CN116217853A - Covalent organic framework material for phthalate adsorption and preparation method and application thereof - Google Patents

Covalent organic framework material for phthalate adsorption and preparation method and application thereof Download PDF

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CN116217853A
CN116217853A CN202310233197.2A CN202310233197A CN116217853A CN 116217853 A CN116217853 A CN 116217853A CN 202310233197 A CN202310233197 A CN 202310233197A CN 116217853 A CN116217853 A CN 116217853A
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phthalate
acid
organic framework
framework material
covalent organic
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王丽艳
姜晓彤
唐艺旻
赵冰
李志刚
阚伟
王秀文
孙立
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Qiqihar University
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Abstract

A covalent organic framework material for phthalate adsorption and a preparation method and application thereof relate to a covalent organic framework material and a preparation method and application thereof. The method aims to solve the technical problems of few types, long adsorption time and low adsorption quantity of the existing phthalate adsorbent. The basic structural units of the covalent organic framework materials of the present invention are as follows:
Figure DDA0004121068050000011
it adopts 3- (5, 10-diamino-1H-phenanthro [9, 10-d)]Imidazole-2-yl) phenol and 4,4' - (phenyl-1, 3, 5-tri-yl) benzaldehyde to obtainA kind of electronic device. The covalent organic framework material is used as an adsorbent, and the content of phthalate in the wastewater is detected by a standard curve method, so that the covalent organic framework material can be used in the field of phthalate detection.

Description

Covalent organic framework material for phthalate adsorption and preparation method and application thereof
Technical Field
The invention relates to a covalent organic framework material, a preparation method and application thereof.
Background
Phthalate (PAE) is mainly used for polyvinyl chloride materials, so that the polyvinyl chloride is changed from hard plastic into elastic plastic, and the plastic acts as a plasticizer. It is commonly used in hundreds of products such as toys, food packaging materials, medical blood bags and tubes, vinyl floors and wallpaper, cleaners, lubricating oils, personal care products (e.g., nail polish, hair sprays, soaps, and shampoos), but these substances pollute the environment by the environment (water, air, and soil) or migrate from the packaging materials, causing health problems due to their toxicity. Therefore, the compounds are widely focused on the environmental science, the public health field, media and even the general public. Studies show that phthalate plays a role similar to female hormone in human and animal bodies, can interfere endocrine, seriously causes testicular cancer, and is a 'culprit' for causing male reproductive problems. Among cosmetics, the phthalate content of nail polish is highest, and many aromatic components of cosmetics also contain this substance. This material in cosmetics can enter the body through the respiratory system and skin of women, and if used too much, can increase the probability of breast cancer in women and can jeopardize the reproductive system of their future born male infants. Therefore, research into materials that can effectively remove phthalates is of great interest and is extremely challenging. Covalent organic framework materials (Covalent Organic Frameworks, COFs) have been focused by researchers because of their advantages of ordered pore structure, large specific surface area, uniform porosity, good chemical stability, and the like, and have broad application prospects in the adsorption field.
At present, the literature on adsorption of esters by covalent organic framework materials has been reported successively, and in 2019, volume 5 of J.chromatography A is reported to in-situ reduce nickel ions on a covalent triazine skeleton matrix by a solvothermal method to prepare a magnetic CTFs/Ni composite material, and under the optimal experimental condition, the detection limit (LOD, S/N=3) of six PAEs is found to be in the range of 0.024-0.085 mg/kg. Magnetic covalent organic framework adsorbents of co-precipitated structure were prepared using 4,4' -diamino-p-terphenyl and 1,3, 5-tricarbonyl-butylene-chloride as monomers as reported in volume 15, J.chromatography A, 2022. Under the optimized condition, the detection limit of the method is 0.8-2.1 mug/L, and the recovery rate is 76.8% -99.2%. The adsorption of phthalate in milk is realized, the adsorption time of dye is effectively reduced as a composite material, but the material synthesis and separation processes are complex.
According to the current literature reports, the existing functional materials for adsorbing phthalate mainly have the following defects:
1. the materials used for adsorbing phthalate are less in variety;
2. the adsorption time required by the adsorption of phthalate esters of most materials is long;
3. the adsorption quantity of the material to phthalic acid ester is low, and the adsorption effect is poor;
4. the materials required for adsorbing phthalates are complex to prepare.
