A metalloporphyrin organic framework derivative, and a preparation method and application thereof

Abstract

The application provides a metal porphyrin organic framework structure derivative, a preparation method and application thereof, and belongs to the technical field of functional organic molecule synthesis. The derivative is prepared from a vanillin porphyrin compound with a nano-particle wrapped I structure, wherein the nano-particle is silica, polyphosphazene or polyaniline. The application also provides a preparation method of the metal porphyrin organic framework structure derivative. The metal porphyrin organic framework structure derivative can be used as a flame retardant and has excellent flame retardant effect.

Description

Technical Field

[0001] This invention belongs to the field of functional organic molecule synthesis technology, specifically relating to a metalloporphyrin organic framework structure derivative, its preparation method, and its application. Background Technology

[0002] Fire is one of the most frequent and widespread disasters threatening public safety and social development. The large amounts of toxic smoke and heat generated in fires pose a serious threat to people's lives and property, which is an urgent problem to be solved. Today, although advancements in polymer materials have contributed to social development, they are one of the causes of fires, and their application is limited due to their flammability and high smoke release.

[0003] Various methods are being used to reduce the fire hazards of polymer materials, among which adding flame retardants is by far the most effective and economical method. As traditional flame retardants such as metal hydroxides, red phosphorus, and halogenated flame retardants can no longer meet the demands of the rapidly developing polymer industry, novel nano-flame retardants have attracted widespread attention for improving the flame retardant properties of polymer materials due to their advantages such as low dosage and high efficiency.

[0004] Porphyrins are 18-π aromatic macromolecules containing four pyrrole rings. Free metal ions can coordinate with the nitrogen atoms of porphyrins through chelation, thereby synthesizing various metalloporphyrin organic framework structures. Metal ions can not only enhance the thermal stability of polymers through crosslinking, but also promote dehydrogenation reactions, increasing residual char content and thus enhancing the flame retardancy of the polymers. However, there are currently few reports on metalloporphyrin organic framework structures as flame retardants. Summary of the Invention

[0005] The purpose of this invention is to provide a metalloporphyrin organic framework structure derivative, its preparation method and application. This metalloporphyrin organic framework structure derivative can be used as a flame retardant and has excellent flame retardant effect.

[0006] This invention first provides a metalloporphyrin organic framework derivative, which is prepared by encapsulating a vanillin porphyrin compound of formula I with nanoparticles. The nanoparticles are silica, polyphosphazene, or polyaniline. The vanillin porphyrin compound of formula I has the following structural formula:

[0007]

[0008] Among them, Me is a chelated metal ion;

[0009] This invention also provides a method for preparing a metalloporphyrin organic framework derivative, comprising:

[0010] Step 1: Prepare by reacting the compound of Formula 1 and the compound of Formula 2 in propionic acid solvent.

[0011] Compounds with the structure of Formula 3;

[0012]

[0013] Step 2: Dissolve the compound of formula 3, the compound of formula 4 and triethylamine in chloroform, stir under an ice-water bath, and then transfer to an oven to react and obtain the compound of formula 5;

[0014]

[0015] Step 3: React the compound with Formula 5 with a metal salt to obtain the vanillin porphyrin compound with Formula I;

[0016]

[0017] Step 4: Coating nanoparticles onto the vanillin porphyrin compound of Formula I to obtain a metalloporphyrin organic framework derivative, wherein the nanoparticles are silica, polyphosphazene, or polyaniline.

[0018] Preferably, the metal salt is one or a mixture of two of FeCl3·6H2O or MgCl2·6H2O.

[0019] Preferably, when the nanoparticles are silicon dioxide, step four specifically involves reacting a vanillin porphyrin compound of formula I with hexadecyltrimethylammonium bromide and tetraethyl orthosilicate under alkaline conditions to obtain a metalloporphyrin organic framework derivative P1.

