have stronger hydrophobicity. The Highest Occupied Molecular Orbital (HOMO) energy of the molecule is-0.1943a.u., which is relatively close to the isobutyl xanthate (HOMO) energy (-0.1946a.u.); the energy of the Lowest Unoccupied Molecular Orbital (LUMO) of the thiourethane group is changed into-0.0467 a.u., which is lower than the LUMO energy (-0.0316a.u.) of the isobutyl xanthate, so that the thiourethane group has stronger collecting power and better selectivity, and the thiourethane group is small in dosage in the use process, and is particularly suitable for flotation of sulphide minerals such as copper sulphide ore, nickel sulphide ore, copper molybdenum ore, lead zinc ore and the like.

FIGS. 6 and 7 are, respectively, optimal configurations of isobutyl xanthate and 2- ((isopropoxymethyl) thio) amino) isopropyl xanthate at the B3LYP/6-311G+ (d) level, the incorporation of xanthate results in an increase in charge density of the C-N bond in the thiourethane group, C=S exhibits more single bond properties, the stability of the resonant formula containing thiol anions is improved, the sulfur atom carries a certain amount of negative charge, and the direction is different from that of xanthate, thereby increasing the probability of molecules contacting the mineral surface and acting, and improving the capture capacity;

FIGS. 8 and 9 are HOMO and LUMO of isobutyl xanthate and 2- ((isopropoxymethyl thio) amino) isopropyl xanthate at B3LYP/6-311G+ (d) levels, respectively, wherein the HOMO of the two ions are not greatly different due to negative charge carried by the xanthate, while the LUMO in the 2- ((isopropoxymethyl thio) amino) isopropyl xanthate molecule is reduced due to the introduction of the thiourethane group and is mainly positioned on the thiourethane group, so that the collector is easier to accept electrons to form a feedback bond, and the selectivity to minerals is improved;

FIGS. 10 and 11 are graphs of the molecular electrostatic potentials of isobutyl xanthate and 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate at the B3LYP/6-311G+ (d) level, respectively, and the introduction of the thiourethane group increases the conjugated structure in the molecule, thereby achieving the effect of dispersing charges, remarkably reducing the charge quantity in the lowest electrostatic potential region of the surface of the molecule, weakening the electrostatic adsorption of the collector in the flotation process, and improving the selectivity.

Example 4

Preparation of potassium O- (1, 6, 11-trimethyl-4, 9-dithiocarbonyl-5, 10-dioxa-3, 8-diazadecyl) xanthate

30.88 parts of potassium 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate obtained in example 3 is added into a reaction vessel, 30 parts of distilled water is added to completely dissolve the potassium 2- ((isopropoxymethyl sulfonyl) amino) isopropyl xanthate, 11.77 parts of sodium chloroacetate with 99% purity is added, the temperature is raised to 80 ℃ for 2 hours, after the reaction is finished, 8.16 parts of isopropanolamine with 92% purity is added, the temperature is kept at 70 ℃ for 2 hours, the mixture is cooled to room temperature and separated into liquid, the oil phase is washed three times by 30ml of water, 40 parts of carbon disulfide with 99% purity is added after the mixture is dried, the temperature of the mixture is kept below 30 ℃ for three times, 6 parts of potassium hydroxide is added in total, the mixture is kept at 25 ℃ for 4 hours for reaction completion, and 34.75g of potassium O- (1, 6, 11-trimethyl-4, 9-dithiocarbonyl-5, 10-dioxa-3, 8-diazadecyl) xanthate product is obtained after the solvent is removed by rotary evaporation.

The infrared detection results of the potassium O- (1, 6, 11-trimethyl-4, 9-dithiocarbonyl-5, 10-dioxa-3, 8-diazadecyl) xanthate prepared in this example are shown in FIG. 5.

The infrared spectrum of potassium O- (1, 6, 11-trimethyl-4, 9-dithiocarbonyl-5, 10-dioxa-3, 8-diazadecyl) xanthate is shown in FIG. 5, and the main characteristic peaks are (cm-1): 3264 is attributed to the-NH stretching vibration peak; 3041. 2873 belonging to a-CH 3 stretching vibration peak; 2933. 2976 ascribes a-CH 2 stretching vibration peak; 1519 belonging to the-NH deformation vibration peak; 1401. 1371 belonging to a-CH 3 deformation vibration peak; 1191 ascribed to a C-O-C stretching vibration peak; 1126. 1099, 1079 have a characteristic absorption peak of c=s; 912 belongs to the C-S stretching vibration peak.

