CN114230821A - Carboxyl functionalized super-crosslinked polymer and preparation method and application thereof - Google Patents

Carboxyl functionalized super-crosslinked polymer and preparation method and application thereof Download PDF

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CN114230821A
CN114230821A CN202111622765.5A CN202111622765A CN114230821A CN 114230821 A CN114230821 A CN 114230821A CN 202111622765 A CN202111622765 A CN 202111622765A CN 114230821 A CN114230821 A CN 114230821A
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黄健涵
舒哲
王悠
王立志
周发
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Central South University
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Abstract

The invention discloses a preparation method of carboxyl functionalized hypercrosslinked polymer, which comprises the following steps of carrying out nucleophilic substitution reaction on chloromethylated polystyrene microspheres and aromatic carboxylic acid monomers in an alkaline environment to obtain carboxylated polystyrene microspheres; the carboxylated polystyrene microsphere and the cross-linking agent are subjected to Friedel-Crafts reaction under the action of an acid catalyst to obtain the carboxyl functionalized super cross-linked polymer. The method can realize the regulation and control of the pore structure size of the hypercrosslinked polymer, form a large number of micropores, endow the hypercrosslinked polymer with a unique pore structure, and effectively regulate the polarity of the hypercrosslinked polymer, so that the hypercrosslinked polymer has a high selective adsorption effect on polar aromatic micromolecules in a water body, and is easy to elute after adsorption and reusable.

Description

Carboxyl functionalized super-crosslinked polymer and preparation method and application thereof
Technical Field
The invention relates to an adsorption material, in particular to a carboxyl functionalized super-crosslinked polymer, and also relates to a preparation method of the carboxyl functionalized super-crosslinked polymer and application of the carboxyl functionalized super-crosslinked polymer in adsorption of polar aromatic organic small molecules in water, belonging to the technical field of synthesis of the functionalized super-crosslinked polymer.
Background
The method for treating the organic wastewater mainly comprises a solvent extraction method, an electrochemical method, a biological treatment method, an adsorption method and the like. The solvent extraction method is generally suitable for treating high-concentration organic wastewater, but is not suitable for use when the content is low, and the used extracting agent is easy to run off, the loss is serious, and the treatment effect is poor; the electrochemical method has high energy consumption and high operating cost; the biological treatment method has incomplete treatment and long process consumption, and particularly, organic pollutants (benzene rings) cannot be effectively removed by the biological method; the solid adsorbent is used for adsorbing aromatic organic matters in water, and is considered to be an effective method due to the advantages of wide application range, low cost, simple and convenient operation, good adsorption effect, high selectivity, stable performance and the like. And it has been widely used in various fields such as metallurgy, chemical industry, medicine and environment. The commonly used solid adsorbent comprises zeolite, mesoporous silica, porous carbon, a metal organic framework and a porous organic polymer, can be used for treating wastewater containing phenol, aniline, organic acid, nitro-compound and the like, and is an effective method for treating organic wastewater. In recent years, the development and research of new porous adsorbents have been rapidly developed.
Hypercrosslinked polymers (HCPs) are due to their higher S contentBETThe adsorbent has the excellent characteristics of large specific surface area, abundant micropores, high repeated utilization rate, higher adsorption performance and the like, and is a high-efficiency adsorbent for removing pollutants in water. In 1969, Davankov first proposed the concept of hypercrosslinked polymers under the action of Lewis acid catalystsHCPs are prepared by high density crosslinking of adjacent benzene rings in linear or low crosslinked polystyrene polymer chains using different external crosslinkers in a suitable solvent by a Friedel-Crafts reaction. In 2006, the Sherrington research group further developed this technology, and they introduced p-vinylbenzyl chloride into this polymer, resulting in a pore structure distribution with a unique range from micropores to macropores. In recent years, due to the characteristics of simple and efficient synthesis method, easy functionalization, low cost, mild synthesis conditions, adjustable pore structure and the like, the hypercrosslinked polymer is widely applied to the fields related to energy and environment, such as natural gas storage, carbon capture, pollutant removal, molecular separation, catalysis, drug delivery and the like. There are also a number of reports of hypercrosslinked polymers on the adsorption of organic contaminants. For example, Kuang et al prepared phenol-modified hypercrosslinked polymers with all micropores/mesopores by Friedel-Crafts alkylation using macroporous low cross-linked chloromethylated polystyrene microspheres, and added phenol in different amounts during the reaction to accurately control the functionalized polarity of these polymers, which have good adsorption properties to aniline. Wang et al first utilize chlorine ball self-crosslinking to form a hypercrosslinked polymer, then utilize hexamethylenetetramine and aniline to functionalize the polymer, introduce amino groups to increase the polarity, thus facilitating the absorption of salicylic acid. However, the materials have the problems of low content of functional groups and uncontrollable property in the using process, so that the adsorption quantity of the organic pollutants is small and the selectivity is low. Polar aromatic organic matters (such as 2, 2' -dihydroxybiphenyl, 1, 5-dihydroxynaphthalene, aniline and the like) which can also carry out Friedel-Crafts alkylation reaction with the chlorine ball are introduced into the Friedel-Crafts alkylation reaction, but the Friedel-Crafts alkylation reaction of the chlorine ball and the polar aromatic organic matters is competitive with the Friedel-Crafts alkylation reaction of the chlorine ball; because the Friedel-Crafts alkylation reaction of the chlorine ball belongs to the similar intramolecular reaction, the amount of the polar aromatic organic matters introduced is not high, and the content of the functional groups is low (less than 5 percent); moreover, since Friedel-Crafts alkylation reaction is not controllable, the content of functional groups loaded on the backbone of the hypercrosslinked polymer obtained after the reaction is also not controllable. By means of post-modificationPolar group modified hypercrosslinked polymers are obtained, but the post-modification methods are limited and are all based on reaction with residual chlorine, which tends to make the previously prepared hypercrosslinked polymers low in specific surface area and lose the advantage of unique pore structure. Therefore, by controlling the reaction conditions, on the premise of ensuring the unique advantages of the pore structure of the existing hypercrosslinked polymer, the content of functional groups on the skeleton structure is increased, and the hypercrosslinked polymer with high specific surface area and high functional group content is synthesized at low cost, which becomes one of the important problems to be solved by materials scientists and chemists at present, and will effectively promote the application of the hypercrosslinked polymer in the aspect of pollutant adsorption, thus having a great development prospect.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the present invention is to provide a carboxyl functionalized hypercrosslinked polymer with a carboxyl functionalized modification and a special pore structure, wherein the hypercrosslinked polymer shows a high selective adsorption capacity to polar aromatic organic small molecules containing hydrogen bond donors with relatively large molecular sizes through the synergistic effect of the modified carboxyl functional groups and the special pore structure, and overcomes the defects of the hypercrosslinked polymer reported in the prior art that the adsorption effect and the selectivity to polar organic small molecule pollutants (aniline, phenol, salicylic acid, etc.) are not ideal.
The second purpose of the invention is to provide a preparation method of the carboxyl functionalized hypercrosslinked polymer, which can realize the arbitrary regulation and control of carboxyl modification and pore structure, so that the preparation method meets the adsorption application requirements of aromatic micromolecules with different polarities, has simple and convenient operation and low cost, and can meet the industrial production.