[0020] Preferably, the vanillin porphyrin compound of formula I: hexadecyltrimethylammonium bromide: tetraethyl orthosilicate is in a mass ratio of 2:2.6:1, the pH value is 8-10, the reaction temperature is room temperature, and the reaction time is 16-20h.

[0021] Preferably, when the nanoparticles are polyphosphazenes, step four specifically involves reacting a vanillin porphyrin compound of formula I with 4,4'-dihydroxydiphenyl sulfone, cyclotriphosphazene, and triethylamine to obtain a metalloporphyrin organic framework derivative P2.

[0022] Preferably, the mass ratio of the vanillin porphyrin compound of Formula I: 4,4'-dihydroxydiphenyl sulfone: cyclotriphosphazene: triethylamine solution is 1:0.7:0.3:1.4, the reaction temperature is room temperature, and the reaction time is 8-12 h.

[0023] Preferably, when the nanoparticles are polyaniline, step four specifically involves: reacting the vanillin porphyrin compound of formula I with aniline and ammonium persulfate under acidic conditions in an ice-water bath with stirring to obtain the metalloporphyrin organic framework derivative P3.

[0024] Preferably, the mass ratio of vanillin porphyrin compound of formula I: aniline: ammonium persulfate is 1:4.6:1.14, the molar concentration of hydrochloric acid is 0.5-1.5M, the reaction temperature is room temperature, and the reaction time is 4-8h.

[0025] The present invention also provides the application of the above-mentioned metalloporphyrin organic framework structure derivatives as flame retardants.

[0026] Beneficial effects of the present invention

[0027] This invention provides a metalloporphyrin organic framework derivative, its preparation method, and its applications. The invention utilizes vanillin to prepare porphyrin organic compounds, and then successfully prepares a series of metalloporphyrins by chelating metal ions. Simultaneously, this series of metalloporphyrins can be prepared by encapsulating nanoparticles of silica (SiO2), polyphosphazene (PZS), and polyaniline (PANI) onto vanillin porphyrin compounds using various simple methods, thus preparing a series of metalloporphyrin derivatives. These derivatives are then added to polymers as flame retardants, and their impact on polymer fire safety is investigated. In this invention, epoxy resin (EP) is used as a typical polymer, and the metalloporphyrin flame retardant is added to it to prepare a series of flame-retardant epoxy resins: EP / P1, EP / P2, and EP / P3. Compared with pure EP, the PHRR of EP / P1, EP / P2, and EP / P3 decreased by 48.1%, 31.7%, and 20.5%, respectively; the THR of EP / P1, EP / P2, and EP / P3 decreased by 25.8%, 21.4%, and 20.8%, respectively; the SPR of EP / P1, EP / P2, and EP / P3 decreased by 52.2%, 17.4%, and 15.2%, respectively; and the TSP of EP / P1, EP / P2, and EP / P3 decreased by 43.3%, 22.4%, and 13.5%, respectively. The metalloporphyrin derivative flame retardants proposed in this invention possess highly efficient flame retardant and smoke-suppressing properties and thermal stability, and have broad application prospects in the field of polymer flame retardancy. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the structure of the metalloporphyrin organic framework derivative of the present invention.

[0029] Figure 2 The 1H NMR spectrum of the vanillin porphyrin compound with structure 5 prepared in Example 1 of this invention.

[0030] Figure 3The images are SEM images of the metalloporphyrin organic framework structure and its derivatives P1 and P2 of this invention.

[0031] Figure 4 The heat release rate (HRR) images of EP, EP / P1, EP / P2, and EP / P3 of this invention.

[0032] Figure 5 The total heat release rate (THR) images of EP, EP / P1, EP / P2, and EP / P3 of this invention.

[0033] Figure 6 The flue gas emission rate (SPR) images for EP, EP / P1, EP / P2, and EP / P3 of this invention.

[0034] Figure 7 The images show the total smoke emissions (TSP) for EP, EP / P1, EP / P2, and EP / P3 of this invention.

