CN110204721B - Linear porphyrin-based polymer and preparation method and application thereof - Google Patents
Linear porphyrin-based polymer and preparation method and application thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011941 photocatalyst Substances 0.000 claims abstract description 25
- GAKFXHZPQGSWHQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol;hydrochloride Chemical compound Cl.NC1=CC(N)=C(O)C=C1O GAKFXHZPQGSWHQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 64
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- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical group C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000126 substance Substances 0.000 description 15
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 14
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- 229910052799 carbon Inorganic materials 0.000 description 13
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 11
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- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
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- SSOLNOMRVKKSON-UHFFFAOYSA-N proguanil Chemical compound CC(C)\N=C(/N)N=C(N)NC1=CC=C(Cl)C=C1 SSOLNOMRVKKSON-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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Abstract
Linear porphyrin-based polymer and a preparation method and application thereof belong to the technical field of functional polymer materials. The invention aims to obtain a photocatalyst which has high catalytic activity, is easy to recover and can be repeatedly used and reduce secondary pollution, and the photocatalyst is used for photocatalytic degradation of organic pollutants. The linear porphyrin-based polymer is linear polyphenylporphyrin benzobisoxazole. The preparation method is that 5, 15-p- (4-carboxyl phenyl) -10, 20-diphenyl porphyrin and 4, 6-diamino resorcinol (hydrochloride) are subjected to high molecular condensation polymerization to form the polymer. The linear porphyrin-based polymer can be used as a photocatalyst for photocatalytic degradation of organic pollutants. On one hand, the expanded pi conjugated system increases the optical contact area and improves the photocatalytic activity; on the other hand, the insolubility of the material is increased, so that after the photocatalytic degradation treatment is finished, the photocatalyst is easily separated from the photocatalytic system and reused after being recovered, the secondary pollution is reduced, and the industrial cost is further reduced.
Description
Technical Field
The invention relates to the technical field of polymer preparation, in particular to a linear porphyrin-based polymer, a preparation method and application thereof, and the linear porphyrin-based polymer is a novel porphyrin-based polymer with a linear structure, which is formed by the high-molecular polycondensation reaction of 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin and 4, 6-diaminoresorcinol (hydrochloride), can be used as a photocatalyst for photocatalytic degradation of organic pollutants, and belongs to the technical field of functional high-molecular materials.
Background
With the rapid development of industry, a large amount of organic pollutants which are not subjected to nontoxic and harmless treatment are directly discharged into rivers, lakes and seas, so that serious environmental pollution is caused, serious harm is caused to the health of people, and even canceration is induced. In recent years, the state has been strongly advocated to protect the environment and maintain ecological balance, meanwhile, experts and scholars have also conducted intensive discussion and research on how to solve the problem of environmental pollution, and developed various methods for treating organic pollutants, and among various feasible environmental protection technologies, the photocatalytic technology is considered to be a green and sustainable organic pollutant treatment technology. By utilizing sunlight, not only can toxic and harmful organic pollutants be efficiently degraded into nuisanceless carbon dioxide, water and the like in a photocatalytic manner, but also the treatment cost is lower.
The photocatalytic technology is not independent of the development of photocatalysts, and porphyrin compounds can effectively absorb visible light and near infrared light in sunlight among numerous organic photocatalysts, and meanwhile, the porphyrin compounds have excellent capacity of generating active oxygen, and are widely used for photocatalytic degradation of organic pollutants as an excellent photocatalyst. However, since porphyrin itself is easily aggregated into a polymer, the catalytic activity is decreased. In addition, porphyrin as a small molecular homogeneous catalyst is difficult to separate and recover after photocatalytic degradation reaction, and secondary pollution is easily caused, and the defects limit the application of porphyrin in the field of catalysis.
Disclosure of Invention
The invention provides a linear porphyrin-based polymer and a preparation method and application thereof, in order to obtain a photocatalyst which has high catalytic activity, is easy to recover, can be repeatedly used and can reduce secondary pollution and is used for photocatalytic degradation of organic pollutants.
The linear porphyrin-based polymer is characterized in that the minimum repeating unit is tetraphenylporphyrin connected with benzobisoxazole, and the structural formula is as follows:
wherein the polymerization degree n is an integer, n is more than 1 and less than 100, preferably n is more than or equal to 11 and less than or equal to 14, the morphology is granular, and the particle diameter is 90 nm.