The invention aims to provide the application of the carboxyl functionalized super-crosslinked polymer in adsorbing polar aromatic organic micromolecules in water, particularly has selective adsorption effect on aniline, phenol, salicylic acid and the like, is easy to elute after adsorbing the polar aromatic micromolecules, can be repeatedly used for many times, and has good repeated use effect.
In order to achieve the above technical objects, the present invention provides a method for preparing a carboxyl-functionalized hypercrosslinked polymer, comprising the steps of:
1) performing nucleophilic substitution reaction on chloromethylated polystyrene microspheres and aromatic carboxylic acid monomers in an alkaline environment to obtain carboxylated polystyrene microspheres;
2) the carboxylated polystyrene microsphere and the cross-linking agent are subjected to Friedel-Crafts reaction under the action of an acid catalyst to obtain the carboxyl functionalized super cross-linked polymer.
The functionalized hypercrosslinked polymer in the prior art has certain adsorbability to aniline, phenol, salicylic acid and the like, but has the defects of small adsorbability, slow adsorption balance, poor selectivity and the like, mainly because the functionalized degree of polarity is limited and is difficult to regulate and control, so that the adsorption selectivity is poor, and the surface area and the pore volume are low, so that the adsorbability is low. The uncontrollable synthesis process of the functionalized hypercrosslinked polymer in the prior art causes the uneven pore distribution and the uncontrollable structure of the hypercrosslinked polymer, and the post-modification process of the polar functional group causes the limited modification of the polar group, the effect is not ideal enough, and the hypercrosslinked polymer with high selectivity and high adsorption capacity is difficult to obtain. The key point of the technical scheme of the invention is that macroporous resin chloromethylated polystyrene microspheres with low crosslinking degree are used as matrix resin to carry out polarity modification and pore structure regulation, residual chlorine in the chloromethylated polystyrene microspheres is firstly utilized to graft and modify carboxyl, modification before crosslinking can greatly improve modification amount of the carboxyl, defects of post-functional modification of porous polymers can be effectively avoided, and the quantity of carboxyl functional groups in carboxyl functional hypercrosslinked polymers can be regulated and controlled only by controlling reaction conditions and selection of aromatic carboxylic acid monomer types, on the basis, crosslinking agents are further introduced from the outside and residual chloromethyl in the carboxylated polystyrene microspheres is utilized to further crosslink, thus realizing regulation and control of the pore structure, and the crosslinking process can also be regulated and controlled by reaction conditions, thereby effectively adjusting the polarity and the pore structure of the carboxyl functionalized hypercrosslinked polymer.
The key point of the technical scheme of the invention is to carry out nucleophilic substitution and then Friedel-Crafts reaction, the chloromethyl contained in the chloromethylated polystyrene microsphere can participate in intramolecular Friedel-Crafts reaction, the nucleophilic substitution is carried out firstly, most chloromethyl is mainly used for grafting modified carboxyl to avoid participating in subsequent Friedel-Crafts reaction, and if excessive chloromethyl participates in intramolecular crosslinking, a crosslinking compact zone is easy to generate, which is not beneficial to improving the adsorption performance of carboxyl functionalized super-crosslinked polymer.
In a preferred embodiment, the aromatic carboxylic acid monomer is at least one of benzoic acid, phthalic acid, trimesic acid, 3, 5-dihydroxybenzoic acid, and 3,4, 5-trihydroxybenzoic acid. The positions and the number of carboxyl groups contained in the aromatic carboxylic acid monomers are different, and the polarity and the pore structure of the carboxyl functionalized super-crosslinked polymer can be effectively regulated and controlled by selecting different aromatic carboxylic acid monomers or combining and matching several aromatic carboxylic acid monomers.
As a preferable embodiment, the molar ratio of the chloromethylated polystyrene microsphere to the aromatic carboxylic acid monomer is measured by that the molar ratio of the carboxyl content in the aromatic carboxylic acid monomer to the chlorine content in the chloromethylated polystyrene microsphere is 1:1 to 1: 3. The content of chloromethyl in chloromethylated polystyrene microsphere determines the highest modification amount of carboxylic acid, and the controllable adjustment of carboxyl modification amount can be realized by adjusting the molar ratio of chloromethylated polystyrene microsphere and aromatic carboxylic acid monomer in a proper range.
As a preferred embodiment, the conditions of the nucleophilic substitution reaction are: reacting for 12-36 h at 80-100 ℃. The high-efficiency nucleophilic substitution reaction between the aromatic carboxylic acid monomer and the chloromethylated polystyrene microsphere can be realized under the preferable reaction condition. The nucleophilic substitution reaction is carried out under an alkaline condition, the alkaline environment is favorable for promoting the nucleophilic substitution reaction to be smoothly carried out, hydrogen chloride micromolecules can be removed in the reaction process, and acid generated in the reaction can be neutralized in the alkaline environment. As a preferred variant, the nucleophilic substitution reaction is effected predominantly by addition of K2CO3、Na2CO3And Cr2CO3At least one of (a) and (b) is such that the reaction is carried out in an alkaline environment, wherein K2CO3、Na2CO3And Cr2CO3The molar ratio of the amount of the chlorine to the chlorine content in the chloromethylated polystyrene is 1: 1.
In a preferred embodiment, the crosslinking agent is at least one of cyanuric chloride, dimethoxymethane, 1, 4-p-dichlorobenzyl, and 4, 4-bis (chloromethyl) -1, 1-biphenyl. The cross-linking agent is mainly used for cross-linking benzene rings in the carboxylated polystyrene microspheres and adjusting the pore structure of the carboxylated polystyrene microspheres.
As a preferred embodiment, the acid catalyst comprises a lewis acid and/or a protonic acid. As a more preferred scheme, the Lewis acid is FeCl3、AlCl3And SnCl4At least one of them. As a more preferred embodiment, the protonic acid is H2SO4And HCl. The acid catalyst is a catalyst commonly used in the Friedel-Crafts reaction process. In a more preferable embodiment, the mass of the cross-linking agent is 50-250% of the mass of the carboxylated polystyrene microspheres. In a more preferable embodiment, the mass of the lewis acid is 100% to 150% of the mass of the carboxylated polystyrene microsphere. In a more preferable embodiment, the mass of the protonic acid is 50% to 100% of the mass of the carboxylated polystyrene microsphere. The crosslinking degree of the carboxyl functionalized super-crosslinked polymer can be effectively regulated and controlled by controlling the dosage of the acid catalyst and the dosage of the crosslinking agent, so that the regulation and control of the microporous structure of the carboxyl functionalized super-crosslinked polymer are realized.
As a preferred scheme, the conditions of the Friedel-Crafts reaction are as follows: reacting for 12-36 h at the temperature of 80-90 ℃. Under the condition of selecting proper acid catalyst dosage and cross-linking agent dosage, the condition of Friedel-Crafts reaction is further controlled, and the cross-linking degree of the carboxyl functionalized super cross-linked polymer can be effectively regulated and controlled. The solvent used in the Friedel-Crafts reaction is dichloroethane.
Before nucleophilic substitution reaction, the chloromethylated polystyrene microsphere is subjected to swelling pretreatment by using a benign solvent, so that chloromethyl in the chloromethylated polystyrene microsphere can be fully exposed, and nucleophilic substitution reaction of chloromethyl in the chloromethylated polystyrene microsphere is facilitated.
