阅读说明：本技术 可同步调控机械强度及交换容量的强碱阴离子交换树脂及其制备方法 (Strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity and preparation method thereof ) 是由 李启蒙 王国祥 韩睿明 刘金娥 陈焱山 许晓光 张新厚 陈赟 于 2021-08-31 设计创作，主要内容包括：本发明公开了一种可同步调控机械强度及交换容量的强碱阴离子交换树脂及其制备方法,所述树脂骨架的结构中包括所示的结构单元,A为含有季铵盐的基团。本发明利用丙烯酸系单体反应物、致孔剂、引发剂组成油相,与含分散剂的水相混合均匀,升温进行悬浮聚合,形成高交联的球体,球体的机械强度和湿真密度均较高,聚合反应后的树脂球体通过控制胺酯交换的胺化反应过程对树脂的机械强度和交换容量进行同步调控,进一步经过烷基化反应形成季铵盐基团,最终制备出丙烯酸系强碱阴离子交换树脂。本发明制备的树脂机械强度较高,磨后圆球率高,且具有较高的湿真密度和沉降速率,可以替代传统强碱阴离子交换树脂,用于分离和去除各种水体中电负性的物质。(The invention discloses a strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity and a preparation method thereof, wherein the structure of a resin framework comprises A is a group containing quaternary ammonium salt. According to the invention, an acrylic acid series monomer reactant, a pore-forming agent and an initiator are utilized to form an oil phase, the oil phase is uniformly mixed with a water phase containing a dispersing agent, the mixture is heated for suspension polymerization to form a high-crosslinked sphere, the mechanical strength and the wet and real density of the sphere are both high, the resin sphere after the polymerization reaction synchronously regulates and controls the mechanical strength and the exchange capacity of the resin by controlling the amination reaction process of amine ester exchange, and a quaternary ammonium salt group is further formed through alkylation reaction, so that the acrylic acid series strong base anion exchange resin is finally prepared. The resin prepared by the invention has higher mechanical strength, high sphericity rate after grinding, higher wet density and sedimentation rate, can replace the traditional strong base anion exchange resin, and is used for separating and removing electronegative substances in various water bodies.)

1. The acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity is characterized in that the structure of the resin skeleton comprisesThe structural unit is shown, wherein A is a group containing quaternary ammonium salt, and the group A is any one of the following 6 groups:

wherein R is₁，R₂，R₃，R₄，R₅Each independently selected from C_1～4Alkyl or hydroxy substituted C_1～4An alkyl group; wherein n in the group a is 0, 1,2, 3, 4, 5 or 6; x represents Cl, Br, I or OH.

2. The acrylic acid based strongly basic anion exchange resin capable of synchronously controlling mechanical strength and exchange capacity as claimed in claim 1, wherein R1, R2, R3, R4 and R5 are independently selected from methyl or ethyl.

3. The acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity as claimed in claim 1, wherein the acrylic acid series strong base anion exchange resin has a particle size of 100-600 μm, a strong base exchange capacity of 2.0-4.5 mmol/g, a water content of 46-68%, a sphericity after grinding of 80-99.9%, a wet true density of 1.1-1.3 g/mL, and a settling rate of 50-90 m/h in pure water at 20 ℃.

4. The preparation method of the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity of the claim 1 comprises the following steps: the method comprises the steps of utilizing acrylic acid series monomer reactants, a pore-forming agent and an initiator to form an oil phase, wherein the acrylic acid series monomer reactants comprise monomers and a cross-linking agent or only comprise the cross-linking agent, uniformly mixing the acrylic acid series monomer reactants with water containing a dispersing agent under the stirring action, heating to carry out suspension polymerization to form a high-cross-linked resin sphere, controlling the amination reaction process of amine ester exchange by the resin sphere after polymerization reaction to synchronously regulate and control the mechanical strength and the exchange capacity of the resin, further carrying out alkylation reaction on the resin after amination reaction to form a quaternary ammonium salt group, and finally preparing the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity.

5. The preparation method of claim 4, wherein the preparation method of the acrylic acid-based strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity preferably comprises the following steps:

(1) adding an oil phase containing an acrylic monomer reactant, a pore-forming agent and an initiator into a water phase in which a dispersing agent is dissolved, stirring for reaction, and extracting or cleaning and airing a sphere after the reaction is finished;

(2) aminating the resin spheres obtained in the step (1) by using one or more of ethylenediamine, N-dimethylpropylenediamine, N-dimethylbutylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine;

(3) cleaning and drying the aminated resin in the step (2);

(4) and (4) reacting the resin spheres obtained in the step (3) with an alkylating reagent in an alkaline solution to obtain the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity.