[0035] Figure 8 Images showing the CO2 release rates (PCO2P) of EP, EP / P1, EP / P2, and EP / P3 in this invention.

[0036] Figure 9 The images show the CO release rate (PCOP) images for EP, EP / P1, EP / P2, and EP / P3 of this invention. Detailed Implementation

[0037] This invention first provides a metalloporphyrin organic framework derivative, which is prepared by encapsulating a vanillin porphyrin compound of formula I with nanoparticles. The nanoparticles are silica, polyphosphazene, or polyaniline. The vanillin porphyrin compound of formula I has the following structural formula:

[0038]

[0039] Me is a chelated metal ion, preferably one or more of Fe, Mg, Zn or Co.

[0040] This invention also provides a method for preparing a metalloporphyrin organic framework derivative, comprising:

[0041] Step 1: React the compound of Formula 1 and the compound of Formula 2 in propionic acid solvent to prepare the compound of Formula 3; the molar ratio of the compound of Formula 1 to the compound of Formula 2 is preferably 1:1; the reaction temperature is preferably 100-160℃, and the reaction time is preferably 1-3h;

[0042]

[0043] Step 2: Dissolve the compound of formula 3, the compound of formula 4, and triethylamine in chloroform, stir under an ice-water bath, and then transfer to an oven to react and obtain the compound of formula 5; the preferred mass ratio of the compound of formula 3, the compound of formula 4, and triethylamine is 1:1.2:1; the preferred ice-water bath temperature is 0-10℃, the preferred oven reaction temperature is 60-80℃, and the preferred reaction time is 10-14h;

[0044]

[0045] Step 3: React the compound of Formula 5 with a metal salt to obtain the vanillin porphyrin compound of Formula I; the preferred mass ratio of the compound of Formula 5 to the metal salt is 1:(1-5); the metal salt is one or a mixture of two of FeCl3·6H2O or MgCl2·6H2O, more preferably FeCl3·6H2O or a mixture of FeCl3·6H2O and MgCl2·6H2O, wherein the preferred mass ratio of FeCl3·6H2O to MgCl2·6H2O is 3:2; when the metal salt is FeCl3·6H2O, the preferred reaction solvent is chloroform; when the metal salt is a mixture of FeCl3·6H2O and MgCl2·6H2O, the preferred solvent is deionized water; the preferred reaction temperature is 50-70℃, and the preferred reaction time is 1-3h;

[0046]

[0047] The preparation process is as follows:

[0048]

[0049] Step 4: Coating nanoparticles onto the vanillin porphyrin compound of Formula I to obtain a metalloporphyrin organic framework derivative, wherein the nanoparticles are silica, polyphosphazene, or polyaniline.

[0050] According to the present invention, when the nanoparticles are silicon dioxide, step four specifically involves reacting a vanillin porphyrin compound of formula I with hexadecyltrimethylammonium bromide and tetraethyl orthosilicate under alkaline conditions to obtain a metalloporphyrin organic framework derivative P1. The preferred mass ratio of the vanillin porphyrin compound of formula I to hexadecyltrimethylammonium bromide to tetraethyl orthosilicate is 2:2.6:1, the pH value is 8-10, the preferred reaction temperature is room temperature, and the preferred reaction time is 16-20 h. In the vanillin porphyrin compound of formula I, Me is Fe.

[0051] According to the present invention, when the nanoparticles are polyphosphazenes, step four specifically involves reacting a vanillin porphyrin compound of formula I with 4,4'-dihydroxydiphenyl sulfone, cyclotriphosphazene, and triethylamine to obtain a metalloporphyrin organic framework derivative P2. The preferred mass ratio of the vanillin porphyrin compound of formula I: 4,4'-dihydroxydiphenyl sulfone:cyclotriphosphazene:triethylamine solution is 1:0.7:0.3:1.4, the preferred reaction temperature is room temperature, and the preferred reaction time is 8-12 h. In the vanillin porphyrin compound of formula I, Me is Fe.