Before Friedel-Crafts reaction, the carboxylated polystyrene microspheres are swelled by a benign solvent to fill the inside of the carboxylated polystyrene microspheres with the solvent to reach an adsorption saturation state, and then are crosslinked under the condition of full swelling, so that a compact crosslinking area generated by internal transitional crosslinking of the carboxylated polystyrene microspheres can be avoided, and a large number of microporous structures can be formed.
The invention also provides a carboxyl functionalized hypercrosslinked polymer which is obtained by the preparation method.
As a preferable scheme, the specific surface area of the carboxyl functionalized hypercrosslinked polymer is 123-478 m2A pore volume of 0.27 to 0.53cm3(ii)/g, the average pore diameter is 2.8 to 11 nm. Before Friedel-Crafts reaction, the chlorine content in the carboxylated polystyrene microspheres is 0.32-0.88 mmol/g, and S isBETThe specific surface area is 14-64 m2Per g, pore volume of 0.17-0.29 cm3The average pore diameter is 18.0-25.7 nm, and the pore structure of the carboxyl functionalized super-crosslinked polymer obtained by Friedel-Crafts reaction is obviously changed, so that the specific surface area is improved, the pore diameter is reduced, the number of micropores is increased, the pore volume is increased, and the physical adsorption performance is favorably improved.
The invention also provides application of the carboxyl functionalized super-crosslinked polymer, which is applied to adsorbing polar aromatic organic small molecules in water.
As a preferred embodiment, the aromatic small molecule is at least one of aniline, salicylic acid and phenol.
After the carboxyl functionalized super-crosslinked polymer adsorbs polar aromatic micromolecules, desorption is carried out by adopting 0.01mol/L HCl and 75% (v/v) ethanol as eluent, and the desorption effect is good, so that the repeated use of the carboxyl functionalized super-crosslinked polymer is facilitated.
The chloromethylated polystyrene microsphere is common commercial crosslinked polystyrene macroporous resin in the market.
The technical proposal of the invention is that after the chloromethylated polystyrene microsphere and the monomer containing aromatic carboxylic acid are subjected to nucleophilic substitution reaction in alkaline environment, introducing a large amount of carboxyl functional groups on a polymer skeleton of the chloromethylated polystyrene microsphere so as to realize the regulation and control of the polarity of the chloromethylated polystyrene microsphere, continuously taking dimethoxymethane (FDA) and the like as cross-linking agents, under the condition of taking Lewis acid or protonic acid as a catalyst, through Friedel-Crafts alkylation reaction, the carboxylated polystyrene microspheres are further subjected to crosslinking reaction, the regulation and control of the pore structure size are realized, a large number of micropores are formed, the polymer is endowed with a unique pore structure, therefore, the polar modification and pore structure conditions of the carboxyl functionalized hypercrosslinked polymer endow the polymer with high selective adsorption effect on polar aromatic micromolecules in water, and the polymer is easy to elute after adsorption and can be repeatedly used.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) according to the technical scheme, the pore size of the super cross-linked polymer can be adjusted and controlled at will by adjusting the using amount of the catalyst and the type of the cross-linking agent, and meanwhile, the polarity of the super cross-linked polymer can be adjusted and controlled by the using amount and the type of the aromatic carboxylic acid monomer. On one hand, the chloromethylated polystyrene and the aromatic carboxylic acid monomer are subjected to nucleophilic substitution reaction in an alkaline environment, functional groups such as carboxyl and the like are introduced to a polymer skeleton, and the selective adsorption on the aromatic micromolecules containing hydrogen bond donors is remarkably improved; on the other hand, the cross-linking agent is added, and under the action of the catalyst, the Friedel-Crafts alkylation reaction is carried out, so that the specific surface area and the pore structure of the polymer can be obviously changed, and the selective adsorption capacity of aromatic organic compounds with different molecular sizes can be increased;
2) the technical scheme of the invention can regulate and control the pore size of the hypercrosslinked polymer in a proper range so as to be suitable for selective adsorption of aromatic organic compounds containing hydrogen bond donors with different molecular sizes, for example, the dosage of a catalyst and the type of an external cross-linking agent are properly changed in the preparation process of the hypercrosslinked polymer so as to improve the selective adsorption capacity of the aromatic organic compounds containing hydrogen bond donors with relatively larger molecular sizes. Overcomes the defects of the reported hypercrosslinked polymer in the prior art that the adsorption effect and the selectivity to polar pollutants (aniline, phenol, salicylic acid and the like) are not ideal.
3) The carboxyl functional super-crosslinked polymer is easy to elute after adsorption, can be repeatedly used, has good repeated use effect, and can be widely applied to the fields of chemical analysis, drug separation and purification, environmental pollution treatment and the like.
4) The method for preparing the carboxyl functionalized super-crosslinked polymer is simple, has lower cost and can be used for industrial production.
Drawings
FIG. 1 is an infrared spectrum of a chloromethylated polystyrene microsphere CMPS, a carboxylated polymer PS-BTCA and a carboxyl functionalized hypercrosslinked polymer PS-BTCA-HCP-X in example 1 of the present invention.
FIGS. 2 and 3 are the nitrogen adsorption/desorption curves and the pore diameter distribution diagrams of the chloromethylated polystyrene microsphere CMPS, the carboxylated polymer PS-BTCA and the carboxyl functionalized hypercrosslinked polymer PS-BTCA-HCP-X in example 1 of the present invention, respectively.
FIG. 4 is a graph showing the adsorption effect of PS-BTCA and PS-BTCA-HCP-X, a carboxylated polymer, on aniline at 298K in example 1 of the present invention.
FIG. 5 is a graph showing the effect of adsorption of the carboxyl-functionalized hypercrosslinked polymer PS-BTCA-HXP-X on aniline at different temperatures in example 1 of the present invention.
FIG. 6 is a graph showing the effect of the kinetic adsorption of the carboxylated polymer PS-BTCA and the carboxyl functionalized hypercrosslinked polymer PS-BTCA-HCP-X on aniline at 298K in example 1 of the present invention.
FIG. 7 is a graph of the reusability of the carboxyl functionalized hypercrosslinked polymer PS-BTCA-HCP-X to aniline adsorption in example 1 of the present invention.
Detailed Description
The following detailed description of the present invention is to be read in connection with the accompanying drawings, which are illustrative and explanatory only and are not restrictive of the scope of the invention, as claimed. Furthermore, features from embodiments in this document and from different embodiments may be combined accordingly by a person skilled in the art from the description in this document.
Example 1
1) Preparation of carboxylated Polymer (PS-BTCA):
10g of macroporous, low-crosslinked, chloromethylated polystyrene microspheres (CMPS) were added to 100mL of N, N-Dimethylformamide (DMF) and the CMPS was allowed to swell fully at room temperature for 12 h. 8.524g of trimesic acid and 20mL of N, N-diisopropylethylamine (the mole ratio of the chlorine content of the CMPS to the organic base to the trimesic acid is 3:3:1) are added, and the temperature of the mixed reaction system is raised to 90 ℃ for continuous reaction for 24 hours. The nucleophilic substitution reaction product is named as PS-BTCA, and is repeatedly washed by deionized water, absolute ethyl alcohol and 1% hydrochloric acid for many times to remove residual organic alkali and other substances. And stopping suction filtration when the pH of the last washing liquid is neutral, putting the product into a Soxhlet extractor for extraction for 24 hours (the extracting solution is clear and transparent), putting the extracted product into a fume hood for about 1 hour, and then putting the product into a vacuum drying oven at 60 ℃ for drying until the weight of the product is constant, wherein the product is white.