Disclosure of Invention
The invention aims to solve the technical problems of few types, long adsorption time and low adsorption quantity of the existing phthalate adsorbent, and provides a covalent organic framework material for phthalate adsorption, a preparation method and application thereof. The covalent organic framework material has the advantages of short adsorption time and high adsorption quantity of the phthalate.
The basic structural unit of the covalent organic framework material for phthalate adsorption is as follows:
Figure BDA0004121068020000021
the covalent organic framework material for phthalate adsorption is prepared by reacting 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol with 4,4' - (phenyl-1, 3, 5-tri) benzaldehyde, and the specific preparation method comprises the following steps:
1. 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol, 4 '- (phenyl-1, 3, 5-triyl) benzaldehyde, an organic solvent I and an acid are sequentially added into a pyrex tube, wherein the mass ratio of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol to 4,4' - (phenyl-1, 3, 5-triyl) benzaldehyde is 1: (1-5);
2. performing liquid nitrogen freezing, vacuumizing and unfreezing operation on the pyrex tube, repeating the operation for 4-5 times, and sealing;
3. heating a pyrex tube to 100-180 ℃, reacting for 3-7 days, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with an organic solvent II, and carrying out vacuum drying to obtain the covalent organic framework material for phthalate adsorption.
Further, the preparation method of the 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol in the step one is carried out according to the following steps:
(1) Adding 1mL of concentrated sulfuric acid with the mass percentage of 95-98% and 2-10 mL of concentrated nitric acid with the mass percentage of 62-65% into a reaction container, fully mixing, cooling to below 0 ℃, adding 1-5 mg of 9, 10-phenanthrenequinone, and uniformly stirring to obtain a reaction mixture; heating the reaction mixture to 80-140 ℃, reacting for 3-8 hours, cooling to room temperature, pouring into ice water, adjusting the pH to be neutral by adopting a sodium hydroxide solution with the mass percent of 1-10%, collecting yellow solid, and drying to obtain dry yellow solid;
(2) Sequentially adding 2mg of dry yellow solid, 0.2-1.0 mg of ammonium acetate, 0.2-1.0 mg of 3-hydroxybenzaldehyde, 0.5-3 mL of acid and 5-20 mL of organic solvent III into a reaction vessel, reacting for 10-24 hours at the temperature of 80-120 ℃, cooling to room temperature, regulating the pH to be neutral by adopting a sodium hydroxide solution with the mass percentage of 1-10%, collecting red solid, and drying to obtain dry red solid; the acid is any one of glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, concentrated hydrochloric acid with the mass percentage concentration of 30-37% and concentrated sulfuric acid with the mass percentage concentration of 95-98%; the organic solvent III is any one of N, N-dimethylformamide, benzene, ethanol, dimethylbenzene, chlorobenzene, o-dichlorobenzene, acetic acid or N-butanol;
(3) Sequentially adding 2mg of dry red solid, 0.5-2 mg of Raney nickel, 10-30 mL of hydrazine hydrate with the mass percentage of 45% and 5-20 mL of organic solvent IV into a reaction container, reacting for 10-36H at the temperature of 60-120 ℃, cooling to room temperature, filtering, collecting gray solid, and drying to obtain 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol; the organic solvent IV is any one of ethanol, acetonitrile, tetrahydrofuran, o-dichlorobenzene, N-butanol, N-dimethylacetamide or acetone.
Further, the organic solvent I in the first step is any two solvents selected from mesitylene, tetrahydrofuran, o-dichlorobenzene, N-butanol, N-dimethylformamide, p-dimethylaminopyridine and dioxane.
Further, the ratio of the mass of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol to the volume of the organic solvent I in the step one is 1mg: (1-4) mL.
Further, the acid in the first step is one or a combination of any two of glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, concentrated hydrochloric acid with the mass percentage concentration of 30-37% and concentrated sulfuric acid with the mass percentage concentration of 95-98%.
Still further, the mass to acid volume ratio of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol of step one is 1mg: (0.05-1.0) mL.
Further, the organic solvent II for washing the filter cake in the third step is methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, o-dichlorobenzene, N-butanol, N-dimethylacetamide or acetone.
