CN115160457B - Preparation method of dialkylphosphinic acid functional group modified extraction resin - Google Patents

Preparation method of dialkylphosphinic acid functional group modified extraction resin Download PDF

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CN115160457B
CN115160457B CN202210616856.6A CN202210616856A CN115160457B CN 115160457 B CN115160457 B CN 115160457B CN 202210616856 A CN202210616856 A CN 202210616856A CN 115160457 B CN115160457 B CN 115160457B
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chlorine
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王俊莲
胡成强
赵鸿儒
崔建国
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University of Science and Technology Beijing USTB
Baotou Rare Earth Research Institute
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Baotou Rare Earth Research Institute
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    • C08F8/00—Chemical modification by after-treatment
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The application discloses a preparation method of dialkyl phosphinic acid functional group modified extraction resin, belonging to the technical field of solid phase extraction separation. Firstly, hydrolyzing chlorine balls or reacting the chlorine balls with polyalcohol to obtain hydroxyl modified chlorine balls; then, utilizing hydroxyl to react with acyl chloride containing carbon-carbon double bonds, and grafting the carbon-carbon double bonds to the surface of the chlorine ball through generated ester groups; and then the free radical addition reaction of the carbon-carbon double bond and the monoalkyl phosphinic acid is utilized to obtain the dialkyl phosphinic acid functional group modified extraction resin. The dialkylphosphinic acid functional group modified extraction resin disclosed by the application has the advantages of high chemical stability, no extraction agent loss, good selectivity, large saturated adsorption capacity, readily available raw materials, lower price, more environment-friendly preparation process, no generation of a large amount of ammonia nitrogen wastewater, easiness in industrial preparation and capability of being widely applied to the fields of low-concentration metal ion enrichment, high-purity rare earth preparation, nuclear zirconium-hafnium separation, metal ion impurity removal and the like.

Description

Preparation method of dialkylphosphinic acid functional group modified extraction resin
Technical Field
The application belongs to the technical field of solid phase extraction separation, and particularly relates to an extraction resin, a preparation method thereof and application thereof in the aspects of low-concentration metal ion enrichment, high-purity rare earth preparation, nuclear-grade zirconium-hafnium separation, metal ion impurity removal and the like.
Background
The key of the extraction chromatography is that the extraction resin needs to have the properties of high extraction speed, large extraction capacity, good selectivity, high mechanical strength, stable physical and chemical properties, good cycle performance, durability and the like. Meanwhile, the extraction resin also needs to have micron-sized particle size (16-200 meshes) so as to ensure that the leaching solution has a certain flow rate in the process of separating metal ions by an industrial extraction chromatography method. At present, the extraction resin suitable for separating rare earth by an industrial extraction chromatography method comprises impregnating resin, TVEX resin, microencapsulated resin and polymer resin with hanging extraction functional groups.
Impregnating resins have been proposed by Warshawsky for 50 years since the 70 s of the 20 th century, and few commercial applications of impregnating resins have been reported. This is mainly because the extractant is adsorbed on the support substrate by weak interaction force (van der waals force), and there is a problem of loss of the extractant during extraction, washing and back extraction, which seriously affects the stability and cycle performance of the impregnated resin. In addition, the impregnated resin prepared by the dry method has the support substrate in a contracted state, the internal pore diameter is reduced, and the extraction time is long; in the process of preparing the impregnating resin by the wet method, the concentration of the extractant is high, the filtering is difficult, the waste water containing the extractant is generated by washing with hot water, and the waste of the extractant is serious.
The reaction conditions (such as stirring speed, pore-forming agent type and dosage) of the TVEX resin need to be strictly controlled in the preparation process so as to obtain the extraction resin with proper granularity, large aperture and high specific surface area, the preparation is more complicated, and the price of the TVEX resin is higher. In addition, part of the extractant is buried in the polymer and cannot be effectively contacted with metal ions, so that the extractant utilization rate is low, the extraction capacity is small, and the problem of extractant loss still exists.
The preparation method of the microencapsulated resin is simple, can effectively inhibit the loss of the extractant, but the metal ions can interact with the extractant only by penetrating through the protective film, so that the extraction time is long, and the requirement of high extraction speed of the extraction resin is difficult to meet.
