CN110975838B - Imino diacetic acid functionalized super-crosslinked polymer, and preparation and application thereof - Google Patents
Imino diacetic acid functionalized super-crosslinked polymer, and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to an iminodiacetic acid functionalized hypercrosslinked polymer, a preparation method and an application thereof. The polymer chelates metal ions with nitrogen on imino groups and oxygen on diacetic acid for efficient environmental remediation. The polymer material provides active imino and carboxyl for coordination of metal ions.
Description
Technical Field
The invention relates to the technical field of hypercrosslinked polymers; in particular to an iminodiacetic acid functionalized hypercrosslinked polymer, a preparation method and an application thereof.
Background
Heavy metals released from mine or industrial wastewater pose a threat to environmental pollution. Surprisingly, contacting these metals even at very low concentrations can cause serious damage. Heavy metal pollution poses serious problems to the public and the environment. Existing techniques can address this problem, and can be expensive or insufficiently clean to the desired level.
The porous polymer material has high surface area and a large amount of metal ion binding functional groups, and plays an important role in absorbing and purifying heavy metals. The development of porous polymers with highly effective metal-binding functional groups to capture heavy metals and purify water is a matter of concern. This is because the adsorption of metals on these materials has the technical promise of simplicity and low cost. Various adsorbents such as activated carbon, zeolites, clays, etc. have been developed to remove heavy metals from water, but they lack high capacity and strong affinity for heavy metals. In addition, metal-organic frameworks can also be used for heavy metal capture due to their large surface area, but generally lack stability in water or have a large pH range in aqueous solutions, and have a low capacity for metal ions and a weak affinity.
The heavy metal removal method is multiple, and reverse osmosis has the defects of high cost, poor selectivity, slow absorption and the like, and is not suitable for water treatment. The other is an ion exchange resin which can adsorb all metal ions including Na + 、K + 、Ca 2+ And the water is free of toxicity and rich in metal ions.
Porous materials such as Metal Organic Frameworks (MOFs) and various porous organic polymer materials are widely applied to the aspects of gas storage, gas separation, catalysis and the like as novel solid adsorbents. Most of these materials have been developed in recent decades and lack preferential binding sites for heavy metal adsorption.
Therefore, there is a need to develop an improved adsorbent for heavy metal adsorption having high adsorption capacity, high selectivity and wide-range stability. In addition to high absorption capacity and selectivity for specific heavy metals, a wide range of stable conditions is important for practical applications.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides an iminodiacetic acid functionalized hypercrosslinked polymer, and a preparation method and an application thereof.
The invention aims to provide an iminodiacetic acid functionalized hypercrosslinked polymer, which is prepared by hypercrosslinking iminodiacetic acid functionalized monomer, a crosslinking agent and a catalyst.
According to some preferred embodiments of the present invention, the pore size distribution of the hypercrosslinked polymer is from 0.53 to 1.47 nm; and/or the surface area of the hypercrosslinked polymer is 400-480m 2 g –1 (ii) a And/or the pore volume of the hypercrosslinked polymer is 0.12-0.18cm 3 g –1 。
According to some preferred embodiments of the invention, the crosslinker is 1, 4-p-xylylene ether.
According to some preferred embodiments of the invention, the catalyst is FeCl 3 。
According to some preferred embodiments of the invention, the monomer is dimethyl 2,2'- ([1,1' -diphenyl ] 4-acetyl) diacetate.
The invention also aims to provide a preparation method of the iminodiacetic acid functionalized hypercrosslinked polymer, which comprises the following steps: carrying out a hypercrosslinking reaction on an iminodiacetic acid functionalized monomer and a crosslinking agent through catalysis to obtain a hypercrosslinked prepolymer; and (3) carrying out post-synthesis and modification on the hypercrosslinked prepolymer to obtain the iminodiacetic acid functionalized hypercrosslinked polymer.
According to some preferred embodiments of the invention, comprising:
(a) adding anhydrous ferric chloride into the solution of the monomer and the 1, 4-p-xylylene ether in the nitrobenzene, and uniformly mixing; heating at 60-80 deg.C, preferably 80 deg.C, for 4-5 hours, preferably 5 hours, and then refluxing at 120-125 deg.C, preferably 120 deg.C, under an inert atmosphere for 24-36 hours, preferably 24 hours, to obtain a hypercrosslinked prepolymer;
(b) the hypercrosslinking prepolymer and H 2 O and CH 3 CH 2 OH is mixed under stirring, preferably the H 2 O and CH 3 CH 2 The volume ratio of OH is 2: 1; then 2N NaOH is added; continuously stirring at 80-100 ℃, preferably 80 ℃, for 24-36 hours, preferably 48 hours, and carrying out post-treatment to obtain the super-crosslinked polymer.