The preparation process of the covalent organic framework material for phthalate adsorption of the invention is represented by the following formula:
Figure BDA0004121068020000041
the covalent organic framework material for phthalate adsorption is used as an adsorbent, the content of phthalate in the wastewater is detected by a standard curve method, and the phthalate in the wastewater is quantitatively analyzed.
The covalent organic framework material for phthalate adsorption is used as an adsorbent, a high performance liquid chromatography is adopted to draw a standard curve, and the content of phthalate in the wastewater is detected by the high performance liquid chromatography against the standard curve, and the specific method is as follows:
1. respectively preparing phthalate aqueous solutions with the concentration of 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L and 100 mg/L;
2. respectively measuring retention time and absorption peak intensity of the phthalate solution with different concentrations by adopting high performance liquid chromatography; recording the absorption peak intensities of phthalate esters with different concentrations under the respective retention time, and drawing a standard curve of phthalate ester concentration-absorption peak intensity;
3. taking 10mL of waste water containing phthalate, adding 1-3 mg of covalent organic framework material for phthalate adsorption into the waste water, and uniformly mixing to obtain a solution to be detected;
4. measuring high performance liquid chromatography of the solution to be measured, recording the absorption peak intensity of phthalate corresponding to retention time, and recording as I A ；
5. Lookup I against a standard curve A The corresponding phthalate concentration is obtainedTo the phthalate concentration in the solution to be tested.
Further, in the step one, the phthalate aqueous solution is any one of deionized water, high-purity water or secondary distilled water;
further, the phthalate is dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP) or di (2-ethylhexyl) phthalate (DEHP), respectively.
The covalent organic framework material for phthalate adsorption has the advantages of simple, efficient and easy operation, the adsorption equilibrium time of dimethyl terephthalate is 90min, and the maximum adsorption quantity is 167 mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The adsorption equilibrium time of diethyl phthalate is 70min, and the maximum adsorption capacity is 136 mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The adsorption equilibrium time of dibutyl phthalate is 60min, and the maximum adsorption quantity is 106 mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The adsorption equilibrium time of the terephthalic acid di (2-ethylhexyl) ester is 100min, and the maximum adsorption quantity is 105 mg.g -1 The adsorption effect is good. Can be used in the field of phthalate detection.
Drawings
FIG. 1 is an infrared spectrum of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol prepared in example step one;
FIG. 2 is a schematic illustration of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] prepared in example step one]Imidazol-2-yl) phenol 1 HNMR spectrogram;
FIG. 3 is a schematic illustration of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] prepared in example step one]Imidazol-2-yl) phenol 13 CNMR spectrogram;
FIG. 4 is an infrared spectrum of a covalent organic framework material for phthalate adsorption prepared in example 1;
FIG. 5 is a graph of nitrogen adsorption and desorption for covalent organic framework materials for phthalate adsorption prepared in example 1;
FIG. 6 is an adsorption isotherm plot of different concentrations of phthalate solutions detected by high performance liquid chromatography for covalent organic framework materials for phthalate adsorption.
Fig. 7 is a graph of adsorption kinetics of covalent organic framework material terephthalic acid esters for phthalate adsorption prepared in example 1.
