CN115160510B - Preparation method of enhanced adsorption resin material - Google Patents

Preparation method of enhanced adsorption resin material Download PDF

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CN115160510B
CN115160510B CN202210812658.7A CN202210812658A CN115160510B CN 115160510 B CN115160510 B CN 115160510B CN 202210812658 A CN202210812658 A CN 202210812658A CN 115160510 B CN115160510 B CN 115160510B
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resin material
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CN115160510A (en
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周庆
张子昂
王星煜
何歆逸
周伟伟
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Nanjing University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
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Abstract

The invention discloses a preparation method of enhanced adsorption resin, and belongs to the field of resin materials. According to the preparation method, GMA, NVP and DVB are used as functional monomers, an oil phase consisting of reactants comprising the functional monomers is divided into three parts, the proportion of chain transfer agent, functional monomers and cross-linking agent in each part of oil phase is regulated and controlled according to different polymerization stages and purposes, then the oligomer is controlled to participate in polymerization reaction in different monomer ratios and polymerization degrees in each polymerization stage through an improved suspension polymerization process, and finally the adsorption resin is generated by amination. The polymerization process can enable GMA, NVP and a cross-linking agent DVB to be copolymerized simultaneously to obtain the target white ball, the white ball can be aminated without using chloromethyl ether, and an amination path is environment-friendly. The prepared enhanced adsorption resin material has stable performance, and has larger ion exchange capacity and specific surface area. In addition, the larger pore size distribution of the outer layer of the resin effectively improves the mass transfer efficiency of the resin, and relieves the problem of pore channel blockage caused by the shrinkage cavity effect of an amination reagent.

Description

Preparation method of enhanced adsorption resin material
Technical Field
The invention belongs to the field of resin materials, and particularly relates to a preparation method of an enhanced adsorption resin material.
Background
In recent years, increasingly serious pollution of aquatic environment has been attracting attention worldwide. Pharmaceutical and Personal Care Products (PPCPs) are an emerging class of pollutants, a wide variety and environmental persistence. Therefore, how to remove PPCPs in water body becomes a research hot spot in the environmental field, and the resin adsorption method is an efficient and economical method for removing PPCPs in water body.
The HLB solid phase extraction material of Waters company has a unique hydrophilic-hydrophobic skeleton, and is widely applied to enrichment and separation of trace organic matters in water. However, a large number of PPCPs exhibit an ionized state in an environmental water body, and the HLB extraction efficiency for such organic matters is poor. For this purpose, waters company further proposes a series of ion exchange extraction materials such as WAX, MAX, WCX, MCX and the like. The ion exchange resins based on the hydrophilic skeleton realize excellent extraction effect on ionized organic matters in water, and the skeleton is vinylpyrrolidone-divinylbenzene, but the preparation process is not disclosed. The applicant's earlier patent ZL202111347253.2 proposes an improved seed swelling polymerization process, and series of enhanced extraction materials are prepared, so that the rapid extraction effect on charged PPCPs in water is good. However, because the skeleton structure of the material is N-vinyl pyrrolidone-divinylbenzene and lacks an action site of an amination reagent, when the anion exchange material is prepared by modification, active chlorine groups are firstly introduced into a resin skeleton through chloromethyl ether to react. However, chloromethyl ether required for the reaction is a highly toxic substance, has strong carcinogenicity to human bodies, and once leaked, can cause irreversible harm to life health and environment. Meanwhile, chloromethylation reaction efficiency on the resin is uncontrollable, ion exchange capacity fluctuation of different batches of resins is large, and repeatability is poor. In addition, the "shrinkage cavity" effect of the amination reagent also causes the pore diameter and specific surface area of the resin to be reduced, reduces the mass transfer rate of the resin, and easily blocks pore channels in the adsorption process.
Glycidyl Methacrylate (GMA) is a common industrial raw material, and epoxy groups inside the molecule are active in nature and are commonly used as functional monomers to participate in copolymerization. The results of Wan et al show that the electron cloud density around the oxygen atom in the epoxy group of GMA is large, and when the nucleophile approaches the epoxy group, the epoxy group is opened to form a hydroxyl group and a target functional group. The results of Wang et al show that the higher the level of GMA in the GMA-DVB resin, the larger the average pore size of the resin, but the smaller the specific surface area. Therefore, the content of GMA in the resin is important to regulating and controlling the ion exchange capacity, specific surface area and pore channel structure of the resin. At present, an example of ternary polymerization by using GMA, NVP (N-vinyl pyrrolidone) and DVB (divinylbenzene) is not reported, because the monomers have large hydrophilic-hydrophobic differences and are difficult to copolymerize, and a proper process is lacking to effectively regulate the proportion of the monomers participating in the reaction in the polymerization process.
Therefore, a process which is environment-friendly, can enable GMA, NVP and DVB to be copolymerized simultaneously and can regulate and control the polymerization proportion is developed, and is an important technical problem of improving the adsorption capacity of the resin, improving the mass transfer efficiency and reducing the problem of pore channel blockage.