6. The preparation method according to claim 5, wherein the monomer reactant in the step (1) comprises a monomer and a crosslinking agent, the weight ratio of the total mass of the monomer reactant to the porogen is 1: 0.1-1: 1.5, and the weight ratio of the monomer to the crosslinking agent in the monomer reactant is (0-0.2): 1.

7. the preparation method according to claim 5, wherein the monomer in the monomer reactant in step (1) is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate and glycidyl methacrylate; the cross-linking agent is selected from one or more of ethylene glycol dimethacrylate, ethylene glycol diethyl diallyl ester, trimethylacrylic acid (trimethylolpropane) ester and divinylbenzene, the cross-linking agent comprises at least one of ethylene glycol dimethacrylate, ethylene glycol diethyl diallyl ester and trimethylacrylic acid (trimethylolpropane) ester, the total mass of one or more of the three accounts for more than 90% of the total mass of the cross-linking agent, the cross-linking agent also comprises divinylbenzene, and the mass of the divinylbenzene accounts for 0-10% of the total mass of the cross-linking agent; the pore-foaming agent is one or more of toluene, xylene, ethyl acetate, 200# solvent oil, isopropanol, n-butanol, liquid wax, n-heptane, n-octane, isooctane and n-decane; the initiator is one or two of azodiisobutyronitrile and benzoyl peroxide.

8. The preparation method according to claim 5, wherein the stirring speed of the stirring reaction in the step (1) is 100-350 rpm, the temperature is controlled at 50-80 ℃, and the temperature is kept at 85-95 ℃ for 4-15 hours after the reaction for 2-8 hours.

9. The preparation method according to claim 5, wherein in the step (2), the resin spheres obtained in the step (1) are aminated with one or more of ethylenediamine, N-dimethylpropylenediamine, N-dimethylbutylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine in an amount of 1-8 times the mass of the resin at 120-260 ℃ for 6-30 hours.

10. The method according to claim 5, wherein the alkylating reagent in step (4) is selected from one or more of methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide and ethyl iodide, and the weight ratio of the alkylating reagent to the resin is 1: 1-8: 1, reacting for 2-48 hours at 40-120 ℃.

Technical Field

The invention belongs to the field of resin materials, and particularly relates to an acrylic acid series strong-base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity and a preparation method thereof.

Background

The ion exchange resin material has the advantages of adjustable structure, high adsorption capacity, strong selectivity, easy desorption and regeneration and the like, and is widely applied to the field of water treatment. The polyacrylic acid anion exchange resin has higher exchange capacity and exchange capacity for electronegative weakly acidic organic matters because the skeleton is hydrophilic. Meanwhile, the polyacrylic acid anion exchange resin has strong capability of resolving organic matters and can resist pollution caused by soluble organic matters. The adsorption effect of the acrylic acid series strong-base anion exchange resin on the humic acid and the fulvic acid of macromolecular organic matters is far better than that of the macroporous styrene series ion exchange resin, and the resin is easier to elute and regenerate. Therefore, the acrylic acid series strong base anion exchange resin is widely applied to the aspects of biomedical engineering, chemical analysis, wastewater treatment, resource utilization and the like.

The synthesis of conventional acrylic anion exchange resins requires the use of acrylate monomers such as methyl acrylate, ethyl acrylate, glycidyl acrylate, and the like. In the synthesis method of the magnetic strong base anion exchange resin mentioned in U.S. Pat. No.5900146, after the polymerization of the active monomer glycidyl methacrylate, the epoxy group is in the resin structure, and the epoxy group can directly react with trimethylamine hydrochloride to generate quaternary ammonium salt, so as to form the acrylic strong base anion exchange resin. Compared with styrene ion exchange resin, the acrylic acid anion exchange resin has poor mechanical strength, and the resin is better than mutual contact and friction when applied to a water treatment process, and can generate 5-10 mu m of resin suspended particles, so that resin loss and secondary pollution of water are caused. In general, the mechanical strength of the resin can be improved by adjusting the pore structure of the resin by increasing the proportion of the crosslinking agent, optimizing the porogen component and proportion, and the like. It has also been reported that the mechanical strength of the resin can be significantly improved by doping inorganic nanoparticles when formed or synthesized in situ inside the resin. However, inorganic nanoparticles also risk secondary contamination due to leaching, and inorganic particles have poor acid-base resistance. Therefore, the preparation of acrylic anion exchange resins with good structural stability and strong mechanical strength remains a technical problem to be solved.