[0052] According to the present invention, when the nanoparticles are polyaniline, step four specifically involves: reacting a vanillin porphyrin compound of formula I with aniline and ammonium persulfate under acidic conditions in an ice-water bath to obtain a metalloporphyrin organic framework derivative P3; the preferred mass ratio of the vanillin porphyrin compound of formula I to aniline to ammonium persulfate is 1:4.6:1.14, the preferred molar concentration of hydrochloric acid is 0.5-1.5M, the preferred reaction temperature is room temperature, and the preferred reaction time is 4-8 hours; wherein Me in the vanillin porphyrin compound of formula I is Fe and Mg.

[0053] The structural formula of the metalloporphyrin organic framework derivatives prepared by this invention is as follows: Figure 1 As shown.

[0054] The present invention also provides the application of the above-mentioned metalloporphyrin organic framework structure derivatives as flame retardants.

[0055] According to the present invention, the metalloporphyrin organic framework structure derivative is used as a flame retardant in composite polymer materials, wherein the preferred addition ratio of the metalloporphyrin organic framework structure derivative in the composite polymer material is 1-10 wt%. As a preferred technical solution for this application, taking epoxy resin as an example, the preparation steps for preparing the epoxy resin / metalloporphyrin organic framework structure derivative composite material are as follows:

[0056] The metalloporphyrin organic framework derivative is dissolved in a solvent, preferably acetone solution, and ultrasonically stirred for 1-3 hours. Preheated epoxy resin is added, and ultrasonic stirring is continued for another 1-3 hours to obtain a mixture. The mixture is then transferred to a temperature of 60-100°C and heated and stirred for 10-14 hours. Pre-melted 4,4-diaminodiphenylmethane solid is added, and the mixture is then transferred to a mold and heated at 80-120°C for 1-3 hours, followed by heating at 130-170°C for another 1-3 hours.

[0057] When the metalloporphyrin organic framework derivative is compound P1, the sample is defined as EP / P1;

[0058] When the metalloporphyrin organic framework derivative is compound P2, the sample is defined as EP / P2;

[0059] When the metalloporphyrin organic framework derivative is compound P3, the sample is defined as EP / P3.

[0060] The present invention will be further described in detail below with reference to specific embodiments. All raw materials involved in the embodiments are commercially available.

[0061] Example 1: Preparation of vanillin porphyrin compounds with structure 5

[0062] Step A: Dissolve the compound of Formula 1 in propionic acid. Under oil bath heating conditions, add the compound of Formula 2, then transfer to a reaction vessel. The oil bath temperature is 140℃, and the reaction vessel temperature is 140℃. The heating time is 2 hours. After the reaction is complete, soak the mixture in deionized water to precipitate the compound of Formula 3. The molar ratio of the compound of Formula 1 to the compound of Formula 2 is 1:1.

[0063] Step B: The compound of formula 3, the compound of formula 4, and triethylamine were dissolved in chloroform and stirred in an ice-water bath at 5°C. The mixture was then transferred to an oven and reacted at 70°C for 12 hours. The mixture was then soaked in alcohol, centrifuged, washed, and dried to prepare the compound of formula 5. The mass ratio of the compound of formula 3 to the compound of formula 4 to triethylamine was 1:1.2:1.

[0064] The NMR spectrum of the compound with the prepared formula 5 structure is shown below. Figure 2 As shown. The chemical shift at 8.7 ppm corresponds to a proton on the porphyrin ring (labeled a); the chemical shift at -2.9 ppm corresponds to an -NH group (labeled e); the chemical shifts at 8.1 ppm and 7.5 ppm correspond to protons on the benzene ring (labeled b and c); the chemical shift at 3.8 ppm corresponds to -CH3 in the pyrrole structure; and the bands from 2.2 ppm to 1.0 ppm correspond to -CH- in the pyrrole structure. The analysis results of the 1H NMR spectrum indicate that the vanillin porphyrin compound was successfully synthesized in this invention.