Disclosure of Invention
1. Object of the invention
Aiming at one of the problems of the prior preparation process and the defects of the adsorption material in practical application, the invention provides a preparation method of an enhanced adsorption resin material and the prepared enhanced adsorption resin, wherein GMA, NVP, DVB is used as a functional monomer, three oil phases are prepared under the condition of existence of a reversible addition-fragmentation chain transfer (RAFT) chain transfer reagent, chain transfer agents and functional monomers in the oil phases are changed to form oligomers, polymerization conditions such as polymerization temperature are controlled to polymerize the three oil phases, the oligomers are controlled to participate in polymerization reaction at different monomer ratios and polymerization degrees in each polymerization stage, GMA, NVP, DVB with larger hydrophilic-hydrophobic difference can participate in the polymerization at the same time, and the resin white ball synthesized by the method, namely, the ternary copolymer of N-vinyl pyrrolidone, glycidyl methacrylate and divinylbenzene with a multilayer structure can realize the amination of the resin without using chloromethyl ether, so as to obtain the enhanced adsorption resin material.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of an enhanced adsorption resin material, which comprises the steps of preparing three oil phases from functional monomers N-vinyl pyrrolidone (NVP), glycidyl Methacrylate (GMA), divinylbenzene (DVB), a chain transfer agent, an initiator and a pore-forming agent, wherein the functional monomers of each oil phase can form an oligomer at the initial stage of polymerization, and controlling the oligomer to participate in polymerization reaction at different monomer ratios and polymerization degrees in each polymerization stage by changing the proportion and polymerization temperature of each functional monomer and the chain transfer agent in the oil phase to obtain a terpolymer of N-vinyl pyrrolidone, glycidyl methacrylate and divinylbenzene with a multi-layer structure, namely resin white balls; and aminating by an amination reagent to obtain a resin material with an ion exchange function, wherein the resin white ball synthesized by the process can realize the amination of the resin without using chloromethyl ether.
Preferably, the preparation method of the reinforced adsorption resin material comprises the following steps:
s1: preparing a disperse phase, adding a dispersing agent and an emulsifying agent into ultrapure water, and uniformly mixing, wherein the dosage of the dispersing agent is 0.1-5% of the mass of the ultrapure water, and the dosage of the emulsifying agent is 0.01-2% of the mass of the ultrapure water;
s2: preparing a first oil phase, and uniformly mixing functional monomers of glycidyl methacrylate, N-vinyl pyrrolidone, divinylbenzene, a chain transfer agent, an initiator and a pore-forming agent, wherein the mass ratio of the functional monomers of glycidyl methacrylate to N-vinyl pyrrolidone to the divinylbenzene is 1:1 (0.1-10), the mass of the chain transfer agent accounts for 0-10% of the total mass of the functional monomers, the mass of the initiator accounts for 1-20% of the total mass of the functional monomers, and the pore-forming agent accounts for 1-30% of the total mass of the functional monomers;
s3: preparing a second oil phase, and uniformly mixing functional monomer glycidyl methacrylate, N-vinyl pyrrolidone, cross-linking agent divinylbenzene, chain transfer agent, initiator and pore-forming agent, wherein the mass ratio of the functional monomer glycidyl methacrylate to the N-vinyl pyrrolidone to the divinylbenzene is 1 (0.1-10): 3, the mass of the chain transfer agent accounts for 0.1-10% of the total mass of the functional monomer, the mass of the initiator accounts for 1-20% of the total mass of the functional monomer, and the pore-forming agent accounts for 1-30% of the total mass of the functional monomer;
s4: preparing a third oil phase, and uniformly mixing functional monomers glycidyl methacrylate, N-vinyl pyrrolidone, a cross-linking agent divinylbenzene, a chain transfer agent, an initiator and a pore-forming agent, wherein the mass ratio of the functional monomers glycidyl methacrylate to the N-vinyl pyrrolidone to the divinylbenzene is (0.1-10): 1:3, the mass of the chain transfer agent accounts for 0.1-10% of the total mass of the functional monomers, the mass of the initiator accounts for 1-20% of the total mass of the functional monomers, and the pore-forming agent accounts for 1-30% of the total mass of the functional monomers;
s5: preparing white balls, heating a disperse phase to 60+/-2 ℃, adding a first oil phase under stirring at 100-1000 rpm, and heating to 80+/-2 ℃ for reaction for 1h; cooling to 60+/-2 ℃, adding a second oil phase under stirring at 100-1000 rpm, prepolymerizing for 20-120 min, and heating to 80+/-2 ℃ for reaction for 1h; cooling to 60+/-2 ℃, adding a third oil phase under the stirring of 100-1000 rpm, pre-polymerizing for 20-120 min, and then heating to 80+/-2 ℃ for reaction for 3h to obtain white balls, wherein the temperatures are the reaction system temperature and not the heating system temperature;
s6: the white balls prepared in the step S5 are added into an amination reagent, the reaction temperature is 55-100 ℃, and the reaction is carried out for 4-24 hours under the stirring of 400-1000 rpm, so that the enhanced adsorption resin material with the ion exchange function is obtained.
Preferably, in the step S1, the dispersant is one or more of polyethylene glycol, sodium hexametaphosphate, liquid paraffin, polyvinylpyrrolidone, and hydroxyethyl cellulose; the emulsifier is one or more of acacia, gelatin, tween 80, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and fatty acid soap.
Preferably, in the step S1, the dispersant is used in an amount of 0.1 to 4% by mass of the ultrapure water.