According to some preferred embodiments of the present invention, in step (a), the preparation of the monomer comprises the steps of: 4-aminobiphenyl, NaI and proton sponge are taken as main raw materials, and the monomer is obtained through nucleophilic substitution reaction; preferably, the method comprises the following steps: placing 4-aminobiphenyl, NaI and proton sponge together; then the gas in the reaction bottle is pumped out and N is used 2 Displacement is carried out for three times; transferring the dried acetonitrile into the reaction mixture, and stirring at room temperature to dissolve reactants; adding methyl bromoacetate, refluxing, cooling to room temperature, and adding toluene; then filtering, washing and drying to obtain the product.
According to some preferred embodiments of the present invention, the step (a), after the reflux treatment, further comprises the steps of cooling the mixture to room temperature, sequentially filtering and washing with methanol, distilled water, dichloromethane and acetone until the filtrate is nearly colorless; performing Soxhlet extraction for purification, preferably extracting with methanol for 24-36 hr, preferably 24 hr, and extracting with dichloromethane for 24-36 hr, preferably 36 hr; the polymer is then freeze-dried for 24-48 hours, preferably 24 hours; and/or
In the step (b), the post-treatment comprises the following steps: the precipitate was collected by filtration, using HCl and H, respectively 2 Washing for three times by using O, and washing for two days by using methanol and dichloromethane respectively by using a Soxhlet extraction method; and then freeze-drying to obtain the product.
The invention also provides application of the iminodiacetic acid functionalized hypercrosslinked polymer in removing heavy metal ions, preferably in adsorbing Pb in aqueous solution 2+ The use of (1).
The invention has the beneficial effects that: the present invention provides a preparation of a porous polymer material containing chelating functional groups for removing heavy metals by binding to designed surface groups. The present invention provides a hypercrosslinked polymer (HCP-N (CH) 2 CO 2 H) 2 ) The metal chelate has the advantages of good chemical and thermodynamic stability, large specific surface area and abundant chelating sites, thereby not only having high absorption capacity and selectivity for transition metals, but also having the advantage of reusability and having longer service cycle. The preparation method has the advantages of cheap and easily obtained raw materials, high synthesis yield and the like.
Drawings
FIG. 1 shows HCP-N (CH) in the present invention 2 CO 2 H) 2 TGA results of (a).
FIG. 2 shows HCP-N (CH) in the present invention 2 CO 2 H) 2 XRD results of (1).
FIG. 3 shows HCP-N (CH) in the present invention 2 CO 2 H) 2 FT-IR results of (1).
FIG. 4 shows HCP-N (CH) at 77k in the present invention 2 CO 2 CH 3 ) 2 And HCP-N (CH) 2 CO 2 H) 2 Nitrogen adsorption-desorption isotherm.
FIG. 5 is a drawing showingHCP-N (CH) calculated by NLDFT in the invention 2 CO 2 CH 3 ) 2 And HCP-N (CH) 2 CO 2 H) 2 Pore size distribution of (2).
FIG. 6 shows HCP-N (CH) in the present invention 2 CO 2 H) 2 For Pb at pH 7 2+ Adsorption profile over time (min) for adsorption in aqueous solution.
FIG. 7 shows Pb in the present invention 2+ HCP-N (CH) at initial concentration of 10ppm, pH 7 2 CO 2 H) 2 For Pb 2+ Adsorption kinetics.
FIG. 8 shows pseudo-divalent Pb at an initial concentration of 10ppm and pH 7 in the present invention 2+ Adsorption kinetics.
FIG. 9 shows Pb at pH 7.0 after 12h in the present invention 2+ Adsorption isotherms.
Figure 10 is the langmuir adsorption model of the present invention fitted with equilibrium adsorption data to perform linear regression. Maximum adsorption capacity (q) m ) 1031mg g -1 The equilibrium constant of the adsorption reaction was 0.539L mg -1 。
FIG. 11 shows pH vs. Pb in the present invention 2+ Influence of adsorption isotherms.
FIG. 12 shows Pb in an aqueous solution according to the present invention 2+ Cycle performance of adsorption.