2) Preparation of carboxyl functionalized hypercrosslinked Polymer (PS-BTCA-HCP-X):
80mL of DCE was placed in a 250mL three-necked flask, and 5g of the nucleophilic substitution reaction carboxylated polymer PS-BTCA prepared in (1) was added to swell for 12 hours. To the swollen reaction system were added 10mL of dimethanol Formal (FDA), 3.4g of FeCl3Stirring at normal temperature for 30min, vacuumizing the mixed system, and stirring2Heating to 90 ℃ under protection, reacting for 24h, increasing the viscosity of the system in the reaction process, generating yellow-green flocculent substances, and generating white flocculent substances after the reaction. The prepared Friedel-Crafts reaction product is named as PS-BTCA-HCP-1 and is repeatedly washed by deionized water, absolute ethyl alcohol and 1% hydrochloric acid for many times. And when the pH value of the washing liquid at the last time is neutral, stopping suction filtration, putting the packed product into a Soxhlet extractor for extraction for 24 hours, and enabling the solvent in the tube to be clear and transparent after extraction. Placing the extracted product in a fume hood for about 1h, drying in a vacuum drying oven (temperature is 60 deg.C) to constant weight, removing water, and making the treated product black brown.
Raw material data for researching the influence of different conditions (solvent type, catalyst type and proportion and the like) on the oxygen-enriched hypercrosslinked polymer are shown in a table, and the experimental steps are consistent with the steps, and the specific contents are as follows:
(1) dichloromethane (DCM) as solvent, FeCl3The Friedel-Crafts reaction product serving as a catalyst is named as PS-BTCA-HCP-2, and the phenomenon that solvent is evaporated to dryness (the boiling point of dichloromethane is only 39.75 ℃) easily occurs in the experimental process, the reaction temperature needs to be well controlled, and the prepared product is black brown.
(2) Dichloroethane (DCE) as solvent, AlCl3The Friedel-Crafts reaction product named PS-BTCA-HCP-3 as catalyst was prepared in white color and AlCl was used in this experiment3Since the powder is white powder, it is easily dispersed in the environment, and particular attention is paid to the weighing.
(3) DCE is solvent, H2SO4The Friedel-Crafts reaction product, which is a catalyst, is named PS-BTCA-HCP-4. Addition of H to swollen PS-BTCA2SO4And then the PS-BTCA gradually turns into black under the stirring condition, and the PS-BTCA is agglomerated, the system still agglomerates at the initial stage of the heating reaction, and the system is gradually and uniformly dispersed along with the reaction.
(4) DCE is solvent, FeCl3The Friedel-Crafts reaction product of the catalyst is named PS-BTCA-HCP-5, the phenomenon of the mixed system in the heating process is basically the same as that of the PS-BTCA-HCP-1 preparation process, but the mixed system for preparing the PS-BTCA-HCP-5 has higher viscosity than that of the PS-BTCA-HCP-1, and finally, more white flocculent substances appear.
Preparation data table of oxygen-enriched hypercrosslinked polymer under different conditions
Figure BDA0003438095790000091
FIG. 1 shows the IR spectra of CMPS, PS-BTCA-HCP-1, and PS-BTCA-HCP-4. Wherein 1260cm-1The peaks of (A) and (B) are characteristic peaks of C-Cl bonds, and it can be seen from the figure that the polymers PS-BTCA, PS-BTCA-HCP-3, PS-BTCA-HCP-4 are 1260cm-1Is much less than the absorption intensity of CMPS,among them, the polymers PS-BTCA-HCP-1 and PS-BTCA-HCP-4 have almost no characteristic peak of C-Cl bond, and the characteristic peak of C-Cl bond of PS-BTCA may be covered by C-O bond stretching vibration peak, so that it can be seen that the chlorine content of the polymer has obvious change. The chlorine content of the product PS-BTCA was 3.99% as measured by the Flohard method. A significant reduction in the 17.3% chlorine content compared to CMPS indicates that trimesic acid is attached to the benzyl group of the CMPS. After Friedel-Crafts alkylation reaction at 90 ℃, the chlorine content of PS-BTCA-HCP-1 and PS-BTCA-HCP-4 is lower and reduced to about 0.3 percent. As can also be seen from FIG. 1, PS-BTCA-HCP-1, PS-BTCA-HCP-4 were found at 3639-3197cm-1Has a new absorption peak, the broad peak is the stretching vibration peak of O-H bond, PS-BTCA is at 1726cm-1The polymer has a new characteristic peak at the left and right, the characteristic peak is a stretching vibration peak of C ═ O bonds, and meanwhile, the polymer is 1229cm-1The left and right have C-O bond stretching vibration peaks, and the successful connection of the trimesic acid to the CMPS is proved again.
FIG. 2 is N at 77K for a carboxyl-functionalized hypercrosslinked polymer2The adsorption-desorption isotherm shows that the adsorption-desorption isotherm of CMPS conforms to the characteristics of the type III isotherm, the polymers PS-BTCA and PS-BTCA-HCP-4 are type IV isotherms, and the N of the prepared hypercrosslinked polymer2The adsorption-desorption isotherms all conform to the type IV isotherm, and the prepared polymer has micropores, mesopores and even macropores. Carboxyl functionalized hypercrosslinked polymers PS-BTCA-HCP-1, PS-BTCA-HCP-2, PS-BTCA-HCP-3, PS-BTCA-HCP-4, PS-BTCA-HCP-5SBETAre respectively 340m2/g、121m2/g、123m2/g、478m2/g、416m2G, S of hypercrosslinked polymers compared to CMPS and PS-BTCABETWith obvious improvement (S of CMPS and PS-BTCA)BETAre respectively 30m2/g、64m2In terms of/g). It is thus understood that the nucleophilic substitution reaction of the first step, linking the carboxyl function to the CMPS, has little effect on the specific surface area of the polymer, while the subsequent Friedel-Crafts alkylation reaction allows the S of the oxygen-rich hypercrosslinked polymerBETHas obvious promotion, which shows that methylene can be effectively used for the post-crosslinking reaction by adding the external crosslinking agentAttached to the polymer, a crosslinked network is formed that greatly increases the specific surface area of the polymer. S of PS-BTCA-HCP-2, PS-BTCA-HCP-3BETAlthough higher than CMPS and PS-BTCA, the increase in specific surface area was lower, indicating that the solvent effect of methylene chloride and the catalytic effect of aluminum trichloride were not very good.