The preparation method of the linear porphyrin-based polymer is characterized by comprising the following steps:
the compound is prepared by dehydrating 5, 15-p- (4-carboxyl phenyl) -10, 20-diphenyl porphyrin and 4, 6-diamino resorcinol hydrochloride through polycondensation reaction.
Preferably, the preparation method specifically comprises the following steps:
step 2, after the reaction is finished and the temperature of the reaction bottle is reduced to room temperature, adding deionized water into the reaction bottle to wash polyphosphoric acid and 4,6 diaminoresorcinol hydrochloride, and simultaneously using pH test paper to test until the washing liquid in the filter flask is neutral; repeatedly washing the reactant with DMF to remove residual 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin in the reactant; repeatedly washing the product with deionized water and then carrying out suction filtration;
Preferably, in the preparation method, the molar ratio of the 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin to the 4, 6-diaminoresorcinol hydrochloride is 1-1.1: 1.
the invention also provides an application of the linear porphyrin-based polymer, and the linear porphyrin-based polymer is used as a photocatalyst for photocatalytic degradation of organic pollutants.
The invention has the technical effects that:
the linear porphyrin-based polymer, namely the linear polyphenylporphyrin benzobisoxazole, can be used as a heterogeneous photocatalyst, so that on one hand, an expanded pi conjugated system increases the optical contact area and improves the photocatalytic activity; on the other hand, the insolubility of the material is increased, so that after the photocatalytic degradation treatment is finished, the photocatalyst is easily separated from the photocatalytic system and reused after being recovered, the secondary pollution is reduced, and the industrial cost is further reduced. FIG. 1 is an infrared spectrum of a polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention, from which 1606cm was observed-1The new absorption peak is attributed to the C ═ N stretching vibration of the oxazole ring in the polymer formed after the reaction. Furthermore, at 1230 and 1078cm-1A vibration band occurs, which is attributed to C-N and ═ C-O-C on the oxazole ring, respectively. The above results demonstrate that polyphenylporphyrin benzobisoxazole has been successfully obtained. FIG. 2 is a solid-state nuclear magnetic carbon spectrum of the polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention, wherein the numbers marked at different chemical shifts in the carbon spectrum respectively correspond to the carbon atoms at the numbers in the structural formula, and the chemical shift is 127ppm, which belongs to the carbon sub-peak of the benzene ring on the porphyrin; chemical shifts of 95 ppm and 111ppm, which are respectively assigned to carbon sub-peaks at positions 3 and 7 on the benzene ring; chemical shifts 139 and 153ppm, which are assigned to the carbon sub-peaks at positions 6,8 and 2,4, respectively; chemical shift 162ppm, assigned to the carbon sub-peak at 1,5 position on the oxazole ring. The above results indicate that the present invention has successfully prepared polyphenylporphyrin benzobisoxazole.
The preparation method of the linear porphyrin-based polymer provided by the invention is a novel porphyrin-based polymer with a linear structure, which is formed by the high-molecular polycondensation reaction of 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin and 4, 6-diaminoresorcinol hydrochloride, the polymer can be used as a photocatalyst for photocatalytic degradation of organic pollutants, and the catalyst has the advantages of being recyclable and reusable, and has potential application prospects.
The linear porphyrin-based polymer can be used as a photocatalyst for photocatalytic degradation of organic pollutants. FIG. 4 shows the ultraviolet-visible absorption spectrum of the polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention as a heterogeneous photocatalyst, and hydrogen peroxide as an oxygen promoter under visible light conditions to photocatalytically degrade rhodamine B, an organic pollutant. It can be seen from the spectrum that with the increase of time, under the action of the polyphenylporphyrin benzobisoxazole photocatalyst, the organic pollutant rhodamine B is obviously photodegraded, and the degradation rate can reach 98% within 150 min.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an infrared spectrum of a polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention.
FIG. 2 shows the solid-state NMR spectrum of a polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention
FIG. 3 is a scanning electron microscope photograph of polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention.
FIG. 4 shows the ultraviolet-visible absorption spectrum of the polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention as a heterogeneous photocatalyst, and hydrogen peroxide as an oxygen promoter under visible light conditions to photocatalytically degrade rhodamine B, an organic pollutant.