[0065] Example 2: Preparation of iron porphyrin organic framework compounds

[0066] The compound of formula 5 prepared in Example 1 was reacted with FeCl3·6H2O in a chloroform solution at 60°C for 2 h, followed by centrifugation, washing, and drying to prepare an iron porphyrin organic framework compound. The mass ratio of the compound of formula 5 to FeCl3·6H2O was 1:2.

[0067] Example 3: Preparation of polymetallic porphyrin organic framework compounds

[0068] The compound of formula 5 prepared in Example 1 was reacted with FeCl3·6H2O and MgCl2·6H2O in deionized water at 60°C for 2 h, followed by centrifugation, washing, and drying to prepare a polymetallic porphyrin organic framework compound. The mass ratio of the compound of formula 5, FeCl3·6H2O, and MgCl2·6H2O was 3:3:2.

[0069] Example 4: Preparation of Derivative P1

[0070] The iron porphyrin organic framework compound prepared in Example 2 was dissolved in ethanol with hexadecyltrimethylammonium bromide and tetraethyl orthosilicate at a mass ratio of 2:2.6:1. The pH was adjusted to 9 using NH3·H2O, and the reaction was carried out at room temperature under alkaline conditions for 18 hours. After centrifugation, washing and drying, derivative P1 was obtained.

[0071] Example 5: Preparation of Derivative P2

[0072] The iron porphyrin organic framework compound prepared in Example 2 was dissolved in methanol solution with 4,4'-dihydroxydiphenyl sulfone, cyclotriphosphazene and triethylamine in a mass ratio of 1:0.7:0.3:1.4. After reacting at room temperature for 10 h, the derivative P2 was obtained by centrifugation, washing and drying.

[0073] Example 6 Preparation of Derivative P3

[0074] The polymetallic porphyrin organic framework compound prepared in Example 3 was dissolved in hydrochloric acid, and then aniline and ammonium persulfate solution were added respectively. After stirring magnetically for 6 hours in an ice-water bath, the mixture was centrifuged, washed, and dried to obtain derivative P3. The mass ratio of the polymetallic porphyrin organic framework compound, aniline, and ammonium persulfate was 1:4.6:1.14, and the molar concentration of hydrochloric acid was 1M.

[0075] Example 7: Preparation of epoxy resin / metalporphyrin organic framework structure derivative composite material

[0076] The metalloporphyrin derivatives prepared in Examples 4-6 were dissolved in acetone and ultrasonically stirred for 2 hours. Then, a certain amount of preheated epoxy resin was added to the solution, and ultrasonic stirring continued for 2 hours. The mixture was transferred to an oil bath and stirred at 80°C for 12 hours. A certain amount of molten 4,4-diaminodiphenylmethane solid was added, and the mixture was quickly poured into a template and transferred to an oven. The template was then cured at 100°C and 150°C for 2 hours each, respectively, to prepare the epoxy resin / metalloporphyrin organic framework structure derivative composite material.

[0077] In EP / P1, the amount of metalloporphyrin derivative P1 added is 5 wt%, and the mass ratio of P1, epoxy resin and 4,4-diaminodiphenylmethane solid is 3:60:12.

[0078] In EP / P2, the amount of metalloporphyrin derivative P2 added is 2wt%, and the mass ratio of P2, epoxy resin and 4,4-diaminodiphenylmethane solid is 1.2:60:12.

[0079] In EP / P3, the amount of metalloporphyrin derivative P3 added is 2wt%, and the mass ratio of P3, epoxy resin and 4,4-diaminodiphenylmethane solid is 1.2:60:12.