The polymer resin suspending the extraction functional group is used for connecting the extraction functional group with the support substrate through a chemical bond, so that the problem of loss of the extractant is fundamentally solved, the physical and chemical properties are stable, and the cycle performance is good. The reported polymer resins with pendant extraction functionalities typically have phosphate, amidoxime, and acyloxyxime extraction functionalitiesAcid groups, phenolic hydroxyl groups (Ar-OH), carboxyl groups, amino groups, amide groups, urea, crown ethers, and the like. Resins containing these extraction functionalities either have poor selectivity or have high extraction acidity ([ H) + ]=6 to 8 mol/L), or weak extraction capacity, it is difficult to achieve effective separation of rare earth, zirconium and hafnium.
Aiming at rare earth low concentration enrichment, high purity heavy rare earth preparation and nuclear grade zirconium-hafnium separation, no extraction resin which has good rare earth and zirconium-hafnium separation performance, high extraction speed, large extraction capacity, low back extraction acidity, stable physicochemical property, good cycle performance and durability is satisfied. The organic phosphorus/phosphonic acid extractant (P204, P507 and Cyanex 272) is the most common extractant for separating rare earth by an industrial solvent extraction method, and particularly the dialkyl phosphinic acid extractant (such as Cyanex 272, P227, INET-3, USTB-1 and the like) has excellent extraction separation performance on rare earth, zirconium and hafnium. There are few reports of dialkylphosphinic extractants attached to the surface of a substrate by chemical bonds.
Disclosure of Invention
The application discloses a preparation method of dialkyl phosphinic acid functional group modified extraction resin, and aims to solve the problems that the original comparison document CN 113527552B utilizes chlorine atoms on chlorine balls to react with compounds containing primary amine functional groups to obtain amino modified chlorine balls, the amount of nitrogen-containing reagents used is large, and ammonia nitrogen wastewater is generated. Meanwhile, the problem that the acidity of the feed liquid and the adsorption rate of the extraction resin on metal ions in the feed liquid are affected by residual amino groups on the surface of the obtained modified chlorine ball modified by the dialkylphosphinic acid functional group in the chlorine ball modification method for modifying the dialkylphosphinic acid functional group disclosed in the comparative document CN 113527552B are solved.
A preparation method of dialkyl phosphinic acid functional group modified extraction resin is characterized in that firstly, hydroxyl modification is carried out on ammonia balls, and two methods are adopted for the hydroxyl modified chlorine balls: one is a hydrolysis process, one is reaction with a polyol; the hydrolysis method comprises alkali catalytic hydrolysis, acid catalytic hydrolysis and metal salt catalytic hydrolysis, and the chlorine ball is hydrolyzed or reacts with the polyol to obtain hydroxyl modified chlorine ball; then, utilizing hydroxyl to react with acyl chloride containing carbon-carbon double bonds, and grafting the carbon-carbon double bonds to the surface of the chlorine ball through generated ester groups; and then the free radical addition reaction of the carbon-carbon double bond and the monoalkyl phosphinic acid is utilized to obtain the dialkyl phosphinic acid functional group modified extraction resin.
The preparation route is shown in figure 1, wherein the chlorine ball is introduced with-CH 2 Styrene-divinylbenzene copolymers with Cl-reactive functional groups; r is R 1 Is H, an aliphatic substituent with 1-8 carbon atoms, or a phenyl or benzene ring-containing substituent with 6-12 carbon atoms; r is R 2 Is an aliphatic alkyl chain with 0-12 carbon atoms or an alkyl chain with 6-16 carbon atoms and containing benzene rings; r is R 3 Is an aliphatic substituent having 4 to 12 carbon atoms or a substituent having 8 to 16 carbon atoms and containing a benzene ring.