Disclosure of Invention

The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides the acrylic acid series strong-base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity, and the resin can control the crosslinking degree and the exchange capacity according to the requirements of the use environment and ensure that the resin has proper exchange capacity and mechanical strength. In addition, the problems of low content of the cross-linking agent of the general acrylic acid series strong base anion exchange resin, poor mechanical strength of the resin and the like are effectively solved.

The invention also aims to provide a preparation method of the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity. The resin can synchronously regulate and control the mechanical strength and the exchange capacity of the resin by controlling the amination reaction process of amine ester exchange, and further synthesize the strong base anion exchange resin by the alkylation process.

The technical scheme is as follows: in order to achieve the above purpose, the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity comprises a resin skeletonThe structural unit is shown, wherein A is a group containing quaternary ammonium salt, and the group A is any one of the following 6 groups:

wherein R is₁，R₂，R₃，R₄，R₅Each independently selected from C_1～4Alkyl or hydroxy substituted C_1～4An alkyl group; n in the group a is 0, 1,2, 3, 4, 5 or 6, preferably n in the group a is 0, 1, 3; x represents Cl, Br, I or OH.

Preferably, R1, R2, R3, R4 and R5 are respectively and independently selected from methyl or ethyl.

Wherein the acrylic acid series strong base anion exchange resin has the particle size of 100-600 mu m, the strong base exchange capacity of 2.0-4.5 mmol/g, the water content of 46-68%, the sphericity ratio after grinding (GB/T12598-2001 method) of 80-99.9%, the wet density of 1.1-1.3 g/mL, and the sedimentation rate in pure water at 20 ℃ of 50-90 m/h.

The preparation method of the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity comprises the following steps: the method comprises the steps of utilizing acrylic monomer reactants, a pore-forming agent and an initiator to form an oil phase, wherein the acrylic monomer reactants comprise a monomer and a cross-linking agent or only comprise the cross-linking agent, uniformly mixing the acrylic monomer reactants and a water phase containing a dispersing agent under the stirring action, heating to carry out suspension polymerization, and forming a high-crosslinked resin sphere after the suspension polymerization due to the fact that an ester-based cross-linking agent accounts for a relatively high ratio in the monomer reactants, wherein the mechanical strength and the wet-real density of the resin sphere are relatively high. The resin ball after polymerization reaction controls the amine ester exchange amination process to synchronously regulate and control the mechanical strength and exchange capacity of the resin, namely, the resin ester group participating in the amination reaction can exchange the resin to generate an amine group, and the ester group not participating in the amination reaction is still used as a crosslinking unit to keep the resin with higher mechanical strength. The resin after amination is further alkylated to form quaternary ammonium salt group, and finally the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity is prepared.

The preparation method of the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity comprises the following steps:

(1) adding an oil phase containing acrylic monomer reactants (monomer and cross-linking agent), a pore-forming agent and an initiator into a water phase in which a dispersing agent is dissolved, stirring and heating, and extracting or cleaning and airing the spheres after the reaction is finished;

(2) aminating the resin spheres obtained in the step (1) by using one or more of ethylenediamine, N-dimethylpropylenediamine, N-dimethylbutylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine;

(3) cleaning and drying the aminated resin in the step (2);

(4) and (4) reacting the resin spheres obtained in the step (3) with an alkylating reagent in an alkaline solution to obtain the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity.

Wherein in the step (1), the monomer reactant comprises a monomer and a cross-linking agent, the weight ratio of the total mass of the monomer reactant to the pore-foaming agent is 1: 0.1-1: 1.5, and the weight ratio of the monomer to the cross-linking agent in the monomer reactant is (0-0.2): 1.

wherein, in the step (1), the monomer in the monomer reactant is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate and glycidyl methacrylate; the cross-linking agent comprises at least one of ethylene glycol dimethacrylate, ethylene glycol diethyl diallyl ester and trimethyl acrylic acid (trimethylolpropane) ester, the total mass of one or more of the three accounts for more than 90% of the total mass of the cross-linking agent, and the cross-linking agent also comprises divinylbenzene, the mass of which accounts for 0-10% of the total mass of the cross-linking agent. (ii) a The pore-foaming agent is one or more of toluene, xylene, ethyl acetate, 200# solvent oil, isopropanol, n-butanol, liquid wax, n-heptane, n-octane, isooctane and n-decane; the initiator is one or two of azodiisobutyronitrile and benzoyl peroxide.