Fig. 13 shows the trapping efficiency of metal ions at pH 7.0 in the mixed solution of the present invention.
FIG. 14 shows HCP-N (CH) at pH 7 in the present invention 2 CO 2 H) 2 For Pb 2+ Adsorption profile over time (min). The inset shows the pseudo-divalent Pb at an initial concentration of 30ppm and pH 7 2+ Adsorption kinetics.
FIG. 15 shows HCP-N (CH) in the present invention 2 CO 2 H) 2 And Pb @ HCP-N (CH) 2 CO 2 H) 2 Ultraviolet and visible absorption spectrum of (1).
FIG. 16 shows HCP-N (CH) in the present invention 2 CO 2 H) 2 ) And Pb @ HCP-N (CH) 2 CO 2 H) 2 Fluorescence emission spectrum of (1).
FIG. 17 shows dimethyl 2,2'- ([1,1' -diphenyl ] group in the present invention]4-Of acetyl) diacetate 1 H NMR results.
FIG. 18 shows dimethyl 2,2'- ([1,1' -diphenyl ] group in the present invention]Process for preparing 4-acetyl) diacetate 13 C NMR results.
FIG. 19 shows the MS results of dimethyl 2,2'- ([1,1' -diphenyl ] 4-acetyl) diacetate according to the present invention.
FIG. 20 is a graph showing the synthesis of a hypercrosslinked polymer (HCP-N (CH) containing an aminoacetic acid functional group similar to the EDTA functional group, provided by the present invention 2 CO 2 H) 2 ) A circuit diagram of (a).
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The instruments and the like are conventional products which are purchased by normal distributors and are not indicated by manufacturers. The chemical raw materials used in the invention can be conveniently bought in domestic chemical product markets.
The synthesis of the compounds of the present invention can be carried out by referring to the method of example 1. The following describes the synthesis of some of the main compounds of the present invention.
Example 1
The embodiment provides a method for synthesizing a monomer of an iminodiacetic acid functionalized hypercrosslinked porous polymer capable of adsorbing heavy metal ions in an aqueous solution, which comprises the following specific steps: 4-aminobiphenyl (0.141g,0.831mmol), NaI (0.106g,0.707mmol), proton sponge (1.15g,5.35mmol) were placed together. Then the gas in the reaction bottle is pumped out and N is used 2 (g) The substitution was carried out three times. Dry acetonitrile (10mL) was transferred to the reaction mixture via syringe and stirred at room temperature to dissolve the reaction. Methyl bromoacetate (0.40mL,4.22mmol) was added via syringe, refluxed for 3 days, and progress monitored by TLC. After refluxing for 3 days, it was cooled to room temperature and toluene (10mL) was added. The filtrate was filtered, washed three times with phosphate buffer (pH 2) and once more with water, and the organic layer was collected. Organic layer in Na 2 SO 4 Drying, and rotary drying under vacuum to obtain monoBulk dimethyl 2,2'- ([1,1' -diphenyl group)]4-acetyl) diacetate. The prepared monomer dimethyl 2,2'- ([1,1' -diphenyl)]4-acetyl) diacetate via 1 H、 13 C NMR and MS (MALDI-TOF) characterization, the results are shown in FIGS. 17-19.