FIG. 3 shows the Pore Size Distribution (PSD) consistent with the above conclusions, in which CMPS and PS-BTCA are mainly wide mesopores (the pore size is mainly distributed at 2-50 nm), but the average pore size of PS-BTCA is smaller than that of CMPS (18 nm and 25nm, respectively), which may be that three carboxyl groups on trimesic acid are connected with adjacent CMPS molecular chains, so that PS-BTCA has a certain degree of crosslinking, the pores of the PS-BTCA-HCP-4 product are mainly micropores, and a part of mesopores (the pore size is mainly distributed at 0.35-2 nm, 2-50 nm, and the average pore size is 4 nm). The pores of the polymers PS-BTCA-HCP-1, PS-BTCA-HCP-4 and PS-BTCA-HCP-5 have microporous and mesoporous structures, the pore diameters of the polymers are mainly distributed in the range of 0.35-2 nm, the content of pores with the diameters of 2-50 nm is low (the average pore diameters are respectively 3.2nm, 4.0nm and 2.8nm), and the product PS-BTCA-HCP-3 mainly takes mesopores as main pores, and the average pore diameter of the product is 11 nm. The average pore diameter of PS-BTCA-HCP-2 reaches 4nm, and the mesopores are the main. DCE as solvent, H, is described above2SO4And FeCl3The catalyst and the prepared super cross-linked polymer have better pore size distribution.
In the figures 4-6, through adsorption isotherms and adsorption kinetics experiments of carboxyl functionalized hypercrosslinked polymer on aniline, the adsorption of the prepared hypercrosslinked polymer on aniline is a heat release process, and the adsorption kinetics of the polymer accords with secondary kinetics characteristics, wherein PS-BTCA-HCP-4 has good adsorption performance and maximum equilibrium adsorption capacity q on anilinemThe adsorption balance can be reached at about 75min when the concentration reaches 395.6 mg/g. The PS-BTCA-HCP-4 products before and after adsorption are characterized, and the results show that the PS-BTCA-HCP-4 and aniline have strong interaction, the adsorption acting force of the polymer on the aniline in the adsorption process has pi-pi accumulation, acid-base action and hydrogen bonds, and in addition, the prepared super-crosslinked polymer has good adsorption effect on the aniline due to the rich micro-mesoporous structure and rich oxygen content. Meanwhile, the experiment also finds that H2SO4When protonic acid is used as a catalyst for Friedel-Crafts reaction, the prepared polymer has better adsorption effect, and simultaneously, the protonic acid is more stable and cannot react with FeCl3The Lewis acid is easy to hydrolyze, which opens up a new direction for the industrialization of the preparation of the hypercrosslinked polymer.
FIG. 7 shows that after 5 cycles of adsorption-desorption of the carboxyl functionalized hypercrosslinked polymer p-aniline solution prepared in example 1, the polymers PS-BTCA-HCP-4 and PS-BTCA-HCP-4 still have a reuse rate of more than 95%, and have good cycle performance and renewability. In practical applications, the polymer can be reused many times.
Example 2
1) Preparation of carboxylated Polymer (PS-PA):
10g of macroporous, low-crosslinked, chloromethylated polystyrene microspheres (CMPS) were added to 100mL of N, N-Dimethylformamide (DMF) and the CMPS was allowed to swell fully at room temperature for 12 h. A reflux condenser tube and a mechanical stirrer are arranged, and 4.04g of phthalic acid and 4.8g of basic catalyst K are added at normal temperature2CO3(the mole ratio of the chlorine content of the CMPS, the alkaline catalyst and the phthalic acid is 2:2:1), stirring for 30min until the CMPS is completely dissolved, heating to 90 ℃, reacting for 24h at the temperature, alternately washing the obtained product for 3-4 times by using 1% hydrochloric acid aqueous solution, ionized water and absolute ethyl alcohol respectively until the product is colorless, extracting the product in a Soxhlet extractor overnight by using ethanol, methanol and water in the volume ratio of 1:1:1, normally drying for 12h, and then drying in vacuum for 24h to obtain a carboxylated polymer PS-PA;
2) preparation of carboxyl-functionalized hypercrosslinked polymers (PS-PA-HCPs):
10g of PS-PA and 100mL of 1, 2-dichloroethane were added to a dry three-necked flask, and the mixture was sealed and swollen overnight at room temperature. A reflux condenser tube and a mechanical stirrer are arranged, and 10g of anhydrous AlCl is added in sequence3This was used as a catalyst and 20g of external crosslinker dimethoxymethane (FDA) were stirred at moderate speed for 30min until complete mixing. The temperature is increased to 90 ℃, and the reflux reaction is carried out for 24 hours. Stopping heating, washing the obtained product with 1% hydrochloric acid aqueous solution, hot water and absolute ethyl alcohol for 3-5 times alternately, and washing with ethyl alcohol, methyl alcohol and water in a volume ratio of 1:1:1Extracting in a extractor overnight, drying for 12h in a common way, and then drying in vacuum for 24h to obtain carboxyl functionalized hypercrosslinked polymers PS-PA-HCPs with different pore structures;
the prepared carboxylated polymer PS-PA has a chlorine content of 0.18mmol/g, SBETSpecific surface area of 32m2Per g, pore volume of 0.20cm3In terms of/g, the mean pore diameter is 20.7 nm. S of prepared carboxyl functionalized hypercrosslinked polymer PS-PA-HCPsBETThe specific surface area is 416m2Per g, pore volume of 0.31cm3In terms of/g, the mean pore diameter is 4.84 nm.
In the isothermal adsorption of the carboxyl functionalized hypercrosslinked polymer PS-PA-HCPs prepared in the example 2 on three polar small molecules, the maximum adsorption amounts of aniline, phenol and salicylic acid are 321.4mg/g, 268.3mg/g and 280.6mg/g respectively, and the adsorption is rapid and reaches equilibrium within 70 min. In the adsorption of the carboxyl functionalized hypercrosslinked polymer PS-PA-HCPs prepared in the example 2 on industrial wastewater (organic pollutant mixed system such as aniline, phenol, salicylic acid, rhodamine B, pyrene, naphthalene and biphenyl) with the simulated concentration of 100mg/L, the maximum adsorption amounts of polar micromolecules such as aniline, phenol and salicylic acid are 82mg/g, 75mg/g and 60mg/g respectively, and the maximum adsorption amounts of other organic pollutants are lower than 20 mg/g.
After the carboxyl functionalized hypercrosslinked polymer prepared in the example 2 is subjected to adsorption-desorption 5 times of cycles, the polymer PS-PA-HCPs still has the reuse rate of more than 95 percent, and has good cycle performance and reproducibility. In practical applications, the polymer can be reused many times.