Preferably, the crosslinking agent is one or both of trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate.

Preferably, the pore-foaming agent is one or more of toluene or xylene. The weight ratio of the total weight of monomer and crosslinker to porogen is preferably 1: 0.1-1: 1.0.

preferably, in step (1) of the present invention, an initiator is added to the oil phase in an amount of 0.5 to 2% by weight of the reactant system, and the mixture is stirred to sufficiently dissolve the initiator.

Wherein the stirring speed of the stirring reaction in the step (1) is 100-350 rpm, the temperature is controlled at 50-80 ℃, and the temperature is kept at 85-95 ℃ for 4-15 hours after the reaction is carried out for 2-8 hours.

Preferably, in step (1) of the present invention, the aqueous phase comprises water, a dispersant and an inorganic salt. The dispersant is selected from one or more of gelatin, polyvinyl alcohol 1788, hydroxyethyl cellulose, sodium dodecyl benzene sulfonate and sodium lignosulfonate; preferably one or two of hydroxyethyl cellulose and polyvinyl alcohol 1788; the inorganic salt is one or two of common salt and sodium sulfate, preferably sodium sulfate; in the water phase, the dispersing agent accounts for 0.2-3% by mass, the salt accounts for 0-20%, the sodium sulfate accounts for 0-10% by mass, and the balance is water;

and (2) aminating the resin spheres obtained in the step (1) with one or more of ethylenediamine, N-dimethylpropylenediamine, N-dimethylbutylamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine which are 1-8 times of the mass of the resin at 120-260 ℃ for 6-30 hours.

Preferably, in step (2) of the present invention, the amination reaction is controlled by controlling the time and temperature of the amination reaction, i.e. the ester groups in the resin spheres participating in the reaction can make the resin generate amine groups, the ester groups not participating in the reaction still serve as crosslinking units to keep the resin at a high mechanical strength, and the mechanical strength and exchange capacity of the resin are synchronously controlled by controlling the amination reaction process of amine transesterification.

Preferably, the resin obtained in the step (3) is repeatedly washed by one or more of methanol, ethanol and acetone, then washed by water for several times, and dried at the temperature of 30-50 ℃.

Wherein, the alkylating reagent in the step (4) is selected from one or more of methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide and ethyl iodide, and the weight ratio of the alkylating reagent to the resin is 1: 1-8: 1, reacting for 2-48 hours at 40-120 ℃.

Preferably, the weight ratio of alkylating agent to resin is 3: 1-6: 1. the specific weight ratio of alkylating agent to resin is 1:1. or 2: 1. or 3: 1. or 3.5: 1. or 4: 1. or 4.5: 1. or 5: 1. or 6: 1. or 7: 1. or 8: 1.

the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity is applied to separating and removing electronegative substances in various water bodies. The principle is as follows: the invention uses acrylic monomer reactant (monomer and cross linker), pore-forming agent and initiator to form oil phase, which is mixed with water phase containing dispersant under agitation, and then heated to carry out suspension polymerization. The resin ball after polymerization synchronously regulates and controls the mechanical strength and exchange capacity of the resin by controlling the amination process of amine ester exchange, quaternary ammonium salt groups are further formed through alkylation reaction, and finally the acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity is prepared.

The crosslinking agent mainly selected by the invention has similar properties with the monomer, can be used as a crosslinking unit and also can be used as a functional unit for amination reaction, the part participating in amination reaction has the same function with the monomer, so that the resin has exchange capacity, and the part not participating in amination reaction can be used as the crosslinking unit to increase the mechanical strength of the resin.

The cross-linking agent can be used as a cross-linking unit and a functional unit to carry out amination reaction, the utilization efficiency of monomers and the cross-linking agent is increased, the exchange capacity is high, and the mechanical strength is high. The invention can control the amination reaction degree, so the exchange capacity and the mechanical strength of the resin can be adjusted and controlled simultaneously by controlling the amination reaction process.

In addition, the crosslinking agent is divinylbenzene in the prior art, which is not easily polymerized with acrylic monomers and thus is not used in too large an amount. In addition, the purity of commercial divinylbenzene is only 50 percent, a large amount of other impurities can be introduced, and the exchange capacity of the resin is greatly reduced when the dosage of the divinylbenzene cross-linking agent is large, so that the application effect is not realized.