Example 2
FIG. 20 shows the synthesis of a hypercrosslinked polymer (HCP-N (CH) containing an aminoethanol functional group similar to the EDTA functional group 2 CO 2 H) 2 ) A circuit diagram of (a). This example synthesizes an iminodiacetic acid functionalized porous prepolymer. The method comprises the following specific steps: anhydrous ferric chloride (1.22g,7.51mmol) was added to dimethyl 2,2'- ([1,1' -diphenyl ] obtained in example 1]4-acetyl) diacetate (0.2615g,0.835mmol) and 1, 4-p-xylylene ether (DMB) (0.345g,2.495mmol) in nitrobenzene (7.5mL) were magnetically stirred at room temperature for 40 minutes to form a homogeneous mixed solution. After dissolution, the initial network was formed by heating at 80 ℃ for 5 hours and then refluxing at 120 ℃ for 24 hours under nitrogen. The mixture was cooled to room temperature, and the precipitated hypercrosslinked polymer was successively filtered and washed with methanol, distilled water, methylene chloride and acetone until the filtrate was nearly colorless. The copolymer was further purified by soxhlet extraction with methanol for 24 hours and dichloromethane for 36 hours. After Soxhlet extraction and washing, the polymer was freeze-dried for 24 hours to obtain a brown solid with a yield of 70%, i.e., the hypercrosslinked prepolymer HCP-N (CH) 2 CO 2 CH 3 ) 2 。
The imino diacetic acid functionalized hypercrosslinked polymer is prepared by utilizing the hypercrosslinked prepolymer through post synthesis and modification. Hypercrosslinked prepolymer (1g), H 2 O (100mL) and CH 3 CH 2 OH (50mL) were mixed together with stirring. NaOH (2N, 100mL) was then added to the mixture solution. After stirring at 80 ℃ for 48 hours, the precipitate was collected by filtration, washed with HCl and H, respectively 2 O washes three times. The product was further purified by soxhlet extraction with methanol and dichloromethane, respectively, for two days. Finally, the product was freeze-dried to obtain the hypercrosslinked polymer HCP-N (CH) 2 CO 2 H) 2 Is brownSolid, yield 60%. FIG. 1 verifies HCP-N (CH) by preparation procedure 2 CO 2 H) 2 Chemical stability under various severe conditions, and excellent thermal stability thereof are shown in fig. 1. FIG. 2 shows the HCP-N (CH) polymer obtained 2 CO 2 H) 2 XRD results of (1). FIG. 3 shows HCP-N (CH) 2 CO 2 H) 2 Fourier transform infrared spectroscopy (FT-IR) of (1), showing an infrared characteristic absorption band of about 3433cm -1 Is O-H on carboxylic acid, and another characteristic peak is 2996cm -1 Is C-H on the alkyl group, 1731cm -1 Is C ═ O (carbonyl) and 1333cm -1 Is a C-O functional group.
Experimental example 1
FIG. 4 shows N at 77K 2 The surface area and the pore volume of the hypercrosslinked polymer material prepared in example 2 were respectively determined by adsorption isotherms to be 474m 2 g –1 And 0.18cm 3 g –1 . The adsorbed NLDFT fitting model showed that HCP-N (CH) was prepared according to example 2 2 CO 2 CH 3 ) 2 And HCP-N (CH) 2 CO 2 H) 2 Pore size distribution mainly in the range of 0.53-1.47 nm (FIG. 5), (Table 1 shows HCP-N (CH) prepared in example 2 2 CO 2 CH 3 ) 2 And HCP-N (CH) 2 CO 2 H) 2 Pore performance analysis of (1). The polymer skeleton is stable when soaked in strong alkali (2N NaOH) at normal temperature and is stable even when heated to about 100 ℃.
TABLE 1HCP-N (CH) 2 CO 2 CH 3 ) 2 And HCP-N (CH) 2 CO 2 H) 2 Pore performance analysis of
| Polymer and method of making same | S BET (m 2 g -1 ) | S micro (m 2 g -1 ) | V total (cm 3 g -1 ) | Pore size (nm) |
| HCP-N(CH 2 CO 2 H) 2 | 400-480 | 248 | 0.12-0.18 | 0.53–1.54 |
| HCP-N(CH 2 CO 2 CH 3 ) 2 | 530-560 | 281 | 0.14-0.29 | 0.53–1.47 |
Experimental example 2
The properties of the hypercrosslinked polymer material prepared in example 2 were examined. Before examining the Pb (II) removing ability of the polymer material prepared in example 2, the adsorption properties thereof at different pH ranges and concentrations were examined. An inductively coupled plasma analysis method is adopted to collect the adsorption isotherm of lead (II) in the aqueous solution. To evaluate HCP-N (CH) 2 CO 2 H) 2 For Pb 2+ Adsorption capacity of (2) Pb 2+ The aqueous slurry was stirred for 12 hours before equilibrium adsorption measurements were taken. As shown in FIG. 9, HCP-N (CH) 2 CO 2 H) 2 For Pb 2+ The adsorption curve of (A) is very steep, indicating that HCP-N (CH) 2 CO 2 H) 2 For Pb 2+ Has strong affinity. Fitting of equilibrium adsorption isotherm and Langmuir modelGood, the correlation coefficient is as high as 0.999.
Notably, the calculated HCP-N (CH) 2 CO 2 H) 2 Has a removing ability of 1031mg g -1 (FIG. 10). To our knowledge, this removal of Pb 2+ Far exceeding the maximum absorption capacity reported for most different types of materials. Surprisingly, this particular ability is due to the high affinity of nitrogen and oxygen like EDTA functional groups, which are located in the porous HCP-N (CH) 2 CO 2 H) 2 The pore walls of the porous membrane are convenient for the chelating material to capture Pb (II) ions.