Further, the preparation method of the dialkylphosphinic acid functional group modified extraction resin comprises the following steps:
(1) The hydroxyl modified chlorine ball is prepared by taking chlorine balls as raw materials through one of the following methods:
(1) reacting chlorine balls, polyalcohol and alkaline substances 1 in an organic solvent A at 40-180 ℃ for 2-24 hours, and obtaining hydroxyl modified chlorine balls after solid-liquid separation; wherein the mass ratio of the chlorine ball to the polyalcohol is 10:1-1:10, and the mass ratio of the chlorine ball to the alkaline substance 1 is 20:1-1:20;
(2) mixing the chlorine ball with the aqueous solution of the alkaline substance 1, reacting for 2-72 h at 25-120 ℃, and obtaining the hydroxyl modified chlorine ball after solid-liquid separation; wherein the mass ratio of the chlorine ball to the alkaline substance 1 is 10:1-1:10, and the mass concentration of the alkaline substance 1 is 1-40%;
(3) mixing chlorine balls with an aqueous solution of acid, reacting for 2-72 hours at 25-120 ℃, and carrying out solid-liquid separation to obtain hydroxyl modified chlorine balls; wherein the mass ratio of the chlorine ball to the acid is 10:1-1:10, and the mass concentration of the acid is 1-40%;
(4) mixing chlorine balls and aqueous solution of metal salt, reacting for 1-24 hours at 0-100 ℃, and obtaining hydroxyl modified chlorine balls after solid-liquid separation; wherein the mass ratio of the chlorine ball to the metal salt is 10:0.1-1:5, and the mass concentration of the metal salt is 0.1-30%;
(2) Adding 1-20 times of water and/or an organic solvent B into the hydroxyl modified chlorine balls obtained in the step (1), and adding an alkaline substance 2, wherein the mass ratio of the alkaline substance 2 to the hydroxyl modified chlorine balls is 0.05:1-2:1;
(3) Dissolving acyl chloride with carbon-carbon double bond by using an organic solvent B, wherein the volume ratio of the acyl chloride to the organic solvent B is 1:0.5-1:10, slowly dripping the acyl chloride to the organic solvent B into the mixed system of the hydroxyl modified chlorine ball and the alkaline substance 2 obtained in the step (2) at the temperature of 0-80 ℃, wherein the mass ratio of the acyl chloride to the hydroxyl modified chlorine ball is 0.05:1-3:1, and reacting for 0-10 hours after the dripping is finished to obtain the carbon-carbon double bond modified chlorine ball. Wherein the mol ratio of the acyl chloride to the alkaline substance 2 is 1:0.5-1:2;
(4) And (3) reacting the carbon-carbon double bond modified chlorine ball obtained in the step (3) with monoalkylphosphinic acid, an initiator and an organic solvent C at 80-150 ℃ for 8-48 h, and carrying out solid-liquid separation to obtain the dialkylphosphinic acid functional group modified extraction resin.
Further, the polyols include, but are not limited to, pentaerythritol, ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolethane, trimethylolpropane, 2-phenyl-1, 3-propanediol, and the like.
Further, the alkaline substance 1 and the alkaline substance 2 may be the same or different, and include, but are not limited to, one or more of triethylamine, pyridine, diisopropylmethylamine, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide or lithium hydroxide.
Further, the acid described in step (1) and the acid described in step (4) may be the same or different, and include, but are not limited to, one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hypochlorous acid, silicic acid, boric acid, formic acid, acetic acid, propionic acid, butyric acid, succinic acid, glutaric acid, adipic acid, suberic acid, citric acid, oxalic acid, azelaic acid, sebacic acid.
Further, the metal salt includes, but is not limited to, one or more of copper sulfate, ferrous sulfate, ferric sulfate, cadmium sulfate, manganese sulfate, zinc sulfate, copper iodide, ferric chloride, and copper acetate.
Further, the organic solvent A is one or more of 1, 4-dioxane, tetrahydrofuran, N-dimethylformamide, toluene or xylene
Further, the organic solvent B is one or more of diethyl ether, petroleum ether, tetrahydrofuran, 1, 4-dioxane, N-octane, cyclohexane, sulfonated kerosene, N-dimethylformamide, toluene or xylene.
Further, the organic solvent C is one or more of N-octane, cyclohexane, petroleum ether, sulfonated kerosene, tetrahydrofuran, 1, 4-dioxane, N-butanol, N-amyl alcohol, N-hexanol, N-octanol, isooctanol, decanol, N-dimethylformamide, toluene or xylene.
Further, the initiator is one or more of tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, dibenzoyl peroxide, lauroyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, diethyl hexyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, diphenyl oxyethyl peroxydicarbonate and azodiisobutyronitrile.
Further, the mass ratio of the carbon-carbon double bond modified chlorine ball to the monoalkyl phosphinic acid is 6:1-1:6, the molar ratio of the monoalkyl phosphinic acid to the acid is 6:1-1:2, and the mass of the initiator is 0.1-10% of the mass of the monoalkyl phosphinic acid.
In the preparation method of the hydroxyl modified chlorine ball, the polyol can be added into the methods (2), (3) and (4), and the mass ratio of the polyol to the chlorine ball is 0-1:1. The hydrolysis method has the advantages of few reagents and simple synthesis method; the reaction with polyols can introduce more hydroxyl groups and thus graft more double bonds.