The invention is mainly characterized in that the strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity is prepared, the problems of single functions of monomers and cross-linking agents and the like in the traditional preparation of acrylic acid anion exchange resin are effectively solved, and the monomers in the prior art are commonly methyl acrylate, ethyl acrylate, glycidyl acrylate (GMA) and the like. Among them, GMA forms a resin having a low exchange capacity and poor mechanical strength, and methyl acrylate and ethyl acrylate, which are both required to undergo an amine transesterification, are more used. The cross-linking agent of the invention selects a specific acrylate cross-linking agent which can be used as both a cross-linking agent and a monomer, so that the cross-linking agent is similar to the monomer in the amine ester exchange reaction, the cross-linking unit can participate in the reaction to generate a functional group, and can also be used as a cross-linking unit only (the higher the cross-linking degree is, the higher the mechanical strength is, the cross-linking degree is reduced after the amination reaction is participated in), and the cross-linking agent can be determined by controlling the amine ester exchange condition, so that the exchange capacity and the mechanical strength of the resin can be synchronously regulated and controlled according to the use requirement.

The particular cross-linking agent used in the present invention is important. Namely an acrylate series cross-linking agent, such as one or more of ethylene glycol dimethacrylate, ethylene glycol diethyl diallyl ester, trimethacrylate (trimethylolpropane) and divinylbenzene. The invention can make the resin have exchange group through special amine ester exchange reaction, and can synchronously regulate and control the exchange capacity and mechanical strength of the resin by controlling the process.

Has the advantages that: compared with the prior art, the invention has the following advantages:

the acrylic acid series strong-base anion exchange resin with adjustable mechanical strength and exchange capacity prepared by the method can simultaneously adjust the exchange capacity and the mechanical strength of the resin by controlling the amination process of amine ester exchange. According to the test of the national test standard of the sphericity rate after resin grinding, the strong base anion exchange resin prepared by the method has higher mechanical strength, and the sphericity rate after resin grinding can reach more than 80% (80-99.9%) and is higher than that of the traditional acrylic acid series anion exchange resin (the sphericity rate after grinding is 55.0-75.0%). The resin has high wet density and sedimentation rate at the same time, so that the resin is easy to separate in the practical application process. In addition, the resin provided by the invention is less broken in the water treatment process, can be recycled for a long time, so that the water treatment cost is reduced, and the resin can be used for separating and removing electronegative substances in various water bodies, such as dissolved organic matters, and various anions such as nitrate and phosphate, instead of the traditional strong base anion exchange resin.

The strong base anion exchange resin capable of synchronously regulating and controlling the mechanical strength and the exchange capacity, which is prepared by the invention, is not added with inorganic nano particles, and is different from the prior strong base anion exchange resin which can enhance the mechanical strength and the stability of the resin through the inorganic nano particles, so that the problem of secondary pollution caused by the loss of the inorganic nano particles does not exist; the exchange capacity and the mechanical strength of the resin can be adjusted according to the use requirement by controlling the amine ester exchange reaction, and the high crosslinking degree of the resin can be ensured due to the high content of the crosslinking agent (0.02-0.2: 1 of the monomer: the crosslinking agent), so that the high mechanical strength and the structural stability of the resin can be ensured, and the pollution caused by 5-10 mu m suspended particles of the resin can not be generated.

The invention has simple preparation and rich raw material sources, and can be produced and applied in large scale.

Drawings

FIG. 1 is a scanning electron microscope image of an acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity.

Detailed Description

The invention will be better understood from the following examples. It is easily understood by those skilled in the art that the descriptions of the embodiments are only for illustrating the present invention and should not be construed as limiting the present invention as detailed in the claims. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The experimental procedures, in which specific conditions are not indicated in the examples, are generally carried out under conventional conditions or conditions recommended by the manufacturer.

Wherein: the wet and real density determination refers to a method for determining the wet and real density of GB 8330-87 ion exchange resin.

The determination of the sphericity after grinding refers to the determination of the permeability sphericity of GB/T12598-2001 ion exchange resin and the sphericity after grinding.

The water content determination refers to a method for determining the water content of GB/T5757-2008 ion exchange resin.

Settlement rate determination reference, Chenxiu Branch, etc. test of hydraulic properties of weak acid exchange resin [ J ] proceedings of Beijing university of science and technology, 2001,23(5): 398-.