In addition to high capacity, HCP-N (CH) 2 CO 2 H) 2 The removal rate of Pb (II) in water is also very high. The coordination kinetics study adopted Pb (NO) 3 ) 2 (50mL,10ppm,pH＝7)，HCP-N(CH 2 CO 2 H) 2 (25mg) was performed at room temperature as shown in FIGS. 6 and 7. We observed that equilibrium removal performance was achieved in 1 hour, increasing the contact time to 10 hours removed more than 99.6% of the pb (ii) ions, and the material could be reduced from 10ppm to 0.038 ppm. This indicates that it has a great potential to purify drinking water below acceptable limits within one hour. The adsorption kinetics process is well fitted with a quasi-secondary kinetics model, and the expression is as follows:
wherein k is 2 (g mg –1 min –1 ) Is a pseudo second order adsorption rate constant, q t (mg g –1 ) Is Pb adsorbed at the time of time t (min) 2+ Amount of (a) q e (mg g -1 ) Is Pb adsorbed at equilibrium 2+ The amount of (c) is shown in fig. 8.
By fitting a pseudo-second order model, the correlation coefficient (R) 2 ) Is 1, adsorption rate constant (k) 2 ) 0.026g mg –1 min –1 . This value is superior to the currently reported BMmCs value (0.0135g mg –1 min –1 ) This is the rate for the same metal in the report is oftenNumber (k) 2 ) The optimum value of (1).
Evaluation of distribution coefficient:
coefficient of distribution (k) d ) Is a parameter that measures the affinity of the adsorbent for the target metal ion.
k d Is defined as:
wherein C is i Is the initial concentration of metal ions, C f Is the final equilibrium metal ion concentration, V is the volume of the treatment solution (mL), and m is the mass of the adsorbent (g) used. k is a radical of d Is an important aspect of the electrical adsorption performance index of any adsorbent metal, wherein K d Value 1.0x 10 5 mL g –1 Is generally considered to be excellent. The test results showed HCP-NCH 2 CO 2 H) 2 K adsorbing P (II) d Value of superior 5.24x 10 5 mL g –1 . This value is the highest reported value of Pb (II) adsorbed by adsorbents to date, and exceeds that reported for a range of reference materials, such as the developed alginate chitosan composite adsorbent (Alg-Chi) (5.88X 10) 3 mL g –1 ) And alginate-melamine mixed adsorbent (Alg-Mel) (8.2X 10) 3 mL g –1 )。
Evaluation of stability:
the stability of the material under severe conditions has high practical value. HCP-N (CH) 2 CO 2 H) 2 The chemical stability of (a) has been verified during the preparation process, showing that it has very good thermal stability. We note that this material exhibits good absorption capacity over a wide range of pH values (1-12), with the Pb (II) concentration decreasing from 10ppm to 2.4ppm and 0.04ppm at pH values 1 and 12, respectively, and that the change in absorption by the adsorbent at the various pH values shown in FIG. 11 may be related to the change in surface charge of the adsorbent. With increasing pH, Pb (II) is in HCP-N (CH) 2 CO 2 H) 2 The amount of adsorption of (2) is increased because the polymer surface is overall negatively charged, which is more favorablePb (II) adsorbed on HCP-N (CH) 2 CO 2 H) 2 The above. This increasing trend continues until the pH reaches neutrality and then reaches equilibrium without significant change. Due to HCP-N (CH) 2 CO 2 H) 2 Is very stable under harsh conditions, so a wide range of pH values is not HCP-N (CH) as other porous materials do 2 CO 2 H) 2 A practical application obstacle. This invention addresses these challenging problems by designing stable HCP materials.
Evaluation of cycle Performance:
for porous materials, the cycling performance is absolutely important for practical applications. Notably, HCP-N (CH) 2 CO 2 H) 2 Trapped Pb (II) in HNO 3 After washing with an aqueous solution (6.0M), the metal can be easily removed, and the metal can be eluted at 100%. The reclaimed polymeric material is then subjected to a subsequent round of pb (ii) removal. In particular, after four cycles, HCP-N (CH) 2 CO 2 H) 2 Does not significantly decrease in absorption capacity as shown in fig. 12. This result is much better than other porous materials, such as BMMCs, BAC and MPPs, which eventually lose their capacity during cycling.