Detailed Description
The beneficial effects of the invention are verified by the following examples:
example 1: the preparation method of the covalent organic framework material for phthalate adsorption in the embodiment is carried out according to the following steps:
1. firstly, preparing 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazole-2-yl) phenol, wherein the specific method comprises the following steps:
(1) Adding 1mL of 98% by mass of concentrated sulfuric acid and 5mL of 65% by mass of concentrated nitric acid into a reaction container, fully mixing, cooling to below 0 ℃, adding 2mg of 9, 10-phenanthrenequinone, and uniformly stirring to obtain a reaction mixture; heating the reaction mixture to 100 ℃, reacting for 6 hours, cooling to room temperature, pouring into ice water, adjusting the pH to be neutral by adopting a sodium hydroxide solution with the mass percent of 5%, collecting yellow solid, and drying to obtain dry yellow solid;
(2) Sequentially adding 2mg of dry yellow solid, 0.5mg of ammonium acetate, 0.5mg of 3-hydroxybenzaldehyde, 2mL of glacial acetic acid and 20mLN, N-dimethylformamide into a reaction vessel, reacting for 20 hours at 100 ℃, cooling to room temperature, adjusting the pH to be neutral by adopting a sodium hydroxide solution with the mass percent of 5%, collecting a red solid, and drying to obtain a dry red solid;
(3) Sequentially adding 2mg of dry red solid, 1mg of Raney nickel, 20mL of hydrazine hydrate with the mass percentage of 45% and 20mL of N, N-dimethylacetamide into a reaction vessel, reacting for 24 hours at the temperature of 100 ℃, cooling to room temperature, filtering, collecting gray solid, and drying to obtain 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol;
2. 2mg of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol and 2mg of 4,4' - (phenyl-1, 3, 5-triyl) trityl aldehyde are added to a mixture of 1mL of mesitylene and 1mL of N, N-dimethylformamide, and the mixture is added to a pyrex tube, and then 0.2mL of glacial acetic acid is added as a catalyst, and the mixture is subjected to ultrasonic mixing to obtain a reaction mixture;
3. performing liquid nitrogen freezing, vacuumizing and unfreezing circulation operation on the pyrex tube, repeating the operation for 4 times, and sealing;
4. heating a pyrex tube to 120 ℃ for reaction for 72h; cooling to room temperature after the reaction is finished to obtain a reaction product;
5. and (3) carrying out suction filtration on the reaction product, repeatedly washing a filter cake by using ethanol and methanol in sequence, and carrying out vacuum drying to obtain the covalent organic framework material for phthalate adsorption, wherein the yield of the covalent organic framework material is 86% through calculation.
3- (5, 10-diamino-1H-phenanthro [9,10-d ] prepared in step one of this example]The IR spectrum of imidazol-2-yl) phenol is shown in FIG. 1, IR (KBr, cm –1 ):3354,1625,1521,1477,1268,950,815,712。
3- (5, 10-diamino-1H-phenanthro [9,10-d ] prepared in step one of this example]Imidazol-2-yl) phenol 1 The H NMR spectrum is shown in figure 2, 1 H NMR(600MHz,DMSO-d 6 )δ13.02(s,1H),9.67(s,1H),8.24(d,J＝11.6Hz,2H),7.79–7.66(m,3H),7.58(s,1H),7.46(s,1H),7.35(t,J＝7.8Hz,1H),6.86(d,J＝9.1Hz,4H),5.27(s,5H)。
3- (5, 10-diamino-1H-phenanthro [9,10-d ] prepared in step one of this example]Imidazol-2-yl) phenol 13 The C NMR spectrum is shown in FIG. 3, 13 C NMR(151MHz,DMSO-d 6 )δ158.18(s),148.52(s),146.52(d,J＝37.5Hz),137.36–135.56(m),132.55(s),130.30(s),127.98(s),127.11(s),123.89(d,J＝47.5Hz),122.40(s),120.08(d,J＝60.6Hz),117.27(s),116.38(s),115.19(d,J＝65.6Hz),113.29(s),104.34(s)。
from the infrared and nuclear magnetic test results, 3- (5, 10-diamino-1H-phenanthro [9, 10-d)]Imidazol-2-yl) phenol has the structural formula:
Figure BDA0004121068020000071
for more clear determination of phthalateThe structure of the adsorbed covalent organic framework material was subjected to infrared spectroscopic test on the covalent organic framework material prepared in example 1, the obtained infrared spectroscopic spectrum is shown in fig. 4, and the test result was analyzed. As can be seen from FIG. 4, the covalent organic framework is at 1685cm -1 And 1604cm -1 There are two characteristic peaks belonging to the asymmetric and symmetric vibration of the c=o group on the imine ring, the c=o group being derived from 4,4',4"- (phenyl-1, 3, 5-triyl) trityl aldehyde, at 1465cm -1 The peak value is the stretching vibration of C-N-C bond, and the imide bond is 3- (5, 10-diamino-1H-phenanthro [9, 10-d)]Imidazol-2-yl) phenol-NH 2 And 4,4', 4' - (phenyl-1, 3, 5-triyl) benzaldehyde. From infrared data analysis, example 1 successfully produced covalent organic framework materials.
Fig. 5 is a graph of nitrogen adsorption and desorption of covalent organic framework materials for phthalate adsorption prepared in example 1. The nitrogen adsorption curve increases rapidly in the relative pressure range of 0.1-0.3, and increases sharply in the relative pressure range of 0.8-1.0. According to IUPAC classification, the nitrogen adsorption-desorption isotherm of the covalent organic framework material for phthalate adsorption prepared in this example shows a type iv curve, indicating that the material is mesoporous and can illustrate the highly ordered arrangement of such pore structures.