The application provides a preparation method of dialkyl phosphinic acid functional group modified extraction resin. The method comprises the following steps: the chlorine balls meeting the granularity, the aperture and the specific surface area of the extraction resin are taken as raw materials, and the requirements of how to meet the granularity, the aperture and the specific surface area of the extraction resin are not needed to be considered any more, so that the preparation method is simple; the skeleton of the chlorine ball is polystyrene-divinylbenzene type copolymer, has stable chemical property and high mechanical strength, and meets the requirements of industry on the mechanical strength and durability of the extraction resin; the dialkyl phosphinic acid is grafted to the surface of the macroporous resin substrate through stable chemical group ester groups, so that the problem of loss of the extractant is avoided, and the requirements of good cycle performance and durability of the extraction resin are met; dialkyl phosphinic acid is used as an extraction functional group, and has good separation performance on rare earth, zirconium hafnium, nickel cobalt and other elements; the extraction resin with large extraction capacity can be obtained by increasing the element number of the polyol and introducing more C=C and extraction functional groups (-POOH) on the surface of the chlorine ball; the hydrophilicity of the surface of the extraction resin can be improved by regulating and controlling the number of hydroxyl groups remained on the surface of the chlorine ball, the extraction speed of metal ions can be increased, and the pH value of feed liquid can not be influenced; meanwhile, the extraction resin can be fully swelled by an organic solvent before use, so that the internal aperture is expanded to the maximum, and the extraction speed is also improved.
The comparative document CN 113527552B is a chlorine sphere modified with an amino group by reacting a chlorine atom on the sphere with a compound containing a primary amine functional group, and then grafting a carbon-carbon double bond to the surface of the sphere by using an amide group generated by the reaction of the amino group with an acid chloride. The application is that the hydroxyl modified chlorine ball is obtained by the hydrolysis of chlorine ball or the reaction with polyalcohol, then the carbon-carbon double bond is grafted on the surface of chlorine ball by utilizing the ester group generated by the reaction of hydroxyl and acyl chloride. Compared with a comparison document CN 113527552B, the preparation method of the dialkylphosphinic acid functional group modified extraction resin disclosed by the application has the advantages that the nitrogen-containing reagent is greatly reduced, the generated ammonia nitrogen wastewater is less, the production process is more environment-friendly, and the cost is lower. According to the chlorine ball modification method for modifying the dialkylphosphinic acid functional group disclosed in the comparative document CN 113527552B, residual amino groups are unavoidable on the surface of the obtained modified chlorine ball modified by the dialkylphosphinic acid functional group, the amino groups can be protonated in an acidic medium, on one hand, the acidity of a feed liquid is influenced, on the other hand, metal anions in the feed liquid can be adsorbed through an anion exchange reaction after the amino groups are protonated, and the selectivity is reduced. The hydroxyl group remains on the surface of the extraction resin modified by the dialkylphosphinic acid functional group disclosed by the application, and the hydroxyl group is a hydrophilic group, so that the adsorption rate of the extraction resin on metal ions in the feed liquid can be improved, the acidity of the feed liquid can not be influenced, the metal anions in the feed liquid can not be adsorbed, and the selectivity is better.
Therefore, the extraction resin obtained by the method has the advantages of high extraction speed, large extraction capacity, good selectivity, high mechanical strength, stable physical and chemical properties, good cycle performance, durability and less ammonia nitrogen wastewater generated in the preparation process, and can be widely used in the fields of industrial low-concentration metal ion enrichment, high-purity rare earth preparation, nuclear zirconium and hafnium separation, metal ion impurity removal and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a schematic diagram of the preparation route of the present application,
FIG. 2 schematic representation of the structure of dialkylphosphinic acid functional group modified extraction resin (example 1),
FIG. 3 schematic representation of the structure of dialkylphosphinic acid functional group modified extraction resin (example 2),
FIG. 4 schematic representation of the structure of dialkylphosphinic acid functional group modified extraction resin (example 3),
FIG. 5 is a schematic representation of the structure of a dialkylphosphinic acid functional group modified extraction resin (example 4).
Detailed Description
The process of the application is further illustrated below with reference to the examples. The examples of the present application are intended to explain the present application and are not to be construed as unduly limiting the present application.