Preferably, in the above steps S2 to S4, the chain transfer agent is one or more of S, S '-bis (α, α' -dimethyl- α "-acetic acid) trithiocarbonate, methyl (phenyl) aminodithioformate cyanomethyl 2- (dodecylthiocarbonylthio) -2-methylpropanoic acid, 4-cyano-4- [ [ (dodecylthio) thiocarbonyl ] thio ] pentanoic acid, and bis (thiobenzoyl) disulfide.
Preferably, in the step S2 to S4, the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, benzoyl peroxide, and ammonium persulfate.
Preferably, in the steps S2 to S4, the pore-forming agent is one or more of toluene, xylene, ethyl acetate, heptane and n-hexane.
Preferably, in the steps S2-S4, the initiator accounts for 1-5% of the total mass of the functional monomer.
Preferably, in the steps S2-S4, the pore-forming agent accounts for 10-30% of the total mass of the functional monomer.
Preferably, in the steps S2 to S4, the ratio of the total mass of the functional monomers in the first oil phase, the second oil phase and the third oil phase is (0.1 to 10): 1.
Preferably, in the steps S2 to S4, the ratio of the total mass of the functional monomers in the first oil phase, the second oil phase, and the third oil phase is 3:2:2.
Preferably, in the step S2, the mass ratio of the functional monomers glycidyl methacrylate, N-vinyl pyrrolidone and divinylbenzene is 1:1 (4-8), more preferably 1:1:6.
Preferably, in the step S2, the chain transfer agent accounts for 0 to 5% of the total mass of the functional monomer.
Preferably, in the step S3, the mass ratio of the functional monomers glycidyl methacrylate, N-vinyl pyrrolidone and divinylbenzene is 1 (1-4): 3.
Preferably, in the step S3, the chain transfer agent accounts for 0.1 to 5% of the total mass of the functional monomer.
Preferably, in the step S4, the mass ratio of the functional monomers glycidyl methacrylate, N-vinyl pyrrolidone and divinylbenzene is (0.5-3): 1:3.
Preferably, in the step S4, the mass of the chain transfer agent is 0.1 to 5% of the total mass of the functional monomer;
preferably, in the step S5, the stirring speed is 800rpm when the first oil phase is added, 650rpm when the second oil phase is added, and 600rpm when the third oil phase is added.
Preferably, in the step S6, the selected amination reagent is one or more of diethylamine, triethylamine, dimethylamine, trimethylamine and dimethylbutylamine.
Preferably, in the step S6, the mass ratio of the white ball to the amination reagent is 1 (2-4). Further, the mass ratio of the white ball to the amination reagent is 1:3.
Preferably, the enhanced adsorbent resin material has an average particle diameter of 30 to 100 μm and a specific surface area of 400 to 1200m 2 And/g, the average pore diameter is 1-100 nm, the contact angle is less than 90 degrees, and the exchange capacity is 0.1-8 mmol/g.
The invention also provides an enhanced adsorption resin material which is prepared by the preparation method of the enhanced adsorption resin.
Preferably, the average particle diameter of the reinforced adsorbent resin material is 30-100 μm, and the specific surface area is 400-1200 m 2 And/g, the average pore diameter is 1-100 nm, the contact angle is less than 90 degrees, and the ion exchange capacity is 0.1-8 mmol/g.
The invention also provides a preparation method of the enhanced adsorption resin material and/or application of the enhanced adsorption resin material in removing PPCPs in water.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the enhanced adsorption resin material, GMA, NVP and DVB are used as functional monomers, the oil phase composed of reactants comprising the functional monomers is divided into three parts, the proportion of chain transfer agent, functional monomer and cross-linking agent is regulated and controlled according to different polymerization stages and purposes, then the polymerization reaction of the oligomer is controlled in different monomer ratios and polymerization degrees in each polymerization stage through an improved suspension polymerization process, so that after the polymerization reaction is started, a polymer chain exists in the form of the oligomer, the oligomer is composed of partial hydrophobic cross-linking agent divinylbenzene and polar monomers GMA and NVP, certain hydrophobicity is realized, micelles are formed in a water body, the hydrophobic effect enables the oligomer with small molecular weight to be continuously absorbed by larger oil drops (hydrophobic phases) in the polymerization process, and the problem that the polymerization reaction is uncontrollable due to the large polarity difference of the functional monomers is effectively avoided.
(2) According to the preparation method of the enhanced adsorption resin material, provided by the invention, the terpolymer of N-vinyl pyrrolidone, glycidyl methacrylate and divinylbenzene with a multilayer structure is prepared by controlling the oligomer in each polymerization stage according to the improved suspension polymerization process and with different monomer ratios and polymerization degrees, the ring-opening reaction of epoxy groups in a GMA structure is utilized, chloromethyl ether is not needed, ion exchange groups can be successfully grafted into the resin structure, and the anion-enhanced hydrophilic enhanced adsorption resin material is obtained through amination reaction, so that the preparation method is green and environment-friendly.
(3) The enhanced adsorption resin material provided by the invention has the characteristics of a multi-layer structure, has higher GMA content of the outer resin layer and larger aperture, effectively improves the mass transfer efficiency of the resin, and relieves the problem of pore channel blockage caused by smaller average aperture of the resin; the DVB content of the inner layer is higher, the inner layer has larger specific surface area and pore canal structure, the adsorption capacity of the resin is improved, the ion exchange capacity can be regulated and controlled by regulating the content of functional monomer GMA in the resin, the performance is stable, and the repeatability is good.