Example 3
1) Preparation of carboxylated Polymer (PS-BA):
10g of macroporous, low-crosslinked, chloromethylated polystyrene microspheres (CMPS) were added to 100mL of N, N-Dimethylformamide (DMF) and the CMPS was allowed to swell fully at room temperature for 12 h. A reflux condenser tube and a mechanical stirrer are arranged, and 6.14g of benzoic acid and 4.8g of alkaline catalyst K are added at normal temperature2CO3(the mole ratio of the chlorine content of the CMPS, the basic catalyst and the trimesic acid is 1:1:1), stirring for 30min until the CMPS is completely dissolved, heating to 90 ℃, reacting for 24h at the temperature, and obtaining the productRespectively washing with 1% hydrochloric acid aqueous solution, ionized water and absolute ethyl alcohol for 3-4 times alternately until colorless, extracting overnight in a Soxhlet extractor with the volume ratio of ethanol to methanol to water being 1:1:1, drying for 12h in a common way, and drying for 24h in vacuum to obtain a carboxylated polymer PS-BA;
2) preparation of carboxyl functional hypercrosslinked polymers (PS-BA-HCPs):
10g of PS-BA and 100mL of 1, 2-dichloroethane were added to a dry three-necked round-bottomed flask, and the mixture was sealed and swollen overnight at ordinary temperature. A reflux condenser tube and a mechanical stirrer are arranged, and 5mL of H is added in sequence2SO4The catalyst and 20g of external crosslinker dimethoxymethane (FDA) were stirred at moderate speed for 30min to complete mixing. The temperature is increased to 90 ℃, and the reflux reaction is carried out for 24 hours. Stopping heating, alternately washing the obtained product for 3-5 times by using 1% hydrochloric acid aqueous solution, hot water and absolute ethyl alcohol in mass fraction, extracting the product in a Soxhlet extractor overnight by using ethanol, methanol and water in a volume ratio of 1:1:1, commonly drying the product for 12 hours, and then drying the product in vacuum for 24 hours to obtain carboxyl functionalized hypercrosslinked polymers PS-BA-HCPs with different pore structures;
the prepared carboxylated polymer PS-BA has the chlorine content of 0.32mmol/g and SBETThe specific surface area is 18m2Per g, pore volume of 0.16cm3In terms of a/g, the mean pore diameter is 25.7 nm. S of prepared carboxyl functionalized hypercrosslinked polymer PS-BA-HCPsBETThe specific surface area is 460m2Per g, pore volume of 0.53cm3In terms of a/g, the mean pore diameter is 3.32 nm.
In the isothermal adsorption of the carboxyl functionalized hypercrosslinked polymer PS-BA-HCPs prepared in the example 3 to the aniline, the maximum adsorption amount of the aniline is 256.4mg/g, the adsorption is rapid, and the equilibrium is reached within 50 min.
In the isothermal adsorption of the carboxyl functionalized hypercrosslinked polymer PS-BA-HCPs prepared in the example 3 on phenol, the maximum adsorption amount on phenol is 166.8mg/g, and the equilibrium is reached within 80 min.
The carboxyl functionalized hypercrosslinked polymer prepared in the example 3 has a reuse rate of more than 95% for the aniline solution and the phenol solution after 5 times of adsorption-desorption cycles, and has good cycle performance and reproducibility. In practical applications, the polymer can be reused many times.
Example 4
1) Preparation of carboxylated Polymer (PS-GA):
10g of chloromethylated polystyrene low-crosslinking polymer was added to 100mL of N, N-Dimethylformamide (DMF), and the mixture was sealed and swollen overnight at room temperature. A reflux condenser tube and a mechanical stirrer are arranged, and 8.28g of 3,4, 5-trihydroxybenzoic acid and 4.8g of alkaline catalyst K are added at normal temperature2CO3(the mole ratio of the chlorine content of the CMPS, the alkaline catalyst and the 3,4, 5-trihydroxybenzoic acid is 1:1:1), stirring for 30min until the CMPS is completely dissolved, heating to 90 ℃, reacting for 24h at the temperature, washing the obtained product for 3-4 times alternately with hot water, cold water and absolute ethyl alcohol respectively until the product is colorless, extracting for 8-24 h in a Soxhlet extractor with the volume ratio of the ethyl alcohol, the methyl alcohol and the water being 1:1:1, drying for 12h in a common way, and drying for 24h in a vacuum way to obtain the carboxylated polymer PS-GA.
2) Preparation of carboxyl-functionalized hypercrosslinked polymers (PS-GA-HCPs):
10g of the carboxylated polymer PS-GA and 100mL of 1, 2-dichloroethane were added to a dry three-necked round-bottomed flask, and the mixture was sealed and swollen overnight at room temperature. A reflux condenser tube and a mechanical stirrer are arranged, and 10g of anhydrous FeCl is added in sequence3As catalyst and external cross-linking agent, cyanuric chloride, dimethoxymethane, 1, 4-p-dichlorobenzyl and 4, 4-bis (chloromethyl) -1, 1-biphenyl were used, respectively. Stirring at medium speed for 30min to completely mix and dissolve. The temperature is increased to 90 ℃, and the reflux reaction is carried out for 24 hours. Stopping heating, alternately washing the obtained product for 3-5 times by using 1% hydrochloric acid aqueous solution and absolute ethyl alcohol, extracting for 8-24 h in a Soxhlet extractor by using ethanol, methanol and water in a volume ratio of 1:1:1, drying for 12h in a common way, and drying for 24h in a vacuum way to obtain carboxyl-rich hypercrosslinked polymers PS-GA-HCPs-1, PS-GA-HCPs-2, PS-GA-HCPs-3 and PS-GA-HCPs-4 with different pore structures; the infrared characterization shows that the concentration is 1260cm-1The absorption peak at (b) almost disappears, and methylene groups crosslink to the polymer, and the degree of crosslinking increases sharply.
The prepared carboxylated polymer PS-GA has a chlorine content of 0.88mmol/g and SBETThe specific surface area is 34m2Per g, pore volume of0.27cm3In terms of/g, the mean pore diameter is 30.9 nm. S of prepared carboxyl functionalized hypercrosslinked polymer PS-GA-HCPs-1BETSpecific surface area of 309m2Per g, pore volume of 0.39cm3In terms of/g, the mean pore diameter is 5.00 nm.
The prepared carboxylated polymer PS-GA has a chlorine content of 0.88mmol/g and SBETThe specific surface area is 34m2G, pore volume of 0.27cm3In terms of/g, the mean pore diameter is 30.9 nm. S of prepared carboxyl functionalized hypercrosslinked polymer PS-GA-HCPs-2BETSpecific surface area of 282m2Per g, pore volume of 0.46cm3In terms of a/g, the mean pore diameter is 6.65 nm.
The prepared carboxylated polymer PS-GA has a chlorine content of 0.88mmol/g and SBETThe specific surface area is 34m2G, pore volume of 0.27cm3In terms of/g, the mean pore diameter is 30.9 nm. S of prepared carboxyl functionalized hypercrosslinked polymer PS-GA-HCPs-3BETSpecific surface area is 168m2G, pore volume of 0.27cm3In terms of/g, the mean pore diameter is 8.12 nm.
The prepared carboxylated polymer PS-GA has a chlorine content of 0.88mmol/g and SBETThe specific surface area is 34m2G, pore volume of 0.27cm3In terms of/g, the mean pore diameter is 30.9 nm. S of prepared carboxyl functionalized hypercrosslinked polymer PS-GA-HCPs-4BETThe specific surface area is 336m2Per g, pore volume of 0.4cm3In terms of a/g, the mean pore diameter is 4.70 nm.
In the isothermal adsorption of the carboxyl functionalized hypercrosslinked polymer PS-GA-HCPs prepared in example 4 on aniline, the maximum adsorption amount of PS-GA-HCPs-4 on aniline is 159.2mg/g, and the adsorption reaches equilibrium within 85 min.
In the isothermal adsorption of the carboxyl functionalized hypercrosslinked polymer PS-GA-HCPs prepared in example 4 to phenol, the maximum adsorption amount of PS-GA-HCPs-4 to phenol was 108.9mg/g, and the adsorption reached equilibrium within 90 min. In the adsorption of the carboxyl functionalized hypercrosslinked polymer PS-GA-HCPs-4 prepared in the example 4 on industrial wastewater (organic pollutant mixed system such as aniline, phenol, salicylic acid, rhodamine B, pyrene, naphthalene and biphenyl) with the simulated concentration of 100mg/L, the maximum adsorption amounts of polar micromolecules such as aniline, phenol and salicylic acid are 63mg/g, 60mg/g and 54mg/g respectively, and the maximum adsorption amounts of other organic pollutants are lower than 10 mg/g.