FIG. 5 is an infrared spectrum of 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin.
FIG. 6 is a nuclear magnetic hydrogen spectrum of 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin.
Detailed Description
The invention idea of the invention is as follows: in order to solve the problems that small molecular porphyrin serving as a photocatalyst is easy to gather into polymers, so that the catalytic activity is reduced, and the small molecular porphyrin is difficult to separate and recover after photocatalytic degradation reaction and is easy to cause secondary pollution, the invention synthesizes novel linear polyphenyl porphyrin benzobisoxazole which can be used as a heterogeneous photocatalyst, so that on one hand, an expanded pi conjugated system is adopted, the optical contact area is increased, and the photocatalytic activity is improved; on the other hand, the insolubility of the material is increased, so that after the photocatalytic degradation treatment is finished, the photocatalyst is easily separated from the photocatalytic system and reused after being recovered, the secondary pollution is reduced, and the industrial cost is further reduced.
In the process of preparing the polyphenyl porphyrin benzobisoxazole, the technical difficulty overcome is the synthesis of 5, 15-p- (4-carboxyphenyl) -10, 20-diphenyl porphyrin which is one of the used monomers, and the porphyrin compound is not sold in the market and is synthesized by the laboratory. The porphyrin compound is rarely reported in domestic and foreign literatures, and even though the individual English literature reports, the porphyrin compound is mostly used for preparing other materials, and how to prepare the porphyrin compound is not described in detail. Experiments prove that in the synthesis process, benzaldehyde, p-aldehyde methyl benzoate and pyrrole are adopted to react to obtain a crude product, and the crude product contains 5, 15-p- (4-ester phenyl) -10, 20-diphenyl porphyrin and other 5 by-products. The 5, 15-p- (4-ester group phenyl) -10, 20-diphenyl porphyrin is separated from the six mixtures by a column chromatography method, the yield is low (only 2%), the separation is difficult, and more difficult, the para-diester group phenyl porphyrin and the ortho-diester group phenyl porphyrin have similar structures, and the adsorption positions on a silica gel column are very close, so the separation is difficult. Hydrolyzing the separated 5, 15-p- (4-ester group phenyl) -10, 20-diphenyl porphyrin under alkaline condition to obtain 5, 15-p- (4-carboxyl phenyl) -10, 20-diphenyl porphyrin. In addition, 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin is prepared by hydrolyzing 5, 15-p- (4-esterylphenyl) -10, 20-diphenylporphyrin, but a crude product with 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin is not prepared firstly, and then the crude product is separated and extracted by a column.
The linear porphyrin-based polymer is characterized in that the minimum repeating unit is tetraphenylporphyrin connected with benzobisoxazole, and the structural formula is as follows:
wherein the polymerization degree n is an integer, n is more than 1 and less than 100, preferably n is more than or equal to 11 and less than or equal to 14, the morphology is granular, and the particle diameter is 90 nm.
The preparation method of the linear porphyrin-based polymer is characterized in that 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin and 4, 6-diaminoresorcinol hydrochloride are subjected to polycondensation reaction and dehydration to prepare the linear porphyrin-based polymer; the method specifically comprises the following steps:
the molar ratio of the 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin to the 4, 6-diaminoresorcinol hydrochloride is 1-1.1: 1;
step 2, after the reaction is finished and the temperature of the reaction bottle is reduced to room temperature, adding deionized water into the reaction bottle to wash polyphosphoric acid and 4,6 diaminoresorcinol hydrochloride, and simultaneously using pH test paper to test until the washing liquid in the filter flask is neutral; repeatedly washing the reactant with DMF to remove residual 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin in the reactant; repeatedly washing the product with deionized water and then carrying out suction filtration;
The synthesis steps of the 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin used by the invention are as follows:
firstly, synthesizing 5, 15-p- (4-ester group phenyl) -10, 20-diphenyl porphyrin by the following specific processes:
the molar ratio of benzaldehyde to methyl p-aldehyde benzoate is 1: 1, and the molar ratio of the total amount of benzaldehyde and methyl p-aldehyde benzoate to pyrrole should be 1: 1. 25mmol (1.76mL) of pyrrole, 12.5mmol (1.2705mL) of benzaldehyde and 12.5mmol (2.052g) of methyl p-aldehyde benzoate are put into an oil bath kettle at 140 ℃ for reaction for 2 hours to form a mixture containing 5, 15-p-esterylphenylporphyrin, and the 5, 15-p (4-esterylphenyl) -10, 20-diphenylporphyrin is purified by column chromatography. The yield was 2%.
