Metalloporphyrin organic framework structure derivative as well as preparation method and application thereof

Abstract

The invention provides a metalloporphyrin organic framework structure derivative as well as a preparation method and application thereof, and belongs to the technical field of functional organic molecule synthesis. The derivative is prepared by coating a vanillin porphyrin compound with a structure as shown in a formula I by nano particles, wherein the nano particles are silicon dioxide, polyphosphazene or polyaniline. The invention also provides a preparation method of the metalloporphyrin organic framework structure derivative. The metalloporphyrin organic framework structure derivative disclosed by the invention can be used as a flame retardant and has an excellent flame-retardant effect.

Description

Technical Field

[0001] The invention belongs to the technical field of functional organic molecule synthesis, and specifically relates to a metal porphyrin organic framework structure derivative and a preparation method and application thereof. Background Art

[0002] Fire is one of the most frequent and common disasters that threaten public safety and social development. The large amount of toxic smoke and heat generated in fires can pose a serious threat to people's lives and property, which is an urgent problem to be solved. Nowadays, although the progress of polymer materials has contributed to the development of society, they are one of the causes of fire and their application is limited due to their flammability and high smoke release.

[0003] People are using various methods 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 halogen flame retardants cannot meet the needs of the rapidly developing polymer industry, new nano flame retardants have received widespread attention in improving the flame retardant properties of polymer materials due to their advantages such as small addition amount and high efficiency.

[0004] Porphyrin is an 18-π aromatic macromolecular compound containing four pyrrole rings. Free metal ions can coordinate with the nitrogen atoms of porphyrin through chelation to synthesize various metalloporphyrin organic framework structures. Metal ions can not only enhance the thermal stability of polymers by cross-linking with polymers, but also promote dehydrogenation reactions and increase the amount of residual coke, thereby enhancing the flame retardancy of polymers. However, there are few reports on metalloporphyrin organic framework structures as flame retardants. Summary of the invention

[0005] The purpose of the present invention is to provide a metal porphyrin organic framework structure derivative and a preparation method and application thereof. The metal porphyrin organic framework structure derivative can be used as a flame retardant and has an excellent flame retardant effect.

[0006] The present invention first provides a metal porphyrin organic framework structure derivative, which is prepared by encapsulating a vanillin porphyrin compound of formula 1 with nanoparticles, wherein the nanoparticles are silicon dioxide, polyphosphazene or polyaniline, and the vanillin porphyrin compound of formula I has the following structural formula:

[0007]

[0008] Wherein, Me is a chelated metal ion;

[0009] The present invention also provides a method for preparing a metal porphyrin organic framework structure derivative, comprising:

[0010] Step 1: Prepare by reacting a compound of formula 1 and a compound of formula 2 in a propionic acid solvent

[0011] A compound of formula 3;

[0012]

[0013] Step 2: dissolving the compound of formula 3, the compound of formula 4 and triethylamine in chloroform, stirring in an ice-water bath, and then transferring to an oven for reaction to obtain a compound of formula 5;

[0014]

[0015] Step 3: reacting the compound of formula 5 with a metal salt to obtain a vanillin porphyrin compound of formula I;

[0016]

[0017] Step 4: Nanoparticles are coated on the vanillin porphyrin compound of formula I to obtain a metal porphyrin organic framework structure derivative, wherein the nanoparticles are silicon dioxide, polyphosphazene or polyaniline.

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

[0019] Preferably, when the nanoparticles are silicon dioxide, step 4 is specifically: reacting the vanillin porphyrin compound of formula I with hexadecyltrimethylammonium bromide and ethyl orthosilicate under alkaline conditions to obtain the metal porphyrin organic framework structure derivative P1.

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

[0021] Preferably, when the nanoparticles are polyphosphazenes, step four is specifically: reacting the vanillin porphyrin compound of formula I with 4,4'-dihydroxydiphenyl sulfone, cyclotriphosphazene and triethylamine to obtain a metal porphyrin organic framework structure 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 hours.

[0023] Preferably, when the nanoparticles are polyaniline, step 4 is specifically: 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 a metal porphyrin organic framework derivative P3.

[0024] Preferably, the mass ratio of the 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 use of the metalloporphyrin organic framework structure derivative as a flame retardant.