Drawings
FIG. 1 is a white ball scanning electron microscope (50 μm) prepared in example 1 of the present invention;
FIG. 2 is a white ball scanning electron microscope (10 μm) prepared in example 1 of the present invention;
FIG. 3 is an infrared spectrum of a white ball prepared in example 1 of the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments.
The terms such as "upper", "lower", "left", "right", "middle" and the like are also used in the present specification for convenience of description, and are not intended to limit the scope of the present invention, but rather to change or adjust the relative relationship thereof, and are also considered to be within the scope of the present invention without substantial change of technical content.
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 term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
As used herein, the term "about" is used to provide the flexibility and inaccuracy associated with a given term, metric or value. The degree of flexibility of a particular variable can be readily determined by one skilled in the art.
As used herein, the term "is intended to be synonymous with" one or more of ". For example, "at least one of A, B and C" expressly includes a only, B only, C only, and respective combinations thereof.
Concentrations, temperatures, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted to include not only the explicitly recited limits of 1 to about 4.5, but also include individual numbers (such as 2, 3, 4) and subranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges reciting only one numerical value, such as "less than about 4.5," which should be construed to include all such values and ranges. Moreover, such an interpretation should apply regardless of the breadth of the range or the characteristics being described.
Any steps recited in any method or process claims may be performed in any order and are not limited to the order set forth in the claims.
Example 1
The embodiment provides a preparation method of enhanced adsorption resin and an adsorption resin material prepared by the method, wherein the method comprises the following steps:
s1: preparing a disperse phase, adding 0.8g of polyvinylpyrrolidone, 0.3g of hydroxyethyl cellulose, 0.3g of gelatin and 0.15g of sodium dodecyl sulfate into 500mL of ultrapure water to serve as the disperse phase, and uniformly mixing at 60 ℃;
s2: preparing a first oil phase, and uniformly mixing 3g of glycidyl methacrylate, 3g of N-vinyl pyrrolidone, 18g of divinylbenzene, 0.96g of azobisisobutyronitrile (initiator) and 4.8g of toluene (pore-forming agent) to form the first oil phase;
s3: preparing a second oil phase, uniformly mixing 3.2g of glycidyl methacrylate, 3.2g of N-vinyl pyrrolidone, 9.6g of divinylbenzene, 0.64g of azobisisobutyronitrile (initiator), 0.64g of S, S ' -bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate (chain transfer agent), 0.64g of methyl (phenyl) amino dithioformate (chain transfer agent) and 4.8g of toluene (porogen);
s4: preparing a third oil phase, uniformly mixing 5.33g of glycidyl methacrylate, 2.67g of N-vinyl pyrrolidone, 8g of divinylbenzene, 0.64g of azobisisobutyronitrile (initiator), 0.53 g of S, S ' -bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate (chain transfer agent), 1.066g of methyl (phenyl) amino dithioformate (chain transfer agent) and 4.8g of toluene (porogen);
s5: preparing white balls, namely raising the temperature of a disperse phase system to 80 ℃, dropwise adding a first oil phase into the disperse phase to react for 1h, and maintaining the stirring speed at 800rpm; dropping the system temperature from 80 ℃ to 60 ℃, dropwise adding and prepolymerizing the second oil phase for 30min, then heating the system to 80 ℃ for reaction for 1h, and maintaining the stirring speed at 650rpm; after the temperature of the system is reduced to 60 ℃, dropwise adding and prepolymerizing the third oil phase for 30min, and then heating the system to 80 ℃ for reaction for 3h to obtain a finished white ball, wherein the stirring speed is maintained at 600rpm;
s6: preparing a functional resin material, adding a certain amount of white balls into trimethylamine according to the mass ratio of 1:3, and reacting for 24 hours at 60 ℃ and 400rpm to obtain the enhanced adsorption resin material.
The white ball scanning electron microscope images prepared in the embodiment are shown in fig. 1 and 2, the microsphere surface is rough, the pore-forming is good, and mass transfer of substances on the microsphere surface is facilitated; as shown in FIG. 3, the white ball infrared spectrogram shows that the GMA-NVP-DVB terpolymer has obvious characteristic peaks at 1733.7 and 1687.4, and the expansion vibration of C=O group in glycidyl acrylate between 1770 and 1720 and the expansion vibration of C=O group in NVP between 1700 and 1630 show that the terpolymer is formed; the element analysis result shows that the N element content of the white ball is 0.91%; the obtained reinforced adsorption resin material is further characterized: the static contact angle is 74.54 degrees, the ion exchange capacity is 2.26mmol/g, the particle size distribution is 30-60 mu m, and the specific surface area is 854m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 2
The present example provides a method for preparing an enhanced adsorption resin and an adsorption resin material prepared by the method, and other conditions are the same as those of the preparation method in example 1, except that the proportion of the monomer in the third oil phase is adjusted, and the monomer proportion and the resin characterization result are shown in table 1.
Table 1 third oil phase monomer formulation and resin characterization results
Example 3
The reinforced adsorbent resin was prepared in this example under the same conditions as in example 1, except that in the first oil phase, the amount of added chain transfer agent S, S '-bis (α, α' -dimethyl- α "-acetic acid) trithiocarbonate was 0.2g and the amount of added methyl (phenyl) amino dithioformate was 0.2g.