The reaction formula is as follows:
secondly, synthesizing 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin by the following specific steps:
dissolving the previously synthesized 5, 15-p- (4-esterylphenyl) -10, 20-diphenylporphyrin (124.7mg) in tetrahydrofuran (13mL), adding 1mol/L KOH (20mL) into a single-neck reaction flask, heating to 66 ℃ by using an oil bath pot, refluxing and stirring for 48 hours, then adding 1mol/L HCl into the hydrolyzed solution, adjusting the pH of the solution to 3, finally performing suction filtration by using water, adjusting the pH of the solution to about 6, and then placing the solution into an oven for drying for 12 hours. The yield was 63%.
The reaction formula is as follows:
FIG. 5 is an infrared spectrum of 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin at 3317cm-1The characteristic peak belongs to the stretching vibration of an N-H bond on porphyrin center pyrrole and is 965cm-1Characteristic ofPeak, which is the bending vibration of the N-H bond on pyrrole; at 2928cm-1The characteristic peak belongs to the characteristic peak of C-H bond stretching vibration on a benzene ring; at 1462cm-1The characteristic peak is attributed to the vibration of C ═ C bond on the benzene ring skeleton, and the characteristic peak proves that the product has a porphyrin structure. At 3431cm-1A strong and broad peak appears at the position, which is attributed to the characteristic peak of O-H stretching vibration on carboxyl, and is 1695cm-1The peak is a characteristic peak attributed to stretching vibration of C ═ O bond in the carboxyl group. Thus, we have succeeded in preparing 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin by hydrolyzing 5, 15-p- (4-esterylphenyl) -10, 20-diphenylporphyrin.
FIG. 6 is a nuclear magnetic hydrogen spectrum of 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin with a chemical shift δ of-2.94 ppm, which is attributed to the hydrogen proton peak of NH-on the pyrrole at the porphyrin center; chemical shifts δ 7.86ppm and δ 8.23ppm, which belong to the hydrogen proton peak on the peripheral phenyl group of 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin; chemical shift δ 8.38ppm, belonging to the hydrogen proton peak on the phenyl group to which the carboxyl group is attached; chemical shift δ 8.85ppm, belonging to the hydrogen proton peak on the carbon of pyrrole; chemical shift δ 13.33ppm, belonging to the peak of hydrogen proton on carboxyl; in conclusion, it was demonstrated that 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin had been successfully prepared.
The invention also provides an application of the linear porphyrin-based polymer, and the linear porphyrin-based polymer is used as a photocatalyst for photocatalytic degradation of organic pollutants.
The process of the present invention is illustrated below.
Example 1
50mL of polyphosphoric acid is measured by a measuring cylinder, poured into a 100mL four-mouth reaction bottle (the main mouth is 24mm, two side mouths are 19mm, and one side mouth is 14mm), the reaction bottle is placed in a heating sleeve, a stirring paddle is inserted into the 24mm main mouth, and a nitrogen protection device is installed (one of the two 19mm side mouths is an air inlet of nitrogen, and the other is an air outlet of nitrogen); then, 4, 6-diaminoresorcinol hydrochloride (0.11mmol, 24.1mg) was added at the 14mm side port, a thermometer was inserted at the side port, the reaction was carried out under nitrogen gas, and the heating mantle was heated to 70 ℃ to remove 4,6-Introducing hydrochloric acid gas discharged from the reaction bottle into NaOH solution for neutralization; finally, after 6h of reaction, the nitrogen vent of the reaction flask was opened while increasing the flow of nitrogen to prevent air from entering the reaction flask, 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin (0.11mmol, 79.3mg) was added to the reaction flask, and the reaction was heated to 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ and held for 4h, respectively. After the reaction is finished and the temperature of the reaction bottle is reduced to room temperature, adding deionized water into the reaction bottle to wash polyphosphoric acid and 4, 6-diaminoresorcinol hydrochloride, and simultaneously using pH test paper to test until the washing liquid in the filter flask is neutral; repeatedly washing the reactant with DMF to remove residual 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin in the reactant; finally, the product was washed repeatedly with deionized water. Pouring the filtered polyphenyl porphyrin benzobisoxazole polymer into a freeze-drying bottle, and freezing the freeze-drying bottle at-30 ℃ for 2 hours; then the freeze-drying bottle is inserted into a vacuum freeze-drying machine for drying for 12 hours, and finally the black green solid of the poly phenyl porphyrin benzobisoxazole is obtained, the polymerization degree n is 11, and the viscosity average molecular weight is 8662 g.mol-1Yield, yield: 84 percent.