The carboxyl functionalized hypercrosslinked polymer PS-GA-HCPs prepared in the example 4 still has the reuse rate of more than 93.6 percent after 5 times of adsorption-desorption cycles on aniline solution. In practical applications, the polymer can be reused many times.
Example 5
1) Preparation of carboxylated Polymer (PS-DA):
10g of macroporous, low-crosslinked, chloromethylated polystyrene microspheres (CMPS) were added to 100mL of N, N-Dimethylformamide (DMF) and the CMPS was allowed to swell fully at room temperature for 12 h. A reflux condenser tube and a mechanical stirrer are arranged, and 7.50g of 3, 5-dihydroxybenzoic acid and 4.8g of basic catalyst K are added at normal temperature2CO3(the mole ratio of the chlorine content of the CMPS, the alkaline catalyst and the trimesic acid is 1:1:1), stirring for 30min until the CMPS is completely dissolved, heating to 90 ℃, reacting for 24h at the temperature, alternately washing the obtained product for 3-4 times by using 1% hydrochloric acid aqueous solution, ionized water and absolute ethyl alcohol respectively until the product is colorless, extracting the product in a Soxhlet extractor overnight by using ethanol, methanol and water in the volume ratio of 1:1:1, normally drying for 12h, and then drying in vacuum for 24h to obtain a carboxylated polymer PS-DA;
2) preparation of carboxyl-functionalized hypercrosslinked polymers (PS-DA-HCPs):
10g of PS-DA and 100mL of 1, 2-dichloroethane were added to a dry three-necked round-bottomed flask, and the mixture was sealed and swollen overnight at ordinary temperature. A reflux condenser tube and a mechanical stirrer are arranged, and 8g, 13g and 18g of anhydrous FeCl are added in sequence3Used as catalyst and external cross-linking agent dimethoxymethane (FDA), and stirred at medium speed for 30min until completely mixed. The temperature is increased to 90 ℃, and the reflux reaction is carried out for 24 hours. Stopping heating, alternately washing the obtained product for 3-5 times by using 1% hydrochloric acid aqueous solution, hot water and absolute ethyl alcohol in mass fraction, extracting the product in a Soxhlet extractor overnight by using ethanol, methanol and water in a volume ratio of 1:1:1, commonly drying the product for 12 hours, and then drying the product in vacuum for 24 hours to obtain carboxyl functionalized hypercrosslinked polymers PS-DA-HCPs-1, PS-DA-HCPs-2 and PS-DA-HCPs-3 with different pore structures; the infrared characterization shows that the concentration is 1260cm-1Almost eliminates the absorption peakThe methylene groups are lost to crosslinking in the polymer and the degree of crosslinking increases dramatically.
The prepared carboxylated polymer PS-DA has a chlorine content of 0.25mmol/g, SBETThe specific surface area is 26m2Per g, pore volume of 0.23cm3In terms of/g, the mean pore diameter was 21.9 nm. S of prepared carboxyl functionalized hypercrosslinked polymer PS-DA-HCPs-1BETThe specific surface area is 360m2Per g, pore volume of 0.40cm3In terms of/g, the mean pore diameter is 4.8 nm.
The prepared carboxylated polymer PS-DA has a chlorine content of 0.25mmol/g, SBETThe specific surface area is 26m2Per g, pore volume of 0.23cm3In terms of/g, the mean pore diameter was 21.9 nm. S of prepared carboxyl functionalized hypercrosslinked polymer PS-DA-HCPs-2BETThe specific surface area is 437m2Per g, pore volume of 0.44cm3In terms of a/g, the mean pore diameter is 4.01 nm.
The prepared carboxylated polymer PS-DA has a chlorine content of 0.25mmol/g, SBETThe specific surface area is 26m2Per g, pore volume of 0.23cm3In terms of/g, the mean pore diameter was 21.9 nm. S of carboxyl functionalized hypercrosslinked polymer PS-DA-HCPs-2BETThe specific surface area is 420m2Per g, pore volume of 0.44cm3In terms of/g, the mean pore diameter is 4.32 nm.
In the isothermal adsorption of the carboxyl functionalized hypercrosslinked polymers PS-DA-HCPs-1, PS-DA-HCPs-2 and PS-DA-HCPs-3 prepared in the example 5 on aniline, the maximum adsorption amounts of aniline are 132.8mg/g, 148.5mg/g and 142.5mg/g respectively, and the adsorption is rapid and reaches equilibrium within 55 min.
In the isothermal adsorption of the carboxyl functionalized hypercrosslinked polymer PS-DA-HCPs-2 prepared in the example 5 to three polar small molecules, the maximum adsorption amounts of the aniline, the phenol and the salicylic acid are 148.5mg/g, 136.8mg/g and 120.9mg/g respectively, the adsorption is rapid, and the equilibrium is reached within 50min
The carboxyl functionalized hypercrosslinked polymer PS-DA-HCPs prepared in the example 5 has a reuse rate of more than 94.2 percent for the PS-DA-HCPs after 5 times of adsorption-desorption cycles on aniline solution. In practical applications, the polymer can be reused many times.
The adsorption performance of the carboxyl-functionalized hypercrosslinked polymers prepared in examples 1 to 5 was tested.
(1) Isothermal adsorption:
aniline (or salicylic acid and phenol) is selected as an adsorbate, and the adsorption performance of the prepared carboxyl functionalized super-crosslinked polymer on the adsorbate in an aqueous solution is compared. The adsorption isotherm was determined as follows:
a group of conical bottles with stoppers are taken, about 0.05g of polymer and 50mL of adsorbate aqueous solutions with different concentrations are respectively added into the conical bottles, and the conical bottles are placed in a water bath oscillator and are subjected to constant temperature oscillation for 4 hours at a certain temperature so as to enable the adsorption to reach equilibrium. Measuring absorbance of the residue at the maximum absorption wavelength of the adsorbate with an ultraviolet-visible spectrophotometer, and converting into equilibrium concentration C of the adsorbate according to a standard curveeThe amount of adsorption was calculated as follows:
qe＝(C0-Ce)V/W
in the formula: q. q.seAs adsorbed amount (mg/g), C0、CeThe concentrations (mg/L) of the adsorbate in the aqueous solution before and after adsorption, respectively, V is the volume (L) of the adsorption solution, and W is the mass (g) of the polymer. At equilibrium concentration CeAs abscissa, adsorption quantity qeAs an ordinate, the adsorption isotherm of the polymer at a certain temperature for adsorbates in an aqueous solution was plotted.