The content of N element in the white ball prepared by the method is 0.93%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 77.31 DEG, the ion exchange capacity is 1.68mmol/g, the particle size distribution is 30-100 mu m, and the specific surface area is 797m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 4
The enhanced adsorbent resin was prepared in this example under the same conditions as in example 1, except that in the second oil phase, the chain transfer agent was S, S '-bis (α, α' -dimethyl- α "-acetic acid) trithiocarbonate and 2- (dodecylthiocarbonylthio) -2-methylpropanoic acid in amounts of 0.64g and 0.64g, respectively.
The content of N element in the white ball prepared by the method is 0.64%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 80.94 DEG, the ion exchange capacity is 1.81mmol/g, the particle size distribution is 30-100 mu m, and the specific surface area is 777m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 5
The enhanced adsorbent resin was prepared in this example under the same conditions as in example 1, except that in the second oil phase, the chain transfer agent was S, S '-bis (α, α' -dimethyl- α "-acetic acid) trithiocarbonate and 4-cyano-4- [ [ (dodecylthio) thiocarbonyl ] thio ] pentanoic acid in amounts of 0.64g and 0.64g, respectively.
The content of N element in the white ball prepared by the method is 0.74%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 75.4 degrees, the ion exchange capacity is 1.71mmol/g, the particle size distribution is 30-100 mu m, and the specific surface area is 711m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 6
The reinforced adsorbent resin was prepared in this example under the same conditions as in example 1, except that in the second oil phase, the chain transfer agent was bis (thiobenzoyl) disulfide and cyanomethyl methyl (phenyl) aminodithioformate in the amounts of 0.56g and 0.56g, respectively.
The content of N element in the white ball prepared by the method is 0.45%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 76.81 degrees, the ion exchange capacity is 1.8mmol/g, the particle size distribution is 30-100 mu m, and the specific surface area is 871m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 7
The enhanced adsorbent resin was prepared in this example under the same conditions as in example 1, except that in the third oil phase, the chain transfer agent was S, S '-bis (α, α' -dimethyl- α "-acetic acid) trithiocarbonate and 2- (dodecylthiocarbonylthio) -2-methylpropanoic acid in amounts of 0.533g and 1.066g, respectively.
The content of N element in the white ball prepared by the method is 0.69%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 86.18 DEG, the ion exchange capacity is 1.12mmol/g, the particle size distribution is 30-100 mu m, and the specific surface area is 814m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 8
The enhanced adsorbent resin was prepared in this example under the same conditions as in example 1, except that in the third oil phase, the chain transfer agent was S, S '-bis (α, α' -dimethyl- α "-acetic acid) trithiocarbonate and 4-cyano-4- [ [ (dodecylthio) thiocarbonyl ] thio ] pentanoic acid in amounts of 0.533g and 1.066g, respectively.
The content of N element in the white ball prepared by the method is 0.82%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 77.24 DEG, the ion exchange capacity is 1.49mmol/g, the particle size distribution is 30-100 mu m, and the specific surface area is 864m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 9
The enhanced adsorbent resin was prepared in this example under the same conditions as in example 1, except that in the third oil phase, the chain transfer agent was bis (thiobenzoyl) disulfide and cyanomethyl methyl (phenyl) aminodithioformate in the amounts of 0.533g and 1.066g, respectively.
The content of N element in the white ball prepared by the method is 0.76%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 86.18 DEG, the ion exchange capacity is 1.74mmol/g, the particle size distribution is 30-100 mu m, and the specific surface area is 752m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 10
The enhanced adsorbent resin was prepared in this example, except that the third oil phase consisted of 2.67g glycidyl methacrylate, 1.33g N-vinylpyrrolidone, 4g divinylbenzene, 0.32g azobisisobutyronitrile (initiator), 0.267g S, S ' -bis (α, α ' -dimethyl- α ' -acetic acid) trithiocarbonate (chain transfer agent), 0.533g cyanomethyl methyl (phenyl) aminodithioformate (chain transfer agent), 2.4g toluene (porogen) as in example 1.
The content of N element in the white ball prepared by the method is 0.64%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 83.31 degrees, the ion exchange capacity is 1.91mmol/g, the particle size distribution is 30-100 mu m, and the specific surface area is 848m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 11
The enhanced adsorbent resin was prepared in this example, except that the preparation method was the same as in example 1, except that the prepolymerization time after the addition of the second oil phase to the system was 60min; the prepolymerization time after the third oil phase is added into the system is 60min. After the temperature of the disperse phase system is raised to 80 ℃, the first oil phase is added into the disperse phase dropwise for reaction for 1h, and the stirring speed is maintained at 100-1000 rpm; dropping the system temperature from 80 ℃ to 60 ℃, dropwise adding and prepolymerizing the second oil phase for 60min, then heating the system to 80 ℃ for reaction for 1h, and maintaining the stirring speed at 100-1000 rpm; after the temperature of the system is reduced to 60 ℃, dropwise adding and prepolymerizing the third oil phase for 60min, and then heating the system to 80 ℃ for reaction for 3h to obtain the finished white ball, wherein the stirring speed is maintained to be 100-1000 rpm.