The covalent organic framework material for phthalate adsorption is used as an adsorbent, a high performance liquid chromatography is adopted to draw a standard curve, and the content of phthalate in the wastewater is detected by the high performance liquid chromatography against the standard curve, and the specific method is as follows:
1. preparing dimethyl phthalate (DMP) aqueous solutions with the concentration of 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L and 100mg/L respectively;
2. and respectively measuring the retention time and the absorption peak intensity of the dimethyl phthalate solution with different concentrations by adopting high performance liquid chromatography. Recording the absorption peak intensities of the dimethyl phthalate with different concentrations under the corresponding retention time respectively, and drawing standard curves of the concentration-absorption peak intensities of the dimethyl phthalate respectively;
3. taking 10mL of waste water containing dimethyl phthalate, and adding 1-3 mg of covalent organic framework material for phthalate adsorption into the waste water to obtain a solution to be detected;
4. measuring high performance liquid chromatography of the solution to be measured, recording the absorption peak intensity of dimethyl phthalate corresponding to retention time, and recording as I A ；
5. Lookup I against a standard curve A The corresponding concentration of the dimethyl phthalate is recorded as the concentration of the dimethyl phthalate in the solution to be detected;
6. the above experiment was repeated with dimethyl phthalate (DMP) replaced with diethyl phthalate (DEP), dibutyl phthalate (DBP) and di (2-ethylhexyl) phthalate (DEHP), respectively.
Using formula q e ＝V(c 0 -c e ) M calculates the equilibrium adsorption of the covalent organic framework material for phthalate adsorption to phthalate, wherein q e (mg·g -1 ) Represents the equilibrium adsorption quantity, q, of the covalent organic framework material for phthalate adsorption to phthalate e Is expressed in mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the V represents the volume of the solution to be tested containing phthalate in the fourth step, and the unit of V is L; c 0 Represents the initial concentration of phthalate in mg.L -1 ；c e Represents the equilibrium concentration of phthalate esters in mg.L when adsorption reaches equilibrium -1 The method comprises the steps of carrying out a first treatment on the surface of the m represents the mass of the covalent organic framework material for phthalate adsorption in g.
FIG. 6 is an adsorption isotherm of a covalent organic framework material for phthalate adsorption to phthalate esters of different concentrations, with the concentration of phthalate esters in solution at equilibrium on the abscissa and the amount of equilibrium adsorbed on the ordinate. As can be seen from fig. 6, the equilibrium adsorption amount of the covalent organic framework material for phthalate adsorption to phthalate shows an increasing trend with increasing phthalate concentration. When the equilibrium adsorption concentration is 300mg/L, the method reachesThe adsorption equilibrium, the equilibrium adsorption capacity of the dimethyl phthalate can reach 155 mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The equilibrium adsorption capacity of diethyl phthalate can reach 125 mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The equilibrium adsorption capacity of dibutyl phthalate can reach 122 mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The equilibrium adsorption capacity of the di (2-ethylhexyl) phthalate can reach 106 mg.g -1 . These results demonstrate that the covalent organic framework material for phthalate adsorption provided in this example can reach adsorption equilibrium in a short time, and the equilibrium adsorption amount is high, so that the covalent organic framework material can be used for measuring phthalate concentration in wastewater.
Fig. 7 is a graph of adsorption kinetics of covalent organic framework material terephthalic acid esters for phthalate adsorption prepared in example 1. As can be seen from fig. 7, the adsorption amount of the covalent organic framework material for phthalate adsorption gradually increases with the increase of the adsorption time. The adsorption is rapid within 0-60 min, and the adsorption rate is high; the adsorption rate is slowed down in 60-90 min; and when the adsorption time is 90min, the adsorption reaches a saturated state. The adsorption time is then continued to increase and the adsorption amount remains substantially constant. This adsorption phenomenon is mainly due to intermolecular hydrogen bonding of hydroxyl functional groups in the covalent organic framework material for phthalate adsorption with phthalate formation.