(2) Adsorption kinetics:
about 0.5g of polymer was weighed into a 500mL Erlenmeyer flask, 250mL of aniline (or salicylic acid, phenol) was added at an original concentration of 500mg/L, and the Erlenmeyer flask was put into a constant temperature shaker and shaken. And (3) timing from the addition of the solution, transferring 0.5mL of the adsorption solution into a small 100mL beaker at a certain time, and measuring the absorbance of the adsorption solution and the absorbance of the original solution at different time points by using an ultraviolet-visible spectrometer. The solution concentration was calculated from the standard curve equation. Then, the adsorption quantity q of the polymer at the time t is calculated according to the following formulat：
qt＝(C0-Ct)V/W
With t (min) as the abscissa and qt(mg/g) is the ordinate and the adsorption kinetics of the polymer on aniline (or salicylic acid, phenol) is plotted.
(3) Adsorption removing effect of p-aniline (or salicylic acid and phenol) by using different polymer amounts
Weighing about 0.02g, 0.05g, 0.1g, 0.2g, 0.3g, 0.4g, 0.5g, 0.6g polymer into a 50mL conical flask, adding 50mL aniline (or salicylic acid, phenol) with 500mg/L original concentration, placing them into a water bath oscillator, and oscillating at constant temperature for 4h to make the adsorption reach equilibrium. Measuring absorbance of the residue at the maximum absorption wavelength of the adsorbate with an ultraviolet-visible spectrophotometer, and converting into equilibrium concentration C of the adsorbate according to a standard curveeAnd calculating the removal efficiency of the p-aniline.
The influence curve of the polymer dosage on the polymer dosage of the aniline (or salicylic acid and phenol) is drawn by taking the polymer dosage m (g) as an abscissa and the removal efficiency (%) as an ordinate.
(3) Adsorption effect of different pH values on aniline (or salicylic acid and phenol)
50mL of aniline (or salicylic acid or phenol) with the original concentration of 500mg/L, 1mol/L of hydrochloric acid aqueous solution and 1mol/L of sodium hydroxide aqueous solution are added into a group of beakers to adjust the pH value of the solution in each beaker to be 2, 4, 6, 7, 8, 10 and 12 respectively, 1mL of the solution is taken respectively, the original concentration is measured, a group of conical flasks with plugs are taken, about 0.05g of polymer is added into the conical flasks respectively, and the two are mixed. Placing them in a water bath oscillator, and oscillating at constant temperature for 4h to make the adsorption reach equilibrium. Measuring absorbance of the residue at the maximum absorption wavelength of the adsorbate with an ultraviolet-visible spectrophotometer, and converting into equilibrium concentration C of the adsorbate according to a standard curveeThe amount of adsorption was calculated as follows:
qe＝(C0-Ce)V/W
with pH as abscissa, qe(mg/g) is the ordinate and the pH influence of the polymer on aniline (or salicylic acid, phenol) is plotted.
(4) Simulating the selective adsorption effect of the polymer on the aniline (or salicylic acid and phenol) in the industrial wastewater mixed system
A group of beakers are taken and added with 10mL of original concentration100mg/L aniline, phenol, salicylic acid, rhodamine B, pyrene, naphthalene and biphenyl solution, 1mL solution, measuring the original concentration of each organic pollutant, a set of conical bottles with stoppers, about 0.07g polymer added thereto, and mixing the two. Placing them in a water bath oscillator, and oscillating at constant temperature for 4h to make the adsorption reach equilibrium. Measuring absorbance of the residue at the maximum absorption wavelength of the adsorbate with an ultraviolet-visible spectrophotometer, and converting into equilibrium concentration C of the adsorbate according to a standard curveeThe amount of adsorption was calculated as follows:
qe＝(C0-Ce)V/W
with different adsorbates as abscissa, qe(mg/g) is the ordinate, and a graph of the selective adsorption effect of the polymer on different adsorbates is drawn.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of carboxyl functionalized hypercrosslinked polymer is characterized in that: the method comprises the following steps:
1) performing nucleophilic substitution reaction on chloromethylated polystyrene microspheres and aromatic carboxylic acid monomers in an alkaline environment to obtain carboxylated polystyrene microspheres;
2) the carboxylated polystyrene microsphere and the cross-linking agent are subjected to Friedel-Crafts reaction under the action of an acid catalyst to obtain the carboxyl functionalized super cross-linked polymer.
2. The method for preparing carboxyl functionalized hypercrosslinked polymer according to claim 1, wherein: the aromatic carboxylic acid monomer is at least one of benzoic acid, phthalic acid, trimesic acid, 3, 5-dihydroxybenzoic acid and 3,4, 5-trihydroxybenzoic acid.
3. The method for preparing carboxyl functionalized hypercrosslinked polymer according to claim 1, wherein: the molar ratio of the chloromethylated polystyrene microspheres to the aromatic carboxylic acid monomers is measured by the molar ratio of the carboxyl content in the aromatic carboxylic acid monomers to the chlorine content in the chloromethylated polystyrene microspheres being 1: 1-1: 3.
4. The method for preparing carboxyl functionalized hypercrosslinked polymer according to claim 1, wherein: the conditions of the nucleophilic substitution reaction are as follows: reacting for 12-36 h at 80-100 ℃.
5. The method for preparing carboxyl functionalized hypercrosslinked polymer according to claim 1, wherein:
the cross-linking agent is at least one of cyanuric chloride, dimethoxymethane, 1, 4-p-dichlorobenzyl and 4, 4-bis (chloromethyl) -1, 1-biphenyl;
the acid catalyst comprises a lewis acid and/or a protic acid;
the Lewis acid is FeCl3、AlCl3And SnCl4At least one of (1);
the protonic acid is H2SO4And HCl.
6. The method for preparing carboxyl functionalized hypercrosslinked polymer according to claim 5, wherein:
the mass of the cross-linking agent is 50-250% of that of the carboxylated polystyrene microspheres;
the mass of the Lewis acid is 100-150% of that of the carboxylated polystyrene microsphere;
the mass of the protonic acid is 50-100% of that of the carboxylated polystyrene microsphere.
7. The method for preparing carboxyl functionalized hypercrosslinked polymer according to claim 1, wherein: the conditions of the Friedel-Crafts reaction are as follows: reacting for 12-36 h at the temperature of 80-90 ℃.
8. A carboxyl-functionalized hypercrosslinked polymer characterized by: the preparation method of any one of claims 1 to 7.
9. The carboxyl-functionalized hypercrosslinked polymer according to claim 8, characterized in that: the specific surface area is 123-478 m2A pore volume of 0.27 to 0.53cm3(ii)/g, the average pore diameter is 2.8 to 11 nm.
10. Use of a carboxy-functional hypercrosslinked polymer according to claim 9, characterised in that: the method is applied to adsorbing polar aromatic organic micromolecules in water.
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CN104945555A (en) * 2015-06-19 2015-09-30 中南大学 Method for preparing polar modified ultra-high crosslinking type interpenetrating polymer network and application thereof
CN105924558A (en) * 2016-06-28 2016-09-07 中南大学 Preparation method and application of hypercrosslinked resin with controllable polarity and pore structure
CN111040226A (en) * 2019-12-02 2020-04-21 中南大学 Preparation method of hypercrosslinked polymer rich in hydrogen bond acceptor oxygen atoms and application of hypercrosslinked polymer

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CN104910313A (en) * 2015-06-24 2015-09-16 中南大学 Method for preparing polar modified ultrahighly-crosslinked resin and application of resin
CN105924558A (en) * 2016-06-28 2016-09-07 中南大学 Preparation method and application of hypercrosslinked resin with controllable polarity and pore structure
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