The reaction formula is as follows:
FIG. 1 is an infrared spectrum of a polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention, from which 1606cm was observed-1The new absorption peak is attributed to the C ═ N stretching vibration of the oxazole ring in the polymer formed after the reaction. Furthermore, at 1230 and 1078cm-1A vibration band occurs, which is attributed to C-N and ═ C-O-C on the oxazole ring, respectively. The above results demonstrate that polyphenylporphyrin benzobisoxazole has been successfully obtained.
FIG. 2 is a solid-state nuclear magnetic carbon spectrum of the polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention, wherein the numbers marked at different chemical shifts in the carbon spectrum respectively correspond to the carbon atoms at the numbers in the structural formula, and the chemical shift is 127ppm, which belongs to the carbon sub-peak of the benzene ring on the porphyrin; chemical shifts of 95 ppm and 111ppm, which are respectively assigned to carbon sub-peaks at positions 3 and 7 on the benzene ring; chemical shifts 139 and 153ppm, which are assigned to the carbon sub-peaks at positions 6,8 and 2,4, respectively; chemical shift 162ppm, assigned to the carbon sub-peak at 1,5 position on the oxazole ring. The above results indicate that the polyphenylporphyrin benzobisoxazole has been successfully prepared.
FIG. 3 is a scanning electron microscope image of polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention, which shows that polyphenylporphyrin benzobisoxazole has a granular morphology and a particle diameter of about 90 nm.
Example 2:
50mL of polyphosphoric acid is measured and poured into a 100mL four-mouth reaction bottle (the main mouth is 24mm, two side mouths are 19mm, and one side mouth is 14mm), the reaction bottle is placed in a heating sleeve, a stirring paddle is inserted into the 24mm main mouth, and a nitrogen protection device is installed (one of the two 19mm side mouths is an air inlet of nitrogen, and the other is an air outlet of nitrogen); then, 4, 6-diaminoresorcinol hydrochloride (0.11mmol, 24.1mg) was added at the side port of 14mm, a thermometer was inserted at the side port, nitrogen gas was introduced to carry out the reaction under the protection of nitrogen gas, the heating mantle was heated to 70 ℃ to remove hydrochloric acid from 4, 6-diaminoresorcinol hydrochloride, and the hydrochloric acid gas discharged from the reaction flask was neutralized by introducing NaOH solution; finally, after 6h of reaction, the nitrogen vent of the reaction flask was opened while increasing the flow of nitrogen to prevent air from entering the reaction flask, 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin (0.11mmol, 79.3mg) was added to the reaction flask, and the reaction was heated to 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ and incubated for 6 h. After the reaction is finished and the temperature of the reaction bottle is reduced to room temperature, adding deionized water into the reaction bottle to wash polyphosphoric acid and 4, 6-diaminoresorcinol hydrochloride, and simultaneously using pH test paper to test until the washing liquid in the filter flask is neutral; repeatedly washing the reactant with DMF to remove residual 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin in the reactant; finally, the product was washed repeatedly with deionized water. Pouring the filtered polyphenyl porphyrin benzobisoxazole polymer into a freeze-drying bottle, and freezing the freeze-drying bottle at-30 ℃ for 2 hours; then the freeze-drying bottle is inserted into a vacuum freeze-drying machine for drying for 12 hours, and finally the polyphenyl porphyrin benzene is obtainedA black green solid of the bisoxazole, a degree of polymerization n of 14 and a viscosity average molecular weight of 11080 g.mol-1Yield, yield: 80 percent.