Example 2: the preparation method of the covalent organic framework material for phthalate adsorption in the embodiment is carried out according to the following steps:
1. the preparation method of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol is the same as that of example 1 to obtain 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol;
2mg of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol and 4mg of 4,4' - (phenyl-1, 3, 5-triyl) trityl aldehyde are added to a mixture of 1mL of dioxane and 2mL of N, N-dimethylformamide, and the mixture is added to a pyrex tube, and 0.5mL of benzenesulfonic acid is added as a catalyst, followed by ultrasonic mixing to obtain a reaction mixture;
2. performing liquid nitrogen freezing, vacuumizing and unfreezing circulation operation on the pyrex tube, repeating the operation for 4 times, and sealing;
3. heating the pyrex tube to 100 ℃ for reaction for 80 hours; cooling to room temperature after the reaction is finished to obtain a reaction product;
4. filtering the reaction product, repeatedly washing a filter cake by acetonitrile and tetrahydrofuran in sequence, and vacuum drying to obtain the covalent organic framework material for phthalate adsorption, wherein the yield is as follows: 79%.
Example 3: the preparation method of the covalent organic framework material for phthalate adsorption in the embodiment is carried out according to the following steps:
1. the preparation method of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol is the same as that of example 1 to obtain 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol;
2mg of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol and 6mg of 4,4' - (phenyl-1, 3, 5-triyl) trityl aldehyde are added to a mixture of 2mL of chlorobenzene and 1mL of isoquinoline, and the mixture is added to a pyrex tube, and then 0.3mL of trifluoroacetic acid is added as a catalyst, and the mixture is ultrasonically mixed to obtain a reaction mixture;
2. performing liquid nitrogen freezing, vacuumizing and unfreezing circulation operation on the pyrex tube, repeating the operation for 4 times, and sealing;
3. heating a pyrex tube to 130 ℃ for reaction for 90h; cooling to room temperature after the reaction is finished to obtain a reaction product;
4. filtering the reaction product, repeatedly washing a filter cake with dichloromethane in sequence, and vacuum drying to obtain the covalent organic framework material for phthalate adsorption, wherein the yield is as follows: 70%.
Example 4: the preparation method of the covalent organic framework material for phthalate adsorption in the embodiment is carried out according to the following steps:
1. the preparation method of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol is the same as that of example 1 to obtain 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol;
2mg of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol and 8mg of 4,4' - (phenyl-1, 3, 5-triyl) trityl aldehyde are added to a mixture of 2mL of n-butanol and 2mL of N, N-dimethylformamide, and the mixture is added to a pyrex tube, and 1.0mL of p-toluenesulfonic acid is added as a catalyst, and the mixture is subjected to ultrasonic mixing to obtain a reaction mixture;
2. performing liquid nitrogen freezing, vacuumizing and unfreezing circulation operation on the pyrex tube, repeating the operation for 4 times, and sealing;
3. heating a pyrex tube to 160 ℃ for reaction for 100h; cooling to room temperature after the reaction is finished to obtain a reaction product;
4. filtering the reaction product, repeatedly washing a filter cake with ethanol and methanol in sequence, and vacuum drying to obtain the covalent organic framework material for phthalate adsorption, wherein the yield is as follows: 82%.
Example 5: the preparation method of the covalent organic framework material for phthalate adsorption in the embodiment is carried out according to the following steps:
1. the preparation method of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol is the same as that of example 1 to obtain 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol;
2mg of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol and 10mg of 4,4' - (phenyl-1, 3, 5-triyl) trityl aldehyde are respectively added into a mixture of 2mL of nitrogen methyl pyrrolidone and 3mL of N, N-dimethylformamide, the mixture is added into a pyrex tube, and then 0.5mL of concentrated hydrochloric acid with the mass percentage concentration of 30% -37% is added as a catalyst, and the mixture is subjected to ultrasonic mixing uniformly to obtain a reaction mixture;
2. performing liquid nitrogen freezing, vacuumizing and unfreezing circulation operation on the pyrex tube, repeating the operation for 4 times, and sealing;
3. heating a pyrex tube to 180 ℃ for reaction for 120h; cooling to room temperature after the reaction is finished to obtain a reaction product;
4. filtering the reaction product, repeatedly washing a filter cake with ethanol and methanol in sequence, and vacuum drying to obtain the covalent organic framework material for phthalate adsorption, wherein the yield is as follows: 68%.