The exchange capacity is determined by reference to the method for determining the exchange capacity of GB/T11992-1989 chlorine type strong base anion exchange resin.

Example 1

500g of a 10% aqueous solution of sodium sulfate containing 2% by weight of hydroxyethyl cellulose was put into a 2L three-necked flask, and the stirring speed was controlled at 150 rpm. Adding a mixed solution of 10g of methyl acrylate, 10g of divinylbenzene, 100g of trimethylolpropane trimethacrylate, 1.0g of azobisisobutyronitrile and 100g of toluene into the three-neck flask, heating to 50 ℃, keeping for 8 hours, heating to 85 ℃, keeping for 15 hours, and discharging; cleaning with ethanol, discharging, air drying to obtain resin spheres, adding ethylenediamine with the weight 4 times that of the resin, keeping at 130 ℃ for 8 hours, and discharging; discharging, cleaning with ethanol, cleaning with water to neutrality, and drying at 30-50 ℃; drying, adding 300mL of 10% liquid caustic soda, adding 450g of chloromethane, reacting for 10 hours at 40 ℃, discharging, transforming with NaCl, and cleaning to obtain the product. The scanning electron micrograph of the resulting resin is shown in example FIG. 1.

The obtained acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity has the particle size mainly distributed in 300-500 mu m, the wet density of 1.14g/mL, the sphericity rate after grinding of 94%, the water content of 63%, the settling speed of 83.2m/h and the strong base exchange capacity of 3.23 mmol/g.

The basic structural formula is determined according to the type of the added amination reagent as follows:

wherein n in the group a is 0.

Example 2

500g of a 15% aqueous solution of sodium chloride containing 0.2% by weight of 1788 polyvinyl alcohol was put into a 2L three-necked flask, and the stirring speed was controlled at 200 rpm. 120g of trimethylolpropane trimethacrylate (all as cross-linking agent, no monomer, and divinylbenzene 0), 1.0g of benzoyl peroxide, 100g of toluene, 2g of 200 g of toluene^#Adding the solvent oil mixture into the three-neck flask, heating to 55 deg.C, maintaining for 8 hr, heating to 85 deg.C, maintaining for 10 hrAnd (6) discharging. Washing with ethanol, discharging, air drying to obtain resin spheres, adding ethylenediamine with the weight of 2.5 times of that of the resin, keeping at 180 ℃ for 20 hours, and discharging. After cleaning, adding 300mL of 10% liquid caustic soda, adding 480g of chloromethane, reacting for 3 hours at 40 ℃, discharging, transforming by using NaCl, and cleaning to obtain the product.

The obtained acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity has the particle size mainly distributed in 200-500 mu m, the wet density of 1.28g/mL, the sphericity rate after grinding of 98%, the water content of 58%, the settling speed of 87.9m/h and the strong base exchange capacity of 3.43 mmol/g.

The basic structural formula is determined according to the type of the added amination reagent as follows:

wherein n in the group a is 0.

In example 2, only the crosslinking agent was used, and there was no monomer in the conventional sense, and the crosslinking agent was used as a monomer, and not only was the strong base exchange capacity excellent, but also the mechanical strength was higher.

Example 3

500g of a 2L three-necked flask containing 1.5% by weight of polyvinyl alcohol 1788, 6% by weight of sodium chloride, and 2% by weight of an aqueous solution of sodium sulfate was placed therein, and the stirring speed was controlled at 300 rpm. A mixed solution of 5g of ethyl acrylate, 70g of trimethylolpropane trimethacrylate, 30g of ethylene glycol dimethacrylate, 1.5g of azobisisobutyronitrile, 1.0g of benzoyl peroxide, 50g of xylene and 65g of isopropanol is added into a three-neck flask, the temperature is raised to 60 ℃, the temperature is maintained for 6 hours, the temperature is raised to 85 ℃, the temperature is maintained for 6 hours, and then the mixture is discharged. Washing with ethanol, discharging, air drying, adding 6 times of diethylenetriamine, and discharging after keeping at 180 deg.C for 20 hr. After cleaning, 350mL of 10% liquid alkali is added, 500g of chloroethane is added, and the mixture is discharged after reacting for 20 hours at 60 ℃. Transforming with NaCl and cleaning.

The obtained acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity has the particle size mainly distributed in 180-500 mu m, the wet density of 1.08g/mL, the sphericity rate after grinding of 88%, the water content of 54%, the settling velocity of 77.9m/h and the strong base exchange capacity of 3.03 mmol/g.