The content of N element in the white ball prepared by the method is 0.55%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 77.1 DEG, the ion exchange capacity is 1.88mmol/g, the particle size distribution is 30-60 mu m, and the specific surface area is 603m 2 And/g, wherein the pore size distribution is 1-100 nm.
Example 12
The enhanced adsorbent resin was prepared in this example, except that the preparation method was the same as in example 1, except that the prepolymerization time after the addition of the second oil phase to the system was 120min; the prepolymerization time after the third oil phase is added into the system is 120min.
The content of N element in the white ball prepared by the method is 0.71%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 84.28 DEG, the ion exchange capacity is 1.39mmol/g, the particle size distribution is 30-60 mu m, and the specific surface area is 598m 2 And/g, wherein the pore size distribution is 1-100 nm.
Comparative example 1
The reinforced adsorbent resin was prepared in this example, except that only the first oil phase was added and the second and third oil phases were not added, as in the preparation method in example 1.
The content of N element in the white ball prepared by the method is 0.16%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 99.17 degrees, the ion exchange capacity is 0.1mmol/g, the particle size distribution is 1-30 mu m, and the specific surface area is 1183m 2 And/g, the pore size distribution is 1-10 nm. The contact angle of the resin material is larger, the hydrophilicity is insufficient, and the resin is judged to be mainly formed by self-polymerization of a hydrophobic monomer DVB. Meanwhile, the resin material of the target particle size distribution and the pore size distribution is not obtained, and the polymerization fails.
Comparative example 2
The reinforced adsorbent resin was prepared in this example, except that only the first oil phase and the second oil phase were added and the third oil phase was not added, as in the preparation method in example 1.
The white ball N-element prepared by the methodThe content of the element is 0.63%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 83.61 DEG, the ion exchange capacity is 0.31mmol/g, the particle size distribution is 1-30 mu m, and the specific surface area is 891m 2 And/g, the pore size distribution is 1-10 nm. The particle size distribution and the pore size distribution of the resin material are unexpected, and the polymerization fails.
Comparative example 3
The enhanced adsorbent resin was prepared in this example, except that no chain transfer agent was added to the second oil phase, under the same conditions as in the preparation method of example 1.
The content of N element in the white ball prepared by the method is 0.21%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 101.22 DEG, the ion exchange capacity is 0.07mmol/g, the particle size distribution is 1-30 mu m, and the specific surface area is 1100m 2 And/g, the pore size distribution is 1-10 nm. The contact angle of the resin is larger, the hydrophilicity is insufficient, the resin is judged to be mainly formed by self-polymerization of a hydrophobic monomer DVB, and functional monomers NVP and GMA do not fully participate in the reaction and the polymerization fails.
Comparative example 4
The enhanced adsorbent resin was prepared in this example, except that no chain transfer agent was added to the third oil phase, under the same conditions as in the preparation method of example 1.
The content of N element in the white ball prepared by the method is 0.68%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 93.71 degrees, the ion exchange capacity is 0.55mmol/g, the particle size distribution is 1-50 mu m, and the specific surface area is 900m 2 And/g, the pore size distribution is 1-10 nm. It was judged that the resin was copolymerized mainly from DVB and partially hydrophilic monomer NVP, GMA did not fully participate in the reaction, the hydrophilicity was poor, the particle size distribution was unexpected, and the polymerization failed.
Comparative example 5
The enhanced adsorbent resin was prepared in this example, except that no chain transfer agent was added to both the second oil phase and the third oil phase, under the same conditions as in the preparation method of example 1.
The content of N element in the white ball prepared by the method is 0.14%;the resulting enhanced adsorbent resin was further characterized: the static contact angle is 96.33 DEG, the ion exchange capacity is 0.13mmol/g, the particle size distribution is 1-30 mu m, and the specific surface area is 1037m 2 And/g, the pore size distribution is 1-10 nm. The contact angle of the resin is larger, the hydrophilicity is insufficient, the resin is judged to be mainly formed by self-polymerization of a hydrophobic monomer DVB, and functional monomers NVP and GMA do not fully participate in the reaction and the polymerization fails.
Comparative example 6
The enhanced adsorbent resin was prepared in this example, except that no functional monomer GMA was added to each of the first oil phase, the second oil phase and the third oil phase, under the same conditions as in the preparation method of example 1.
The content of N element in the white ball prepared by the method is 0.74%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 78.49 DEG, the ion exchange capacity is 0.06mmol/g, the particle size distribution is 1-50 mu m, and the specific surface area is 810m 2 And/g, the pore size distribution is 1-10 nm. The ionic capacity of the resin material is low and the target pore size distribution and particle size distribution cannot be obtained, and polymerization fails.
Comparative example 7
The reinforced adsorbent resin was prepared in this example, except that the second oil phase and the third oil phase were not prepolymerized at 60℃but were directly heated to 80℃for reaction, after the addition of the second oil phase and the third oil phase, respectively, in the same manner as in example 1.
The content of N element in the white ball prepared by the method is 0.24%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 97.59 DEG, the ion exchange capacity is 0.18mmol/g, the particle size distribution is 1-50 mu m, and the specific surface area is 920m 2 And/g, the pore size distribution is 1-10 nm. The contact angle of the resin is larger, the hydrophilicity is insufficient, the resin is judged to be mainly formed by self-polymerization of a hydrophobic monomer DVB, and functional monomers NVP and GMA do not fully participate in the reaction and the polymerization fails.