Example 1
(1) Hydroxyl modified chlorine balls: 8.5g of dried chlorine balls were weighed, 120mL of 1, 4-dioxane was added to swell for 24 hours, 11.7g of 1, 6-hexanediol and 9.8g of triethylamine were added to react at 80℃for 8 hours. Cooling to room temperature, filtering, washing with water until the filtrate is neutral, washing with ethanol for times, and vacuum drying to obtain hydroxyl modified chlorine balls.
(2) Preparation of acyl chloride containing carbon-carbon double bond: to 16.8g of undecylenic acid, 16.0g of thionyl chloride was added, reacted at 80℃for 2 hours, cooled to room temperature, excess thionyl chloride was removed by a rotary evaporator, and 30mL of dehydrated diethyl ether was added to obtain an diethyl ether solution of undecylenoyl chloride.
(3) Preparing a carbon-carbon double bond modified chlorine ball: 10.0g of hydroxyl modified chlorine ball is taken, 45mL of anhydrous diethyl ether and 8.2g of diisopropylmethylamine are added, an diethyl ether solution of undecyl chloride is slowly added through a constant pressure funnel under magnetic stirring at normal temperature, and the reaction is carried out for 18h after the dripping is finished. Filtering, washing with deionized water until the filtrate is neutral, washing with ethanol, and air drying at room temperature.
(4) Preparation of dialkylphosphinic acid functional group modified extraction resin: 15.0g of chlorine ball grafted with carbon-carbon double bond, 1.5g of glacial acetic acid, 6.8g of mono (2, 3-dimethylbutyl) phosphinic acid, 0.52g of di-tert-butyl peroxide and 20mL of n-octane are taken for reflux reaction for 8h, 0.35g of di-tert-butyl peroxide is added for further reaction for 12h. Cooling to room temperature, washing with ethanol for 4 times, and air drying at room temperature to obtain dialkylphosphinic acid functional group modified extraction resin (structure schematic diagram is shown in figure 2).
Example 2
(1) Hydroxyl modified chlorine balls: 22.6g of dried chlorine ball is weighed, 220mL of N, N-dimethylformamide is added for swelling for 18h, 22.4g of trimethylolpropane and 20.6g of anhydrous potassium carbonate are added, and reflux reaction is carried out for 18h. Cooling to room temperature, filtering, washing with water until the filtrate is neutral, washing with ethanol for times, and vacuum drying to obtain hydroxyl modified chlorine balls.
(2) Preparing a carbon-carbon double bond modified chlorine ball: 25.0g of hydroxyl modified chlorine ball is taken, 80mL of tetrahydrofuran and 20.2g of sodium bicarbonate are added, a tetrahydrofuran solution containing 48.5g of undecyl chloride is slowly added through a constant pressure funnel under magnetic stirring at normal temperature, and the reaction is carried out for 6h after the dripping is finished. Filtering, washing with deionized water until the filtrate is neutral, washing with ethanol, and air drying at room temperature.
(3) Preparation of dialkylphosphinic acid functional group modified extraction resin: 26.0g of chlorine ball grafted with carbon-carbon double bond, 20mL of 1, 4-dioxane, 1.5mL of adipic acid, 20.2g of mono (2, 3-dimethylbutyl) phosphinic acid and 0.85g of dibenzoyl peroxide are taken and reacted in a reaction kettle at 125 ℃ for 8 hours, 0.44g of dibenzoyl peroxide is added, the reaction is carried out for 8 hours again, 0.44g of dibenzoyl peroxide is added, and the reaction is carried out for 8 hours again. Cooling to room temperature, washing with ethanol for 4 times, and air drying at room temperature to obtain dialkylphosphinic acid functional group modified extraction resin (structure schematic diagram is shown in figure 3).
Example 3
(1) Hydroxyl modified chlorine balls: 6.2g of dried chlorine balls are weighed, 80mL of toluene is added for swelling for 10 hours, 8.4g of 2-phenyl-1, 3-propanediol and 5.6g of sodium hydroxide are added, and reflux reaction is carried out for 24 hours. Cooling to room temperature, filtering, washing with ethanol for 3 times, washing with water until the filtrate is neutral, washing with ethanol again, and vacuum drying to obtain hydroxyl modified chlorine spheres.
(2) Preparation of acyl chloride containing carbon-carbon double bond: to 6.5g of 5-hexenoic acid was added 10.2g of thionyl chloride, reacted at 80℃for 4 hours, cooled to room temperature, excess thionyl chloride was removed by rotary evaporator, and 25mL of dried 1, 4-dioxane was added to give a 1, 4-dioxane solution of 5-hexenoyl chloride.