[0026] Beneficial Effects of the Invention

[0027] The present invention provides a metal porphyrin organic framework structure derivative and its preparation method and application. The present invention uses vanillin to prepare porphyrin organic compounds, and then successfully prepares a series of metal porphyrins by chelating metal ions. At the same time, the series of metal porphyrins can be prepared by wrapping nanoparticles of silicon dioxide (SiO2), polyphosphazene (PZS) and polyaniline (PANI) on the vanillin porphyrin compound through a variety of simple methods to prepare a series of metal porphyrin derivatives, and add them to polymers as flame retardants to study the impact on the fire safety of polymers. In the present invention, epoxy resin (EP) is used as a typical polymer, and metal porphyrin flame retardants are added thereto 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 were reduced by 48.1%, 31.7% and 20.5% respectively; the THR of EP / P1, EP / P2 and EP / P3 were reduced by 25.8%, 21.4% and 20.8% respectively; the SPR of EP / P1, EP / P2 and EP / P3 were reduced by 52.2%, 17.4% and 15.2% respectively; the TSP of EP / P1, EP / P2 and EP / P3 were reduced by 43.3%, 22.4% and 13.5% respectively. The metal porphyrin derivative flame retardant proposed in the present invention has high efficient flame retardant and smoke suppression performance and thermal stability, and has broad application prospects in the field of flame retardant of polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a schematic diagram of the structure of the metal porphyrin organic framework derivative of the present invention.

[0029] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of the vanillin porphyrin compound of formula 5 prepared in Example 1 of the present invention.

[0030] Figure 3The SEM scanning electron microscope images of the metalloporphyrin organic framework structure and its derivatives P1 and P2 of the present invention.

[0031] Figure 4 Heat release rate (HRR) images of EP, EP / P1, EP / P2 and EP / P3 of the present invention

[0032] Figure 5 Total heat release rate (THR) graph of EP, EP / P1, EP / P2 and EP / P3 of the present invention

[0033] Figure 6 The smoke release rate (SPR) images of EP, EP / P1, EP / P2 and EP / P3 of the present invention are shown in FIG.

[0034] Figure 7 The total smoke release (TSP) images of EP, EP / P1, EP / P2 and EP / P3 of the present invention are shown in FIG.

[0035] Figure 8 The CO2 release rate (PCO2P) graph of EP, EP / P1, EP / P2 and EP / P3 of the present invention is shown in FIG.

[0036] Fig. 9 The graphs are the CO release rates (PCOP) of EP, EP / P1, EP / P2 and EP / P3 of the present invention. DETAILED DESCRIPTION

[0037] The present invention first provides a metal porphyrin organic framework structure derivative, which is prepared by encapsulating a vanillin porphyrin compound of formula 1 with nanoparticles, wherein the nanoparticles are silicon dioxide, polyphosphazene or polyaniline, and the vanillin porphyrin compound of formula I has the following structural formula:

[0038]

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

[0040] The present invention also provides a method for preparing a metal porphyrin organic framework structure derivative, comprising:

[0041] Step 1: reacting a compound of Formula 1 and a compound of Formula 2 in a propionic acid solvent to prepare a 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° C., and the reaction time is preferably 1-3 h;

[0042]

[0043] Step 2: dissolving the compound of formula 3, the compound of formula 4 and triethylamine in chloroform, stirring in an ice-water bath, and transferring to an oven for reaction to obtain a compound of formula 5; the mass ratio of the compound of formula 3, the compound of formula 4 and triethylamine is preferably 1:1.2:1; the temperature of the ice-water bath is preferably 0-10°C, the oven reaction temperature is preferably 60-80°C, and the reaction time is preferably 10-14h;

[0044]

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

[0046]

[0047] The preparation process is as follows:

[0048]

[0049] Step 4: Nanoparticles are coated on the vanillin porphyrin compound of formula I to obtain a metal porphyrin organic framework structure derivative, wherein the nanoparticles are silicon dioxide, polyphosphazene or polyaniline.

[0050] According to the present invention, when the nanoparticles are silicon dioxide, step 4 is specifically: reacting the vanillin porphyrin compound of formula I with hexadecyltrimethylammonium bromide and tetraethyl orthosilicate under alkaline conditions to obtain the metal porphyrin organic framework structure derivative P1. The mass ratio of the vanillin porphyrin compound of formula I: hexadecyltrimethylammonium bromide: tetraethyl orthosilicate is preferably 2:2.6:1, the pH value is 8-10, the reaction temperature is preferably room temperature, the reaction time is preferably 16-20h, and the vanillin porphyrin compound of formula I, wherein Me is Fe;

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

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

[0053] The structural formula of the metal porphyrin organic framework derivative prepared by the present invention is as follows: Figure 1 shown.

[0054] The present invention also provides the use of the metalloporphyrin organic framework structure derivative as a flame retardant.

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

[0056] The metal porphyrin organic framework structure derivative is dissolved in a solvent, wherein the solvent is preferably an acetone solution, and ultrasonic stirring is performed, wherein the stirring time is preferably 1-3 hours. Preheated epoxy resin is added, and ultrasonic stirring is continued, wherein the stirring time is preferably 1-3 hours to obtain a mixture. The mixture is transferred to 60-100° C. and heated and stirred for 10-14 hours, and then the pre-melted 4,4-diaminodiphenylmethane solid is added. The mixture is then transferred to a mold and heated at 80-120° C. for 1-3 hours, and then heated 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 is further described in detail below with reference to specific examples, and the raw materials involved in the examples are all commercially available.