Example 5

Preparation of O-isopropyl-N-hydroxy-N-propyl thiocarbamate

Adding 20.45 parts of sodium isopropyl xanthate with the purity of 85% into a reaction container, adding 30 parts of distilled water to completely dissolve the sodium isopropyl xanthate, adding 11.77 parts of sodium chloroacetate with the purity of 99%, heating to 80 ℃ for reaction for 2 hours, adding 7.60 parts of N-propanolamine with the purity of 99% after the reaction is finished, preserving heat for 2 hours at 70 ℃, cooling to room temperature, separating liquid, washing an oil phase with 30ml of water for three times, and drying to obtain 17.20 parts of O-isopropyl-N-hydroxy N-propyl thiocarbamate product. The product purity was 97% and the yield based on n-propanolamine was 94%.

Example 6

Preparation of Potassium 2- ((isopropoxymethyl sulfonyl) amino) n-propyl xanthate

17.2 parts of O-isopropyl-N-hydroxy-N-propyl thiocarbamate with the purity of 97% obtained in example 4 is transferred into a reaction vessel, 40 parts of carbon disulfide with the purity of 99% is added, the temperature of the mixture is kept below 30 ℃, 6.6 parts of potassium hydroxide is added in three times, the temperature is kept at 25 ℃ for 4 hours, the reaction is completed, and 33.09g of 2- ((isopropoxymethyl sulfonyl) amino) N-propyl potassium xanthate product is obtained after removing the solvent by rotary evaporation.

Example 7

Preparation of O-isobutyl-N-hydroxyethyl thiocarbamate

Adding 22.56 parts of sodium isobutyl xanthate with the purity of 84% into a reaction vessel, adding 30 parts of distilled water to completely dissolve the sodium isobutyl xanthate, adding 11.77 parts of sodium chloroacetate with the purity of 99%, heating to 80 ℃ for reaction for 2 hours, adding 6.17 parts of ethanolamine with the purity of 99% after the reaction is finished, preserving heat for 1 hour at 70 ℃, cooling to room temperature, separating liquid, washing an oil phase with 30ml of water for three times, and drying to obtain 17.63 parts of O-isobutyl-N-hydroxyethyl thiocarbamate product. The product purity was 98% and the yield based on ethanolamine was 97%.

Example 8

Preparation of Potassium 2- ((isobutoxymethyl) sulfonyl) amino) ethyl xanthate

17.63 parts of O-isobutyl-N-hydroxyethyl thiocarbamate with the purity of 98% obtained in example 2 is transferred into a reaction vessel, 40 parts of carbon disulfide with the purity of 99% are added, the temperature of the mixture is kept below 30 ℃, 6.62 parts of potassium hydroxide is added in three times, the temperature is kept at 25 ℃ for 4 hours, the reaction is completed, and 30.44g of 2- ((isobutoxymethyl) amino) ethyl potassium xanthate product is obtained after the solvent is removed by rotary evaporation.

The nuclear magnetic hydrogen spectrum and the nuclear magnetic carbon spectrum of the 2- ((isobutoxymethyl) amino) ethyl potassium xanthate prepared by the invention are shown in fig. 3 and 4, and table 2 and table 3.

TABLE 2 Nuclear magnetic resonance Hydrogen Spectrometry analysis

TABLE 3 Nuclear magnetic resonance carbon Spectrometry analysis

Example 9

Flotation of chalcopyrite by potassium O- (1, 6, 11-trimethyl-4, 9-dithiocarbonyl-5, 10-dioxa-3, 8-diazadecyl) xanthate

In the presence of potassium O- (1, 6, 11-trimethyl-4, 9-dithiocarbonyl-5, 10-dioxa-3, 8-diazadecyl) xanthate at a concentration of 2x10 ^-5 The mol/L, the pH value of ore pulp is 8.0, the concentration of foaming agent methyl isobutyl carbinol (MIBC) is 7.5mg/L, the rotating speed is 1992r/min, the chalcopyrite with the granularity of-0.076 mm to +0.038mm is floated for 5 minutes, and the floatation recovery rate of the chalcopyrite is 93.67 percent.

Example 10

Flotation of copper sulfide ore in northeast by thiourethane-based xanthate

Copper is extracted from certain dew in northeast, the copper content of raw ore is 0.45%, main copper ore is chalcopyrite, and primary roughing is carried out. The medicament system is as follows: the fineness of the ore is 65% of-200 meshes, the lime consumption is 2000g/t, the pH value of ore pulp is about 11.0, the foaming agent is 2# oil, the collecting agents are respectively 2- ((isopropoxymethyl sulfonyl) amino) isopropyl potassium xanthate, 2- ((isobutoxymethyl sulfonyl) amino) ethyl potassium xanthate, 2- ((isobutoxymethyl sulfonyl) amino) isopropyl potassium xanthate and commercial sodium isobutyl xanthate (content is 85%), commercial sodium isopentyl xanthate (content is 80%), and other flotation test conditions and results are shown in Table 4. The flotation results show that under the same medicament conditions, compared with sodium isobutyl xanthate and sodium isopentyl xanthate, potassium 2- ((isopropoxymethyl thio) amino) isopropyl xanthate, potassium 2- ((isobutyloxymethyl thio) amino) ethyl xanthate and potassium 2- ((isobutyloxymethyl thio) amino) isopropyl xanthate all obtain better flotation results, and the thiourethane-based xanthate series collectors have stronger collecting capacity.