(3) Preparing a carbon-carbon double bond modified chlorine ball: 6.6g of hydroxyl modified chlorine ball is taken, 25mL of normal hexane and 7.2g of potassium carbonate solution are added, 1, 4-dioxane solution of 5-hexenoyl chloride is slowly added through a constant pressure funnel under magnetic stirring at normal temperature, and the reaction is carried out for 10h after the addition is finished. Filtering, washing with deionized water until the filtrate is neutral, washing with ethanol for 2 times, and air drying at room temperature.
(4) Preparation of dialkylphosphinic acid functional group modified extraction resin: 7.8g of carbon-carbon double bond modified chlorine ball, 20mL of octanol, 0.8mL of butyric acid, 15.0g of mono (2-ethylhexyl) phosphinic acid and 0.82g of diisopropyl peroxydicarbonate are taken and reacted for 8 hours at 90 ℃, 0.58g of diisopropyl peroxydicarbonate is added, the reaction is carried out for 8 hours again, 0.58g of diisopropyl peroxydicarbonate is added again, and the reaction is carried out for 8 hours again. Cooling to room temperature, washing with ethanol for 4 times, and air drying at room temperature to obtain dialkylphosphinic acid functional group modified extraction resin (structure schematic diagram is shown in figure 4).
Example 4
(1) Hydroxyl modified chlorine balls: 10.0g of chlorine balls were weighed, 15g of sodium carbonate and 50mL of water were added, and reacted at reflux for 48 hours. Cooling to room temperature, filtering, washing with water until the filtrate is neutral, washing with ethanol, and vacuum drying to obtain hydroxyl modified chlorine balls.
(2) Preparation of acyl chloride containing carbon-carbon double bond: to 12.6g of 5-hexenoic acid was added 20.5g of thionyl chloride, reacted at 60℃for 6 hours, cooled to room temperature, excess thionyl chloride was removed by a rotary evaporator, and 50mL of dried tetrahydrofuran was added to obtain a tetrahydrofuran solution of 5-hexenoyl chloride.
(3) Preparing a carbon-carbon double bond modified chlorine ball: 8.0g of hydroxyl modified chlorine ball is taken, 50mL of dry tetrahydrofuran and 11.2g of N, N-diisopropylethylamine are added, a tetrahydrofuran solution of 5-hexenoyl chloride is slowly added through a constant pressure funnel under magnetic stirring at normal temperature, and the reaction is carried out for 24 hours after the addition is finished. Filtering, washing with deionized water until the filtrate is neutral, washing with ethanol, and air drying at room temperature.
(4) Preparation of dialkylphosphinic acid functional group modified extraction resin: 8.0g of chlorine ball grafted with carbon-carbon double bond, 2.5g of butyric acid, 6.0g of mono (2, 4-trimethyl amyl) phosphinic acid, 0.65g of di-tert-butyl peroxide and 20mL of n-octane are taken for reflux reaction for 8h, 0.32g of di-tert-butyl peroxide is added for further reaction for 8h. Cooling to room temperature, washing with ethanol for 4 times, and air drying at room temperature to obtain the extract resin with suspended dialkylphosphinic acid functional groups (the structure schematic diagram is shown in figure 5).
Example 5
Preparation of hydroxyl modified chlorine balls: 15.0g of chlorine balls are weighed, 50mL of 4mol/L HCl is added, and the mixture is reacted for 24 hours at 90 ℃. Cooling to room temperature, filtering, washing with water until the filtrate is neutral, washing with ethanol, and vacuum drying to obtain hydroxyl modified chlorine spheres.
Example 6
Preparation of hydroxyl modified chlorine balls: 50g of chlorine balls are weighed, 35g of ferric sulfate and 100mL of water are added, and reflux reaction is carried out for 5h at 80 ℃. Cooling to room temperature, filtering, washing with water until the filtrate is neutral, washing with ethanol for times, and vacuum drying to obtain hydroxyl modified chlorine balls.
Example 7
Hydroxyl modified chlorine balls: 8.2g of chlorine balls are weighed, 2g of potassium hydroxide, 50mL of water and 1g of pentaerythritol are added, and the mixture is reacted for 18 hours under reflux. Cooling to room temperature, filtering, washing with water until the filtrate is neutral, washing with ethanol, and vacuum drying to obtain hydroxyl modified chlorine balls.