The basic structural formula is determined according to the type of the added amination reagent as follows:

wherein n in the group a is 1.

Example 4

500g of a 2L three-necked flask containing 2.0% by weight of gelatin and 15% by weight of an aqueous sodium chloride solution was placed therein, and the stirring rate was controlled at 150 rpm. A mixed solution of 40g of butyl methacrylate, 100g of trimethylolpropane trimethacrylate, 1g of azobisisobutyronitrile, 1.5g of benzoyl peroxide, 80g of xylene and 60g of n-heptane is added into a three-neck flask, the temperature is raised to 70 ℃, the temperature is maintained for 6 hours, the temperature is raised to 92 ℃, the temperature is maintained for 5 hours, and then the mixture is discharged. Washing with ethanol, discharging, air drying, adding 8 times of tetraethylenepentamine, keeping at 170 deg.C for 20 hr, and discharging. After cleaning, 400mL of 10% caustic soda liquid is added, 900g of chloromethane is added, and the mixture is discharged after reacting for 25 hours at 80 ℃. Transforming with NaCl and cleaning.

The obtained acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity has the particle size mainly distributed in 200-500 mu m, the wet density of 1.15g/mL, the sphericity rate after grinding of 88%, the water content of 52%, the settling speed of 82.5m/h and the strong base exchange capacity of 3.37 mmol/g.

The basic structural formula is determined according to the type of the added amination reagent as follows:

wherein n is 3 in the group A.

Example 5

500g of an aqueous solution containing 1.0% by weight of hydroxyethyl cellulose, 0.2% by weight of sodium lignin sulfonate and 3% by weight of sodium sulfate was put into a 2L three-necked flask, and the stirring speed was controlled at 250 rpm. Adding a mixed solution of 120g of trimethylolpropane trimethacrylate, 10g of divinylbenzene, 2.0g of azobisisobutyronitrile, 80g of toluene and 50g of cyclohexanol into a three-neck flask, heating to 70 ℃, keeping for 5 hours, heating to 95 ℃, keeping for 6 hours, and discharging. Washing with ethanol, discharging, air drying, adding 5 times of tetraethylenepentamine, keeping at 180 deg.C for 10 hr, and discharging. After cleaning, adding 400mL of 10% liquid alkali, adding 800g of chloroethane, reacting for 20 hours at 120 ℃, discharging, transforming by using NaCl, and cleaning to obtain the product.

The obtained acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity has the particle size mainly distributed in 200-500 mu m, the wet density of 1.18g/mL, the sphericity rate after grinding of 98%, the water content of 57%, the settling speed of 80.9m/h and the strong base exchange capacity of 3.23 mmol/g.

The basic structural formula is determined according to the type of the added amination reagent as follows:

wherein n is 3 in the group A.

Example 6

500g of a 2L three-necked flask containing 1.0% by weight of gelatin, 0.5% by weight of sodium lignin sulfonate and 15% by weight of an aqueous sodium chloride solution was placed therein, and the stirring speed was controlled at 150 rpm. Adding a mixed solution of 120g of ethylene glycol dimethacrylate, 10g of methyl acrylate, 2g of divinylbenzene, 1.75g of benzoyl peroxide, 100g of xylene and 50g of isooctane into a three-neck flask, heating to 70 ℃, keeping for 4 hours, heating to 95 ℃, keeping for 5 hours, and discharging. Washing with ethanol, discharging, air drying, adding 7 times of diethylenetriamine, and discharging after keeping at 160 deg.C for 16 hr. After cleaning, adding 500mL of 10% liquid caustic soda, adding 650g of chloromethane, reacting for 18 hours at 60 ℃, discharging, transforming by using NaCl, and cleaning to obtain the product.

The obtained acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity has the particle size mainly distributed in 200-500 mu m, the wet density of 1.18g/mL, the sphericity rate after grinding of 91%, the water content of 55%, the settling speed of 77.9m/h and the strong base exchange capacity of 3.43 mmol/g.

The basic structural formula is determined according to the type of the added amination reagent as follows:

wherein n in the group a is 1.