[0080] The structures and morphologies of metalloporphyrins and their organic framework derivatives were observed using scanning electron microscopy. For example... Figure 3 As shown, Figures a through f represent vanillin porphyrin, iron porphyrin, metalloporphyrin derivative P1, metalloporphyrin derivative P2, iron-magnesium bimetallic porphyrin, and metalloporphyrin derivative P3, respectively. Scanning electron microscopy images of vanillin porphyrin show a bulk structure ranging in size from 0.8 μm to 1.5 μm. Figure 3 a) This is a result of the π-π bond interactions between the vanillin porphyrin benzene rings. The microstructure of iron metal porphyrins is bulky, ranging in size from 0.5 to 0.6 micrometers. Figure 3 (b) This is because coordination with Fe(Ⅲ) disrupts the π-π bond interaction. In contrast, the metalloporphyrin organic framework derivative P1 exhibits a cauliflower-like structure, and numerous rough microspheres representing SiO2 can be seen on its surface. Figure 3 c) This increases the specific surface area of ​​the metalloporphyrin. Compared to iron porphyrin, the surface of the metalloporphyrin organic framework derivative P2 is rougher, and a large number of PZS microspheres can be clearly observed. Figure 3 d) indicates that PZS microspheres have been successfully loaded onto the surface of the metalloporphyrin organic framework structure. The iron-magnesium bimetallic porphyrin exhibits a spindle-shaped structure ( Figure 3 e) This is because the coordination of the iron-magnesium bimetallic compound further disrupts the π-π bond interaction of the vanillin porphyrin benzene ring. Compared to iron-magnesium bimetallic porphyrins, the metalloporphyrin organic framework derivative P3 is uniformly doped with nano-PANI microspheres ( Figure 3 f) indicates that PANI microspheres have been successfully loaded onto the surface of the metalloporphyrin organic framework structure.

[0081] See appendix Figure 4 The graphs show the heat release rates (HRR) of EP, EP / P1, EP / P2, and EP / P3 measured using cone calorimetry. The peak heat release rate (PHRR) of pure EP is 1329.3 kW / m³. 2 When a metalloporphyrin organic framework derivative was added, the PHRR of the polymers decreased significantly. The PHRRs of EP / P1, EP / P2, and EP / P3 were 689.4, 907.3, and 923.3 kW / m, respectively. 2Compared to pure EP, these figures decreased by 48.1%, 31.7%, and 20.5%, respectively.

[0082] See appendix Figure 5 The graph shows the total heat release rate (THR) of EP, EP / P1, EP / P2, and EP / P3 as measured using cone calorimetry. The THR of pure EP is 93.91 MJ / m³. 2 When a metalloporphyrin organic framework derivative was added, the THR of the polymer was significantly reduced. The THR of EP / P1, EP / P2, and EP / P3 were 67.9, 73.8, and 74.4 MJ / m, respectively. 2 Compared to pure EP, these figures decreased by 25.8%, 21.4%, and 20.8%, respectively.

[0083] See appendix Figure 6 The graphs show the flue gas release rates (SPR) for EP, EP / P1, EP / P2, and EP / P3, measured using cone calorimetry. The SPR for pure EP is 0.46 m. 2 / s, when the metalloporphyrin organic framework derivative was added, the SPR of the polymer was significantly reduced, and the PHRR of EP / P1, EP / P2 and EP / P3 were 0.22, 0.38 and 0.39 m, respectively. 2 / s, which are 52.2%, 17.4% and 15.2% lower than pure EP, respectively.

[0084] See appendix Figure 7 The image shows the total smoke emissions (TSP) for EP, EP / P1, EP / P2, and EP / P3 measured using cone calorimetry. The TSP for pure EP is 41.6 m³ / s. 2 When a metalloporphyrin organic framework derivative was added, the TSP of the polymers decreased significantly. The TSPs of EP / P1, EP / P2, and EP / P3 were 23.6, 32.3, and 36.0 m, respectively. 2 Compared to pure EP, these figures decreased by 43.3%, 22.4%, and 13.5%, respectively.