Claims (10)

1. A preparation method of dialkyl phosphinic acid functional group modified extraction resin is characterized in that firstly, hydroxyl modification is carried out on chlorine balls, and two methods are adopted for the hydroxyl modification of the chlorine balls: one is a hydrolysis process, one is reaction with a polyol; the hydrolysis method comprises alkali catalytic hydrolysis, acid catalytic hydrolysis and metal salt catalytic hydrolysis, and the chlorine ball is hydrolyzed or reacts with the polyol to obtain hydroxyl modified chlorine ball; then, utilizing hydroxyl to react with acyl chloride containing carbon-carbon double bonds, and grafting the carbon-carbon double bonds to the surface of the chlorine ball through generated ester groups; then the free radical addition reaction of the carbon-carbon double bond and the monoalkylphosphinic acid is utilized to obtain dialkylphosphinic acid functional group modified extraction resin; the preparation route is as follows: firstly, reacting chlorine balls with polyalcohol and alkaline substances 1 or hydrolyzing to obtain hydroxyl modified chlorine balls, secondly, reacting the hydroxyl modified chlorine balls with acyl chloride and alkaline substances 2 to obtain carbon-carbon double bond modified chlorine balls, and thirdly, reacting the carbon-carbon double bond modified chlorine balls with monoalkylphosphinic acid, an initiator and acid to obtain dialkylphosphinic acid functional group modified extraction resin;
wherein the chlorine ball is introduced into-CH 2 Styrene-divinylbenzene copolymers with Cl-reactive functional groups; the acyl chloride isThe method comprises the steps of carrying out a first treatment on the surface of the R in acyl chloride 1 Is H, an aliphatic substituent with 1-8 carbon atoms, or a phenyl or benzene ring-containing substituent with 6-12 carbon atoms; r in acyl chloride 2 An aliphatic alkylene chain having 0 to 12 carbon atoms or an alkylene chain having 6 to 16 carbon atoms and containing a benzene ring; monoalkylphosphinic acid is->R in monoalkylphosphinic acid 3 Is an aliphatic substituent having 4 to 12 carbon atoms or a substituent having 8 to 16 carbon atoms and containing a benzene ring.
2. The method for preparing dialkylphosphinic acid functional group modified extraction resin as claimed in claim 1, wherein the specific preparation steps are as follows:
(1) The hydroxyl modified chlorine ball is prepared by taking chlorine balls as raw materials through one of the following methods:
(1) reacting the chlorine ball, the polyol and the alkaline substance 1 in an organic solvent A at 40-180 ℃ for 2-24 hours, and carrying out solid-liquid separation to obtain hydroxyl modified chlorine balls; wherein the mass ratio of the chlorine ball to the polyol is 10:1-1:10, and the mass ratio of the chlorine ball to the alkaline substance 1 is 20:1-1:20;
(2) mixing the chlorine ball with the aqueous solution of the alkaline substance 1, reacting for 2-72 hours at 25-120 ℃, and carrying out solid-liquid separation to obtain hydroxyl modified chlorine balls; wherein the mass ratio of the chlorine ball to the alkaline substance 1 is 10:1-1:10, and the mass concentration of the alkaline substance 1 is 1-40%;
(3) mixing the chlorine ball with an acid aqueous solution, reacting for 2-72 hours at 25-120 ℃, and carrying out solid-liquid separation to obtain hydroxyl modified chlorine balls; wherein the mass ratio of the chlorine ball to the acid is 10:1-1:10, and the mass concentration of the acid is 1-40%;
(4) mixing chlorine balls and an aqueous solution of metal salt, reacting for 1-24 hours at 0-100 ℃, and carrying out solid-liquid separation to obtain hydroxyl modified chlorine balls; wherein the mass ratio of the chlorine ball to the metal salt is 10:0.1-1:5, and the mass concentration of the metal salt is 0.1-30%;
(2) Adding 1-20 times of water and/or an organic solvent B into the hydroxyl modified chlorine ball obtained in the step (1), and adding an alkaline substance 2, wherein the mass ratio of the alkaline substance 2 to the hydroxyl modified chlorine ball is 0.05:1-2:1;
(3) Dissolving acyl chloride with carbon-carbon double bonds by using an organic solvent B, slowly dropwise adding the acyl chloride and the organic solvent B into a mixed system of the hydroxyl modified chlorine balls and the alkaline substance 2 obtained in the step (2) at the temperature of 0-80 ℃ in a volume ratio of 1:0.5-1:10, wherein the mass ratio of the acyl chloride to the hydroxyl modified chlorine balls is 0.05:1-3:1, and reacting for 0-10 hours after the dropwise adding is finished to obtain the carbon-carbon double bond modified chlorine balls; wherein the mol ratio of the acyl chloride to the alkaline substance 2 is 1:0.5-1:2;
(4) And (3) reacting the carbon-carbon double bond modified chlorine ball obtained in the step (3) with monoalkylphosphinic acid, an initiator and an organic solvent C at 80-150 ℃ for 8-48 h, and carrying out solid-liquid separation to obtain the dialkylphosphinic acid functional group modified extraction resin.