Example 7

500g of an aqueous solution containing 0.8% by weight of hydroxyethyl cellulose, 0.5% by weight of sodium lignin sulfonate and 2% by weight of sodium sulfate was put in a 2L three-necked flask, and the stirring speed was controlled at 100 rpm. A mixed solution of 100g of trimethylolpropane trimethacrylate, 10g of divinylbenzene, 1.5g of azobisisobutyronitrile and 160g of toluene is added into a three-neck flask, the temperature is raised to 70 ℃, the mixture is kept for 4 hours, the temperature is raised to 95 ℃, the mixture is kept for 8 hours, and then the mixture is discharged. Washing with ethanol, discharging, air drying, adding tetraethylenepentamine 4 times of the weight of the resin, keeping at 180 ℃ for 10 hours, and discharging. After cleaning, adding 350mL of 10% liquid alkali, adding 750g of chloroethane, reacting for 24 hours at 100 ℃, discharging, transforming with NaCl, and cleaning to obtain the product.

The obtained acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity has the particle size mainly distributed in 200-500 mu m, the wet density of 1.12g/mL, the sphericity rate after grinding of 96%, the water content of 58%, the settling speed of 82.3m/h and the strong base exchange capacity of 3.13 mmol/g.

The basic structural formula is determined according to the type of the added amination reagent as follows:

wherein n is 3 in the group A.

Example 8

500g of a 2L three-necked flask containing 1.5% by weight of polyvinyl alcohol 1788, 0.2% by weight of hydroxyethyl cellulose and 8% by weight of an aqueous solution of sodium chloride was placed therein, and the stirring rate was controlled at 100 rpm. A mixed solution of 10g of ethyl acrylate, 50g of trimethylolpropane trimethacrylate, 50g of ethylene glycol dimethacrylate, 1.5g of azobisisobutyronitrile, 1.5g of benzoyl peroxide, 70g of xylene and 55g of isopropanol is added into a three-neck flask, the temperature is raised to 60 ℃, the temperature is maintained for 6 hours, the temperature is raised to 85 ℃, the temperature is maintained for 8 hours, and then the mixture is discharged. Washing with ethanol, discharging, air drying, adding 7 times of diethylenetriamine, and discharging after keeping at 190 deg.C for 22 hr. After cleaning, 400mL of 10% liquid alkali is added, 500g of chloroethane is added, and the mixture is discharged after reacting for 20 hours at 60 ℃. Transforming with NaCl and cleaning.

The obtained acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity has the particle size mainly distributed in 180-500 mu m, the wet density of 1.13g/mL, the sphericity rate after grinding of 91%, the water content of 55%, the settling speed of 73.9m/h and the strong base exchange capacity of 3.09 mmol/g.

The basic structural formula is determined according to the type of the added amination reagent as follows:

wherein n in the group a is 1.

Comparative example 1

Comparative example 1 the preparation of example 1 was followed with the following exceptions: without the use of the cross-linking agent of the invention: any one or more of ethylene glycol dimethacrylate, ethylene glycol diethyl diallyl ester, and (trimethylolpropane) trimethacrylate, the resulting resin was similar to commercial strong base anion exchange resin D213.

The preparation process comprises the following steps:

500g of a 10% aqueous solution of sodium sulfate containing 2% by weight of hydroxyethyl cellulose was put into a 2L three-necked flask, and the stirring speed was controlled at 150 rpm. Adding a mixed solution of 110g of methyl acrylate, 10g of divinylbenzene, 1.0g of azobisisobutyronitrile and 100g of toluene into the three-neck flask, heating to 50 ℃, keeping for 8 hours, heating to 85 ℃, keeping for 15 hours, and discharging; cleaning with ethanol, discharging, air drying to obtain resin spheres, adding ethylenediamine with the weight 4 times that of the resin, keeping at 130 ℃ for 8 hours, and discharging; discharging, cleaning with ethanol, cleaning with water to neutrality, and drying at 30-50 ℃; drying, adding 300mL of 10% liquid caustic soda, adding 450g of chloromethane, reacting for 10 hours at 40 ℃, discharging, transforming with NaCl, and cleaning to obtain the product.

The obtained acrylic acid series strong base anion exchange resin capable of synchronously regulating and controlling mechanical strength and exchange capacity has the particle size mainly distributed in 250-500 mu m, the wet density of 1.11g/mL, the sphericity rate after grinding of 56%, the water content of 60%, the settling speed of 78.9m/h and the strong base exchange capacity of 3.33 mmol/g.

Comparative example 1 shows that the exchange capacity can be controlled without using the specific crosslinking agent of the present invention, the resin has poor mechanical strength, and the exchange capacity and the mechanical strength cannot be controlled at the same time.