Example 6: the preparation method of the covalent organic framework material for phthalate adsorption in the embodiment is carried out according to the following steps:
1. the preparation method of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol is the same as that of example 1 to obtain 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol;
2mg of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol and 10mg of 4,4' - (phenyl-1, 3, 5-triyl) trityl aldehyde are respectively added into a mixture of 2mL of nitrogen methyl pyrrolidone and 2mL of isoquinoline, the mixture is added into a pyrex tube, and then 0.5mL of concentrated sulfuric acid with the mass percentage concentration of 95% -98% is added as a catalyst, and the mixture is ultrasonically mixed uniformly to obtain a reaction mixture;
2. performing liquid nitrogen freezing, vacuumizing and unfreezing circulation operation on the pyrex tube, repeating the operation for 4 times, and sealing;
3. heating a pyrex tube to 160 ℃ for reaction for 150 hours; cooling to room temperature after the reaction is finished to obtain a reaction product; 4. filtering the reaction product, repeatedly washing a filter cake with ethanol and methanol in sequence, and vacuum drying to obtain the covalent organic framework material for phthalate adsorption, wherein the yield is as follows: 65%.

Claims (10)

1. A covalent organic framework material for phthalate adsorption, characterized in that the basic structural units of the material are as follows:
Figure FDA0004121068010000011
2. a process for preparing a covalent organic framework material for phthalate adsorption according to claim 1 characterized in that the process is carried out as follows:
1. 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol, 4 '- (phenyl-1, 3, 5-triyl) benzaldehyde, an organic solvent I and an acid are sequentially added into a pyrex tube, wherein the mass ratio of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol to 4,4' - (phenyl-1, 3, 5-triyl) benzaldehyde is 1: (1-5);
2. performing liquid nitrogen freezing, vacuumizing and unfreezing operation on the pyrex tube, repeating the operation for 4-5 times, and sealing;
3. heating a pyrex tube to 100-180 ℃, reacting for 3-7 days, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with an organic solvent II, and carrying out vacuum drying to obtain the covalent organic framework material for phthalate adsorption.
3. A method for covalent organic framework material for phthalate adsorption according to claim 2 characterized in that said method for preparing 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol in step one is performed by the steps of:
(1) Adding 1mL of concentrated sulfuric acid with the mass percentage of 95-98% and 2-10 mL of concentrated nitric acid with the mass percentage of 62-65% into a reaction container, fully mixing, cooling to below 0 ℃, adding 1-5 mg of 9, 10-phenanthrenequinone, and uniformly stirring to obtain a reaction mixture; heating the reaction mixture to 80-140 ℃, reacting for 3-8 hours, cooling to room temperature, pouring into ice water, adjusting the pH to be neutral by adopting a sodium hydroxide solution with the mass percent of 1-10%, collecting yellow solid, and drying to obtain dry yellow solid;
(2) Sequentially adding 2mg of dry yellow solid, 0.2-1.0 mg of ammonium acetate, 0.2-1.0 mg of 3-hydroxybenzaldehyde, 0.5-3 mL of acid and 5-20 mL of organic solvent III into a reaction vessel, reacting for 10-24 hours at the temperature of 80-120 ℃, cooling to room temperature, regulating the pH to be neutral by adopting a sodium hydroxide solution with the mass percentage of 1-10%, collecting red solid, and drying to obtain dry red solid; the acid is any one of glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, concentrated hydrochloric acid with the mass percentage concentration of 30-37% and concentrated sulfuric acid with the mass percentage concentration of 95-98%; the organic solvent III is any one of N, N-dimethylformamide, benzene, ethanol, dimethylbenzene, chlorobenzene, o-dichlorobenzene, acetic acid or N-butanol;
(3) Sequentially adding 2mg of dry red solid, 0.5-2 mg of Raney nickel, 10-30 mL of hydrazine hydrate with the mass percentage of 45% and 5-20 mL of organic solvent IV into a reaction container, reacting for 10-36H at the temperature of 60-120 ℃, cooling to room temperature, filtering, collecting gray solid, and drying to obtain 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol; the organic solvent IV is any one of ethanol, acetonitrile, tetrahydrofuran, o-dichlorobenzene, N-butanol, N-dimethylacetamide or acetone.