Comparative example 8
The enhanced adsorbent resin was prepared in this example, except that the preparation method of the white ball in example 1 was the same, except that the prepolymerization was performed at a temperature of 70℃after the addition of the second oil phase and the third oil phase, respectively.
The content of N element in the white ball prepared by the method is 0.34%; the resulting enhanced adsorbent resin was further characterized: the static contact angle is 94.67 DEG, the ion exchange capacity is 1.27mmol/g, the particle size distribution is 1-100 mu m, and the specific surface area is 310m 2 And/g, the pore size distribution is 1-50 nm. The particle size distribution of the resin is too dispersed, the hydrophilicity is insufficient, the specific surface area is small, and the ion exchange capacity is less and the polymerization fails.
The above description of the invention and its embodiments has been given by way of illustration and not limitation, and the examples shown are merely examples of embodiments of the invention, without limitation to the actual embodiments. According to the reagent and proportion in the technical scheme, for example, the consumption of the dispersing agent in the disperse phase is 0.1-5% of the mass of the ultrapure water, and the consumption of the emulsifying agent is 0.01-2% of the mass of the ultrapure water; the mass ratio of the glycidyl methacrylate, the N-vinyl pyrrolidone and the divinylbenzene in the first oil phase is 1:1 (0.1-10), the chain transfer agent accounts for 0-10% of the total mass of the functional monomers, the initiator accounts for 1-20% of the total mass of the functional monomers, and the pore-forming agent accounts for 1-30% of the total mass of the functional monomers; the mass ratio of the functional monomer glycidyl methacrylate, N-vinyl pyrrolidone and divinylbenzene in the second oil phase is 1 (0.1-10): 3, the chain transfer agent accounts for 0.1-10% of the total mass of the functional monomers, the initiator accounts for 1-20% of the total mass of the functional monomers, and the pore-forming agent accounts for 1-30% of the total mass of the functional monomers; the mass ratio of the functional monomer glycidyl methacrylate, N-vinyl pyrrolidone and divinylbenzene in the third oil phase is (0.1-10) 1:3, the chain transfer agent accounts for 0.1-10% of the total mass of the functional monomers, the initiator accounts for 1-20% of the total mass of the functional monomers, and the pore-forming agent accounts for 1-30% of the total mass of the functional monomers; the ratio of the total mass of the functional monomers in the first oil phase, the second oil phase and the third oil phase is (0.1-10): 1; the dispersing agent is one or more of polyethylene glycol, sodium hexametaphosphate, liquid paraffin, polyvinylpyrrolidone and hydroxyethyl cellulose; the emulsifying agent is acacia, gelatin, tween 80,One or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and fatty acid soap; the chain transfer agent is S, S ' -di (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate, methyl (phenyl) amino dithiomethyl formate, 2- (dodecyl thio-carbonyl thio) -2-methylpropanoic acid, 4-cyano-4 [ (dodecyl thio) thiocarbonyl]Thio group]One or more of valeric acid and bis (thiobenzoyl) disulfide; the initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, dibenzoyl peroxide, benzoyl peroxide and ammonium persulfate; the pore-forming agent is one or more of toluene, xylene, ethyl acetate, heptane and n-hexane; the amination reagent is one or more of diethylamine, triethylamine, dimethylamine, trimethylamine and dimethylbutylamine; when the mass ratio of the white ball to the amination reagent is 1 (2-4), the white ball can be prepared to have the average grain diameter of 30-100 mu m and the specific surface area of 400-1200 m 2 And/g, the average pore diameter is 1-100 nm, the contact angle is less than 90 degrees, and the exchange capacity is 0.1-8 mmol/g. Therefore, if one of ordinary skill in the art is informed by this disclosure, embodiments and examples similar to the technical solution are not creatively devised without departing from the gist of the present invention, and all the embodiments and examples are considered to be within the protection scope of the present invention.