[0085] See appendix Figure 8 The figures show the CO2 release rates (PCO2P) of EP, EP / P1, EP / P2, and EP / P3 measured using cone calorimetry. The PCO2P of pure EP is 0.91 g / s. Upon addition of the metalloporphyrin organic framework derivative, the PCO2P of the polymers significantly decreased. The PHRRs of EP / P1, EP / P2, and EP / P3 were 0.45, 0.60, and 0.61 g / s, respectively, representing reductions of 50.5%, 34.1%, and 33.0% compared to pure EP.

[0086] See appendix Figure 9The figures show the CO release rate (PCOP) images of EP, EP / P1, EP / P2, and EP / P3 measured using cone calorimetry. The PCOP of pure EP is 0.106 g / s. Upon addition of the metalloporphyrin organic framework derivative, the PCOP of the polymers significantly decreased. The PHRR of EP / P1, EP / P2, and EP / P3 were 0.051, 0.028, and 0.035 g / s, respectively, representing reductions of 51.9%, 73.6%, and 67.0% compared to pure EP.

[0087] The relevant data of EP, EP / P1, EP / P2 and EP / P3 measured by cone calorimetry are shown in Table 1.

[0088] Table 1

[0089]

[0090]

Claims

1. A metalloporphyrin organic framework derivative, characterized in that, This derivative is prepared by encapsulating a vanillin porphyrin compound of formula I with nanoparticles, wherein the nanoparticles are polyphosphazene or polyaniline, and the vanillin porphyrin compound of formula I has the following structural formula: Formula I Among them, Me is a chelated metal ion; The method for preparing a metalloporphyrin organic framework derivative includes: Step 1: React the compound of Formula 1 and the compound of Formula 2 in propionic acid solvent to prepare the compound of Formula 3; Step 2: React the compound of formula 3 to obtain the compound of formula 5. The reaction conditions are: dissolve the reactants and triethylamine in chloroform, stir under an ice-water bath, and then transfer to an oven for reaction. Step 3: React the compound with Formula 5 with a metal salt to obtain the vanillin porphyrin compound with Formula I; Formula I Step 4: Coating nanoparticles onto the vanillin porphyrin compound of Formula I to obtain a metalloporphyrin organic framework derivative, wherein the nanoparticles are polyphosphazene or polyaniline; The metal salt is one or a mixture of two of FeCl3·6H2O or MgCl2·6H2O.

2. The metalloporphyrin organic framework derivative according to claim 1, characterized in that, When the nanoparticles are polyphosphazenes, step four specifically involves reacting a vanillin porphyrin compound of formula I with 4,4'-dihydroxydiphenyl sulfone, cyclotriphosphazene, and triethylamine to obtain a metalloporphyrin organic framework derivative P2.

3. The metalloporphyrin organic framework derivative according to claim 2, characterized in that, The vanillin porphyrin compound of formula I has a solution mass ratio of 4,4'-dihydroxydiphenyl sulfone: cyclotriphosphazene:triethylamine of 1:0.7:0.3:1.4, the reaction temperature is room temperature, and the reaction time is 8-12 h.

4. A metalloporphyrin organic framework derivative according to claim 1, characterized in that, When the nanoparticles are polyaniline, step four specifically involves reacting the vanillin porphyrin compound of formula I with aniline and ammonium persulfate under acidic conditions in an ice-water bath with stirring to obtain the metalloporphyrin organic framework derivative P3.

5. A metalloporphyrin organic framework derivative according to claim 4, characterized in that, The vanillin porphyrin compound of formula I has a mass ratio of aniline to ammonium persulfate of 1:4.6:1.14, a molar concentration of hydrochloric acid of 0.5-1.5 M, a reaction temperature of room temperature, and a reaction time of 4-8 h.

6. The application of the metalloporphyrin organic framework structure derivative of claim 1 as a flame retardant.

Images