3. The process for preparing dialkylphosphinic acid functional group modified resin extract according to claim 2, wherein the polyhydric alcohol comprises, but is not limited to, pentaerythritol, ethylene glycol, 1, 2-propylene glycol, 1, 4-butylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolethane, trimethylolpropane, 2-phenyl-1, 3-propanediol.
4. The process for preparing a dialkylphosphinic acid functional group modified resin according to claim 2, wherein the basic material 1 and the basic material 2 may be the same or different and include, but are not limited to, one or more of triethylamine, pyridine, diisopropylmethylamine, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide or lithium hydroxide.
5. The process for preparing dialkylphosphinic acid functional group modified resin extract according to claim 2, wherein the acid in step (1) and the acid in step (4) may be the same or different and include, but are not limited to, one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hypochlorous acid, silicic acid, boric acid, formic acid, acetic acid, propionic acid, butyric acid, succinic acid, glutaric acid, adipic acid, suberic acid, citric acid, oxalic acid, azelaic acid, sebacic acid.
6. The method for preparing dialkylphosphinic acid functional group modified resin according to claim 2, wherein the metal salt comprises one or more than one of copper sulfate, ferrous sulfate, ferric sulfate, cadmium sulfate, manganese sulfate, zinc sulfate, copper iodide, ferric chloride and copper acetate.
7. The preparation method of the dialkylphosphinic acid functional group modified extraction resin according to claim 2, wherein the organic solvent A is one or more of 1, 4-dioxane, tetrahydrofuran, N-dimethylformamide, toluene or xylene; the organic solvent B is one or more of diethyl ether, petroleum ether, tetrahydrofuran, 1, 4-dioxane, N-octane, cyclohexane, sulfonated kerosene, N-dimethylformamide, toluene or xylene; the organic solvent C is one or more of N-octane, cyclohexane, petroleum ether, sulfonated kerosene, tetrahydrofuran, 1, 4-dioxane, N-butanol, N-amyl alcohol, N-hexanol, N-octanol, isooctanol, decanol, N-dimethylformamide, toluene or xylene.
8. The method for preparing the dialkylphosphinic acid functional group modified extraction resin according to claim 2, wherein the initiator is one or more of tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, dibenzoyl peroxide, lauroyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, diethyl hexyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, diphenyl oxyethyl peroxydicarbonate and azobisisobutyronitrile.
9. The preparation method of the dialkylphosphinic acid functional group modified extraction resin according to claim 2, wherein the mass ratio of the carbon-carbon double bond modified chlorine ball to the monoalkylphosphinic acid is 6:1-1:6, the molar ratio of the monoalkylphosphinic acid to the acid is 6:1-1:2, and the mass of the initiator is 0.1-10% of the mass of the monoalkylphosphinic acid.
10. The method for preparing dialkylphosphinic acid functional group modified resin according to claim 2, wherein in the method for preparing hydroxyl modified chlorine balls in the step (1), polyhydric alcohol is added in the methods (2), (3) and (4), and the mass ratio of polyhydric alcohol to chlorine balls is 0-1:1.
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CN102690286A (en) * 2012-05-22 2012-09-26 清华大学 Synthetic method of high-purity asymmetrical dialkyl phosphinic acid
CN113527552A (en) * 2021-07-08 2021-10-22 北京科技大学 Chlorine ball modification method for modifying dialkyl phosphinic acid functional group

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Publication number Priority date Publication date Assignee Title
CN102690286A (en) * 2012-05-22 2012-09-26 清华大学 Synthetic method of high-purity asymmetrical dialkyl phosphinic acid
CN113527552A (en) * 2021-07-08 2021-10-22 北京科技大学 Chlorine ball modification method for modifying dialkyl phosphinic acid functional group

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