TABLE 4 flotation experiments on copper sulfide ores in northeast

Example 11

Flotation experiment of hydroxyl thiourethane on Yunnan certain ore

Copper is extracted from certain dew in northeast, the copper content of raw ore is 0.45%, main copper ore is chalcopyrite, and primary roughing is carried out. The medicament system is as follows: the flotation results of the copper flotation results of the ore grinding fineness of-200 meshes accounting for 65%, the lime consumption of 2000g/t, the ore pulp pH value of about 11.0, the foaming agent of 2# oil, the collecting agent of O-isobutyl-N-hydroxyethyl thiocarbamate, O-isopropyl-N-hydroxyethyl thiocarbamate and commercial Z-200 (with the content of 98%) which are directly synthesized by the method disclosed by the application are shown in Table 5, and the flotation results show that under the same medicament condition, compared with the traditional medicament Z-200, the O-isopropyl-N-hydroxyethyl thiocarbamate improves the grade of copper concentrate by 0.13%, the copper recovery rate of 12.34%, the O-isopropyl-N-hydroxyethyl thiocarbamate improves the grade of copper concentrate by 0.42%, the copper recovery rate of 5.4%, and the O-isobutyl-N-hydroxyethyl thiocarbamate improves the copper recovery rate by 4.36%.

TABLE 5 floatation experiment of copper sulfide ore in Shanglira

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In addition, the method of substitution reaction of xanthate and sodium chloroacetate in the preparation of xanthate according to the present invention is similar to the method illustrated in this example, and other methods of xanthate preparation known in the art are applicable to the present invention.

The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims

1. A method for preparing a hydroxythiourethane compound and a derivative thereof, comprising the steps of:

step 1, preparation of xanthate: carrying out substitution reaction on xanthate with a structure of formula IV and sodium chloroacetate to obtain sodium xanthate with a structure of formula V;

step 2, preparing hydroxyl thiourethane: carrying out ammonolysis reaction on the sodium xanthate prepared in the step S1 and alcohol amine with a structure of a formula VI to obtain the hydroxysulfamonium compound with a structure of a formula I, wherein the molar ratio of the sodium xanthate to the alcohol amine is 1:1-1.5;

step 4, preparation of a hydroxythiourethane derivative: repeating the steps 1 and 2 by taking the thiourethane xanthate prepared in the step 3 as a raw material to obtain the polythiourethane derivative with the structure shown in the formula III and n=2 polythiourethane groups;

wherein, formula I structure is:

the structure of the formula II is as follows:

the structure of the formula III is as follows:

the structure of the formula IV is as follows:

the structure of formula V is:

the structure of formula VI is:

HO-R ² -NH ₂ ；

wherein M is Na or K; the R is ¹ One selected from isopropyl and isobutyl; r is R ² One selected from 1, 2-ethylene, 1, 2-isopropylidene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 4-phenylene, m=1 to 6, n=2 to 6.

2. The method for producing a hydroxythiourethane compound and derivative thereof according to claim 1, wherein in the step 1, the xanthate and the sodium chloroacetate are dissolved in water, respectively, and then heated to perform substitution reaction; wherein the molar ratio of the xanthate to the sodium chloroacetate is 1:0.8-1.5; the concentration of the sodium chloroacetate is 2-20mol/L; in the step 3, the molar ratio of the hydroxyl thiourethane, caustic alkali and carbon disulfide is 1:0.8-1.5:1-8; the solvent is at least one of water, carbon disulfide, methylene dichloride and tetrahydrofuran.

3. A mineral flotation collector which is characterized by comprising hydroxythiourethane and/or derivatives thereof, wherein the hydroxythiourethane is a hydroxythiourethane compound shown in a formula I prepared by the method of claim 1 or 2, and the derivatives thereof are derivatives of hydroxythiourethane compound shown in a formula II or III prepared by the method of claim 1 or 2;

and at least one of xanthate, thiourethane and azothionate.

4. A mineral flotation collector according to claim 3 wherein the mineral comprises at least one of copper sulphide ore, lead zinc sulphide ore, nickel sulphide ore or copper molybdenum sulphide ore.