And (3) selectivity evaluation:
selectivity is another important factor for the actual removal of pb (ii) from water. As shown in FIG. 13, HCP-N (CH) 2 CO 2 H) 2 Can remove toxic heavy metal ions such as Pb (II), Hg (II), Cd (II) and the like, but has no affinity to metals such as Mg (II), Na (I) and the like. HCP-N (CH) in comparison with alkali metal in a mixture of transition metal ions (Pb (II), Hg (II), Cd (II), Co (II), Fe (III) and Zn (II) and alkali metal ions (Mg (II) and Na (I)) having a pH of 7 and a single ion concentration of 10ppm 2 CO 2 H) 2 Maintaining higher efficiency for transition metals demonstrates that HCP-N (CH) provided by the invention 2 CO 2 H) 2 Has higher selectivity to transition metal. Pb (NO) 3 ) 2 (50mL) for further kinetic studies; 30ppm at room temperature, pH 7) and HCP-N (CH) 2 CO 2 H) 2 (25mg) (FIG. 14). On this basis, we observed that the score is less than 3The adsorption equilibrium is reached in a few minutes, more than 98% of Pb (II) is removed, and the material can be reduced from the high concentration of 30ppm to 0.6ppm in a few minutes. HCP-N (CH) shown in FIG. 15 2 CO 2 H) 2 And Pb @ HCP-N (CH) 2 CO 2 H) 2 The ultraviolet-visible absorption spectrum of (A) and the fluorescence spectrum shown in FIG. 16 indicate that Pb is present 2+ The signal of the loaded polymer is highly suppressed and is approximately the parent polymer HCP-N (CH) 2 CO 2 H) 2 Half of that. This indicates that there is a coordination reaction between the chelate surface and the metal ion.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The iminodiacetic acid functionalized hypercrosslinked polymer is characterized in that the hypercrosslinked polymer is prepared by hypercrosslinking iminodiacetic acid functionalized monomer, a cross-linking agent and a catalyst; the method specifically comprises the following steps: carrying out a hypercrosslinking reaction on an iminodiacetic acid functionalized monomer and a crosslinking agent through catalysis to obtain a hypercrosslinked prepolymer; post-synthesizing and modifying the hypercrosslinked prepolymer to obtain an iminodiacetic acid functionalized hypercrosslinked polymer; the cross-linking agent is 1, 4-p-xylylene ether; the catalyst is FeCl 3 (ii) a The monomer is dimethyl 2,2'- ([1,1' -diphenyl)]4-acetyl) diacetate.
2. The hypercrosslinked polymer of claim 1 wherein the pore size distribution of the hypercrosslinked polymer is 0.53-1.47 nm; and/or the surface area of the hypercrosslinked polymer is 400-480m 2 g –1 (ii) a And/or the pore volume of the hypercrosslinked polymer is 0.12-0.18cm 3 g –1 。
3. The process for preparing a hypercrosslinked polymer according to claim 1 or 2, characterized in that it comprises in particular the following steps: carrying out a hypercrosslinking reaction on an iminodiacetic acid functionalized monomer and a crosslinking agent through catalysis to obtain a hypercrosslinked prepolymer; and (3) carrying out post-synthesis and modification on the hypercrosslinked prepolymer to obtain the iminodiacetic acid functionalized hypercrosslinked polymer.
4. The method of claim 3, comprising:
(a) adding anhydrous ferric chloride into the solution of the monomer and the 1, 4-p-xylylene ether in the nitrobenzene, and uniformly mixing; heating at 60-80 deg.C for 4-5 hr, and refluxing at 120-125 deg.C under inert atmosphere for 24-36 hr to obtain hypercrosslinked prepolymer;
(b) the hypercrosslinking prepolymer and H 2 O and CH 3 CH 2 OH is mixed under stirring, the H 2 O and CH 3 CH 2 The volume ratio of OH is 2: 1; then 2N NaOH is added; continuously stirring for 24-36 hours at the temperature of 80-100 ℃, and carrying out post-treatment to obtain the super-crosslinked polymer.