4. A method for covalent organic framework material for phthalate adsorption according to claim 1 or 2 characterized in that said organic solvent i of step one is a mixture of mesitylene, tetrahydrofuran, o-dichlorobenzene, N-butanol, N-dimethylformamide and any two solvents of p-dimethylaminopyridine and dioxane.
5. A method for covalent organic framework material for phthalate adsorption according to claim 1 or 2 characterized in that the ratio of the mass of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol to the volume of organic solvent i of step one is 1mg: (1-4) mL.
6. A method for covalent organic framework material for phthalate adsorption according to claim 1 or 2, characterized in that the acid in step one is one of glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, concentrated hydrochloric acid with a mass percentage concentration of 30-37% and concentrated sulfuric acid with a mass percentage concentration of 95-98% or a combination of any two thereof.
7. A method for phthalate adsorbed covalent organic framework material according to claim 1 or 2 wherein in step one said ratio of mass of 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol to volume of acid is 1mg: (0.05-1.0) mL.
8. A method for covalent organic framework material for phthalate adsorption according to claim 1 or 2, characterized in that in step three said organic solvent ii for washing the filter cake is methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, o-dichlorobenzene, N-butanol, N-dimethylacetamide or acetone.
9. Use of the covalent organic framework material for phthalate adsorption according to claim 1 characterized in that it is used as adsorbent for quantitative analysis of phthalate in wastewater by detecting the content of phthalate in wastewater by standard curve method.
10. The use of the covalent organic framework material for phthalate adsorption according to claim 9, characterized in that the covalent organic framework material for phthalate adsorption is used as an adsorbent, a standard curve is drawn by high performance liquid chromatography, and the phthalate content in the wastewater is detected by high performance liquid chromatography against the standard curve by the following specific method:
(1) Adding 1mL of concentrated sulfuric acid with the mass percentage of 95-98% and 2-10 mL of concentrated nitric acid with the mass percentage of 62-65% into a reaction container, fully mixing, cooling to below 0 ℃, adding 1-5 mg of 9, 10-phenanthrenequinone, and uniformly stirring to obtain a reaction mixture; heating the reaction mixture to 80-140 ℃, reacting for 3-8 hours, cooling to room temperature, pouring into ice water, adjusting the pH to be neutral by adopting a sodium hydroxide solution with the mass percent of 1-10%, collecting yellow solid, and drying to obtain dry yellow solid;
(2) Sequentially adding 2mg of dry yellow solid, 0.2-1.0 mg of ammonium acetate, 0.2-1.0 mg of 3-hydroxybenzaldehyde, 0.5-3 mL of acid and 5-20 mL of organic solvent III into a reaction vessel, reacting for 10-24 hours at the temperature of 80-120 ℃, cooling to room temperature, regulating the pH to be neutral by adopting a sodium hydroxide solution with the mass percentage of 1-10%, collecting red solid, and drying to obtain dry red solid; the acid is any one of glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, concentrated hydrochloric acid with the mass percentage concentration of 30-37% and concentrated sulfuric acid with the mass percentage concentration of 95-98%; the organic solvent III is any one of N, N-dimethylformamide, benzene, ethanol, dimethylbenzene, chlorobenzene, o-dichlorobenzene, acetic acid or N-butanol;
(3) Sequentially adding 2mg of dry red solid, 0.5-2 mg of Raney nickel, 10-30 mL of hydrazine hydrate with the mass percentage of 45% and 5-20 mL of organic solvent IV into a reaction container, reacting for 10-36H at the temperature of 60-120 ℃, cooling to room temperature, filtering, collecting gray solid, and drying to obtain 3- (5, 10-diamino-1H-phenanthro [9,10-d ] imidazol-2-yl) phenol; the organic solvent IV is any one of ethanol, acetonitrile, tetrahydrofuran, o-dichlorobenzene, N-butanol, N-dimethylacetamide or acetone.
CN202310233197.2A 2023-03-13 2023-03-13 Covalent organic framework material for phthalate adsorption and preparation method and application thereof Pending CN116217853A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115029731B (en) * 2022-07-18 2024-02-09 齐齐哈尔大学 Heteroatom doped covalent organic framework material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115029731B (en) * 2022-07-18 2024-02-09 齐齐哈尔大学 Heteroatom doped covalent organic framework material and preparation method and application thereof

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