Claims (10)

1. The preparation method of the enhanced adsorption resin material is characterized by comprising the following steps:
s1: preparing a disperse phase, adding a dispersing agent and an emulsifying agent into ultrapure water, and uniformly mixing, wherein the dosage of the dispersing agent is 0.1-5% of the mass of the ultrapure water, and the dosage of the emulsifying agent is 0.01-2% of the mass of the ultrapure water;
s2: preparing a first oil phase, and uniformly mixing functional monomers of glycidyl methacrylate, N-vinyl pyrrolidone, divinylbenzene, a chain transfer agent, an initiator and a pore-forming agent, wherein the mass ratio of the functional monomers of glycidyl methacrylate to N-vinyl pyrrolidone to the divinylbenzene is 1:1 (0.1-10), the mass of the chain transfer agent accounts for 0-10% of the total mass of the functional monomers, the mass of the initiator accounts for 1-20% of the total mass of the functional monomers, and the pore-forming agent accounts for 1-30% of the total mass of the functional monomers;
s3: preparing a second oil phase, and uniformly mixing functional monomer glycidyl methacrylate, N-vinyl pyrrolidone, cross-linking agent divinylbenzene, chain transfer agent, initiator and pore-forming agent, wherein the mass ratio of the functional monomer glycidyl methacrylate to the N-vinyl pyrrolidone to the divinylbenzene is 1 (0.1-10): 3, the mass of the chain transfer agent accounts for 0.1-10% of the total mass of the functional monomer, the mass of the initiator accounts for 1-20% of the total mass of the functional monomer, and the pore-forming agent accounts for 1-30% of the total mass of the functional monomer;
s4: preparing a third oil phase, and uniformly mixing functional monomer glycidyl methacrylate, N-vinyl pyrrolidone, cross-linking agent divinylbenzene, chain transfer agent, initiator and pore-forming agent, wherein the mass ratio of the functional monomer glycidyl methacrylate to the N-vinyl pyrrolidone to the divinylbenzene is (0.1-10): 1:3, the mass of the chain transfer agent accounts for 0.1-10% of the total mass of the functional monomer, the mass of the initiator accounts for 1-20% of the total mass of the functional monomer, and the pore-forming agent accounts for 1-30% of the total mass of the functional monomer;
s5: preparing white balls, heating the disperse phase to 60+/-2 ℃, adding the first oil phase under the stirring of 100-1000 rpm, and heating to 80 ℃ for reaction for 1h; cooling to 60+/-2 ℃, adding a second oil phase under stirring at 100-1000 rpm, prepolymerizing for 20-120 min, and heating to 80+/-2 ℃ for reaction for 1h; cooling to 60+/-2 ℃, adding a third oil phase under the stirring of 100-1000 rpm, pre-polymerizing for 20-120 min, and then heating to 80+/-2 ℃ for reaction for 3h to obtain white balls, wherein the temperatures are the temperature of a reaction system and not the temperature of a heating system;
s6: the white balls prepared in the step S5 are added into an amination reagent to react for 4 to 24 hours at the reaction temperature of 55 to 100 ℃ and the stirring speed of 400 to 1000rpm, so as to obtain the enhanced adsorption resin material with the ion exchange function.
2. A method for producing an enhanced adsorbent resin material according to claim 1, wherein,
the emulsifier in the step S1 is one or more of acacia, gelatin, tween 80, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and fatty acid soap;
and/or the dispersing agent in the step S1 is one or more of polyethylene glycol, sodium hexametaphosphate, liquid paraffin, polyvinylpyrrolidone and hydroxyethyl cellulose;
and/or the initiator in the steps S2 to S4 is one or more of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, dibenzoyl peroxide, benzoyl peroxide and ammonium persulfate;
and/or the chain transfer agent in the steps S2-S4 is one or more of S, S ' -bis (alpha, alpha ' -dimethyl-alpha ' -acetic acid) trithiocarbonate, methyl (phenyl) amino dithiomethyl formate, 2- (dodecyl thio carbonyl thio) -2-methylpropanoic acid, 4-cyano-4- [ [ (dodecyl thio) thio carbonyl ] thio ] pentanoic acid and bis (thio benzoyl) disulfide;
and/or the pore-forming agent in the steps S2 to S4 is one or more of toluene, xylene, ethyl acetate, heptane and n-hexane;
and/or the amination reagent in the step S6 is one or more of diethylamine, triethylamine, dimethylamine, trimethylamine and dimethylbutylamine.
3. The method for preparing an enhanced adsorbent resin material according to claim 1 or 2, wherein in the step S1, the dispersant is used in an amount of 0.1% to 4% of the mass of ultrapure water; and/or in the steps S2-S4, the initiator accounts for 1-5% of the total mass of the functional monomer; and/or in the steps S2-S4, the pore-forming agent accounts for 10-30% of the total mass of the functional monomer.
4. The method for producing an enhanced adsorbent resin material according to claim 3, wherein in steps S2 to S4, the ratio of the total mass of the functional monomers in the first oil phase, the second oil phase and the third oil phase is (0.1 to 10): 1.
5. The method of preparing an enhanced adsorbent resin material according to claim 4, wherein in steps S2 to S4, the ratio of the total mass of the functional monomers in the first oil phase, the second oil phase, and the third oil phase is 3:2:2.
6. The method for preparing an enhanced adsorbent resin material according to claim 5, wherein in the step S2, the mass ratio of the functional monomers glycidyl methacrylate, N-vinylpyrrolidone and divinylbenzene is 1:1 (4-8);
and/or in the step S3, the mass ratio of the functional monomers glycidyl methacrylate, N-vinyl pyrrolidone and divinylbenzene is 1 (1-4): 3;
and/or in the step S4, the mass ratio of the functional monomers glycidyl methacrylate, N-vinyl pyrrolidone and divinylbenzene is (0.5-3) 1:3.
7. The method of producing an enhanced adsorbent resin material according to claim 6, wherein in said step S6, the mass ratio of white balls to aminating agent is 1 (2-4).
8. The method for producing an enhanced adsorbent resin material according to claim 7, wherein said enhanced adsorbent resin material has an average particle diameter of 30 to 100. Mu.m, and a specific surface area of 400 to 1200. Mu.m 2 And/g, the average pore diameter is 1-100 nm, the contact angle is less than 90 degrees, and the ion exchange capacity is 0.1-8 mmol/g.
9. A reinforced adsorbent resin material, characterized in that it is prepared by a method according to any one of claims 1 to 8.
10. A method of preparing an enhanced adsorbent resin material according to any one of claims 1-8 or the use of an enhanced adsorbent resin material according to claim 9 for removing PPCPs from a body of water.
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