5. The method of claim 4, comprising:
(a) adding anhydrous ferric chloride into the solution of the monomer and the 1, 4-p-xylylene ether in the nitrobenzene, and uniformly mixing; heating at 80 deg.C for 5 hr, and refluxing at 120 deg.C under inert atmosphere for 24 hr to obtain hypercrosslinked prepolymer;
(b) the hypercrosslinking prepolymer and H 2 O and CH 3 CH 2 OH is mixed under stirring, the H 2 O and CH 3 CH 2 The volume ratio of OH is 2: 1; then 2N NaOH is added; continuously stirring the mixture for 48 hours at the temperature of 80 ℃, and carrying out post-treatment to obtain the super-crosslinked polymer.
6. The method according to claim 5, wherein in the step (a), the monomer is usedThe preparation method comprises the following steps: 4-aminobiphenyl, NaI and proton sponge are taken as main raw materials, and the monomer is obtained through nucleophilic substitution reaction; the method comprises the following steps: placing 4-aminobiphenyl, NaI and proton sponge together; then the gas in the reaction bottle is pumped out and N is used 2 Displacement is carried out for three times; transferring the dried acetonitrile into the reaction mixture, and stirring at room temperature to dissolve reactants; adding methyl bromoacetate, refluxing, cooling to room temperature, and adding toluene; then filtering, washing and drying to obtain the product.
7. The production method according to claim 6,
in the step (a), after the reflux treatment, the method further comprises the steps of cooling the mixture to room temperature, sequentially filtering and washing the mixture with methanol, distilled water, dichloromethane and acetone until the filtrate is nearly colorless; performing Soxhlet extraction for purification, extracting with methanol for 24-36 hr, and extracting with dichloromethane for 24-36 hr; then freeze-drying the polymer for 24-48 hours; and/or
In the step (b), the post-treatment comprises the following steps: the precipitate was collected by filtration, using HCl and H, respectively 2 Washing for three times by using O, and washing for two days by using methanol and dichloromethane respectively by using a Soxhlet extraction method; and then freeze-drying to obtain the product.
8. The production method according to claim 7,
in the step (a), after the reflux treatment, the method further comprises the steps of cooling the mixture to room temperature, sequentially filtering and washing the mixture with methanol, distilled water, dichloromethane and acetone until the filtrate is nearly colorless; performing Soxhlet extraction purification, extracting with methanol for 24 hours, and extracting with dichloromethane for 36 hours; the polymer was then freeze dried for 24 hours; and/or
In the step (b), the post-treatment comprises the following steps: the precipitate was collected by filtration, using HCl and H, respectively 2 Washing for three times by using O, and washing for two days by using methanol and dichloromethane respectively by using a Soxhlet extraction method; and then freeze-drying to obtain the product.
9. Use of the iminodiacetic acid-functionalized hypercrosslinked polymer according to claim 1 or 2 for removing heavy metal ions.
10. The iminodiacetic acid-functionalized hypercrosslinked polymer of claim 1 or 2 for adsorbing Pb in aqueous solution 2+ The use of (1).
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| CN102603973A (en) * | 2012-03-07 | 2012-07-25 | 苏州大学 | High polymer with N-dicarboxyl in side chains and application thereof |
| WO2016147116A1 (en) * | 2015-03-19 | 2016-09-22 | Sol S.P.A. | A gas-adsorbing porous aromatic hyper-cross-linked polymer and a method of preparing thereof |
| CN107759796A (en) * | 2017-11-21 | 2018-03-06 | 齐鲁工业大学 | The preparation method of a kind of porous super cross-linked polymer |
| CN108940361A (en) * | 2018-08-02 | 2018-12-07 | 吉林大学 | A kind of chiral ion type porous organic polymer material and the preparation method and application thereof |
| CN109776764A (en) * | 2019-01-23 | 2019-05-21 | 北京化工大学 | A kind of super organic cross-linked polymeric object material, preparation method and application |
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| CN107709375B (en) * | 2015-06-22 | 2020-10-02 | 三菱化学株式会社 | Iminodiacetic acid type chelate resin and process for producing the same |
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| WO2016147116A1 (en) * | 2015-03-19 | 2016-09-22 | Sol S.P.A. | A gas-adsorbing porous aromatic hyper-cross-linked polymer and a method of preparing thereof |
| CN107759796A (en) * | 2017-11-21 | 2018-03-06 | 齐鲁工业大学 | The preparation method of a kind of porous super cross-linked polymer |
| CN108940361A (en) * | 2018-08-02 | 2018-12-07 | 吉林大学 | A kind of chiral ion type porous organic polymer material and the preparation method and application thereof |
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