Example 3
The process of degrading organic pollutant solution with the polyphenyl porphyrin and the benzobisoxazole under photocatalysis is as follows:
40mL of prepared rhodamine B (1X 10)-5mol/L) solution, adding 10mg of the polyphenylporphyrin benzobisoxazole photocatalyst obtained in the example 1, adding 2mL of hydrogen peroxide as an oxygen-assisting agent, placing a magnetic stirrer in the reactor, introducing circulating condensed water to the outer layer of the reactor for cooling, wrapping the reactor by tinfoil, and stirring for 30min under a dark condition to ensure that the catalyst is in adsorption-desorption balance; after 30min, a xenon lamp light source (PLS-SXE 300, 400nm short-wave cut-off filter of Beijing Pofely science and technology Limited) is turned on, and an experiment for photocatalytic degradation of rhodamine B is started; and sucking the supernatant liquid in the reactor once every 30min by using an injector, testing by using an ultraviolet spectrometer, and tracking and monitoring the absorption peak at the wavelength of 554 nm.
The formula of the photocatalytic degradation rate of rhodamine B is as follows:
wherein: a. the0And the absorbance value measured by the rhodamine B solution before the catalytic degradation by turning on the light source is shown.
A represents the absorbance value measured by rhodamine B solution after the xenon lamp is turned on and the rhodamine B solution is catalytically degraded for a period of time.
FIG. 4 shows the ultraviolet-visible absorption spectrum of the polyphenylporphyrin benzobisoxazole obtained in example 1 of the present invention as a heterogeneous photocatalyst, and hydrogen peroxide as an oxygen promoter under visible light conditions to photocatalytically degrade rhodamine B, an organic pollutant. It can be seen from the spectrum that with the increase of time, under the action of the polyphenylporphyrin benzobisoxazole photocatalyst, the organic pollutant rhodamine B is obviously photodegraded, and the degradation rate can reach 98% within 150 min.
Claims (6)
1. Linear porphyrin-based polymers characterized by the fact that the smallest repeating unit is tetraphenylporphyrin linked to benzobisoxazole of the following structural formula:
wherein the polymerization degree n is an integer, and n is more than or equal to 11 and less than or equal to 14.
2. The linear porphyrin-based polymer of claim 1, wherein the morphology is granular and the particle diameter is 90 nm.
3. The method for preparing a linear porphyrin-based polymer according to claim 1, comprising the steps of:
the compound is prepared by dehydrating 5, 15-p- (4-carboxyl phenyl) -10, 20-diphenyl porphyrin and 4, 6-diamino resorcinol hydrochloride through polycondensation reaction.
4. The method for preparing a linear porphyrin-based polymer according to claim 3, comprising the following steps:
step 1, adding polyphosphoric acid into a reaction bottle, then placing the reaction bottle into a heating sleeve, adding 4, 6-diaminoresorcinol hydrochloride into the reaction bottle, reacting under the protection of nitrogen, and heating the heating sleeve to 70 ℃ to remove hydrochloric acid on the 4, 6-diaminoresorcinol hydrochloride; after the reaction is carried out for 6 hours, opening a nitrogen gas outlet of a reaction bottle, simultaneously increasing the airflow of nitrogen to prevent air from entering the reaction bottle, adding 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin into the reaction bottle, then respectively heating the reaction to 100 ℃, 120 ℃, 140 ℃, 160 ℃ and 180 ℃ and preserving heat for 4-6 hours;
step 2, after the reaction is finished and the temperature of the reaction bottle is reduced to room temperature, adding deionized water into the reaction bottle to wash polyphosphoric acid and 4,6 diaminoresorcinol hydrochloride, and simultaneously using pH test paper to test until the washing liquid in the filter flask is neutral; repeatedly washing the reactant with DMF to remove residual 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin in the reactant; repeatedly washing the product with deionized water and then carrying out suction filtration;
step 3, pouring the filtered polyphenyl porphyrin benzobisoxazole polymer into a freeze-drying bottle, and freezing the freeze-drying bottle at-30 ℃ for 2 hours; and then inserting the freeze-drying bottle on a vacuum freeze-drying machine for drying for 12 hours to finally obtain the black green solid of the polyphenyl porphyrin benzobisoxazole.
5. The method for preparing a linear porphyrin-based polymer according to claim 3 or 4, wherein the molar ratio of 5, 15-p- (4-carboxyphenyl) -10, 20-diphenylporphyrin to 4, 6-diaminoresorcinol hydrochloride is 1-1.1: 1.
6. use of a linear porphyrin-based polymer according to claim 1 or 2 as a photocatalyst for photocatalytic degradation of organic contaminants.
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