[0061] Example 1 Preparation of Vanillin Porphyrin Compound of Formula 5

[0062] Step A: dissolving the compound of formula 1 in propionic acid, adding the compound of formula 2 under oil bath heating conditions, and then transferring to a reactor, the oil bath temperature is 140°C, the reactor temperature is 140°C, and the heating time is continued for 2 hours. After the reaction is completed, the mixture is soaked 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 are dissolved in chloroform and stirred in an ice water bath at 5°C, and then transferred to an oven for reaction at 70°C for 12 hours. The mixture is soaked in alcohol, centrifuged, washed and dried to prepare a compound of formula 5. The mass ratio of the compound of formula 3: the compound of formula 4: triethylamine is 1:1.2:1.

[0064] The NMR spectrum of the prepared compound of formula 5 is as follows Figure 2 As shown. The chemical shift at 8.7ppm is the proton on the porphyrin ring (marked as a); the chemical shift at -2.9ppm is the -NH group (marked as e); the chemical shifts at 8.1ppm and 7.5ppm are the protons on the benzene ring (marked as b and c); the chemical shift at 3.8ppm is -CH3 in the pyrrole structure, and the band at 2.2ppm to 1.0ppm is -CH- in the pyrrole structure. The analysis results of the nuclear magnetic resonance hydrogen spectrum show that the present invention successfully synthesized the vanillin porphyrin compound.

[0065] Example 2 Preparation of iron porphyrin organic framework compound

[0066] The compound of formula 5 prepared in Example 1 and FeCl3·6H2O were heated in chloroform solution at 60°C for 2 hours, and centrifuged, washed and dried 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 Multimetallic Porphyrin Organic Framework Compounds

[0068] The compound of formula 5 prepared in Example 1 was heated with FeCl3·6H2O and MgCl2·6H2O in deionized water at 60°C for 2 hours, and then centrifuged, washed and dried to prepare a multimetallic 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, hexadecyltrimethylammonium bromide and ethyl orthosilicate were dissolved in ethanol at a mass ratio of 2:2.6:1, and the pH value was adjusted to 9 using NH3·H2O. After reacting at room temperature under alkaline conditions for 18 hours, the mixture was centrifuged, washed and dried to obtain derivative P1.

[0071] Example 5 Preparation of derivative P2

[0072] The iron porphyrin organic framework compound prepared in Example 2 was dissolved in a methanol solution with a mass ratio of 1:0.7:0.3:1.4, respectively, and reacted at room temperature for 10 hours, followed by centrifugation, washing and drying to obtain a derivative P2.

[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, and magnetic stirring was performed in an ice-water bath for 6 hours, followed by centrifugal washing and drying 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 / metal porphyrin organic framework structure derivative composite material

[0076] The metal porphyrin derivative prepared in Example 4-6 was dissolved in acetone and ultrasonically stirred for 2 hours. Then a certain amount of preheated epoxy resin was added to the above solution and ultrasonic stirring was continued for 2 hours. The mixed solution was transferred to an oil bath pot and stirred at 80°C for 12 hours. After a certain amount of molten 4,4-diaminodiphenylmethane solid was added thereto, it was quickly poured into the template and transferred to an oven. It was cured at 100°C and 150°C for 2 hours respectively to prepare an epoxy resin / metal porphyrin organic framework structure derivative composite material.

[0077] In EP / P1, the addition amount of the metal porphyrin derivative P1 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 addition amount of the metal porphyrin derivative P2 is 2 wt %, and the mass ratio of P2, epoxy resin and 4,4-diaminodiphenylmethane solid is 1.2:60:12.

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

[0080] The structure and morphology of metalloporphyrin and metalloporphyrin organic framework derivatives were observed using scanning electron microscopy. Figure 3 As shown in Figures a to f, vanillin porphyrin, iron porphyrin, metal porphyrin derivative P1, metal porphyrin derivative P2, iron-magnesium bimetallic porphyrin, and metal porphyrin derivative P3, respectively. The scanning electron microscope image of vanillin porphyrin shows a block structure with a size ranging from 0.8 microns to 1.5 microns ( Figure 3 a), which is the result of the π-π bond interaction between the benzene rings of vanillin porphyrin. The microstructure of iron metalloporphyrin is blocky and the size is between 0.5 and 0.6 microns ( Figure 3 b), this is because the coordination with Fe(III) destroys the interaction of π-π bonds. In contrast, the metal porphyrin organic framework derivative P1 presents a cauliflower-like structure, and a large number of rough microspheres representing SiO2 can be seen on its surface ( Figure 3 c), which increases the specific surface area of ​​the metalloporphyrin. Compared with the 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), indicating that the PZS microspheres have been successfully loaded onto the surface of the metalloporphyrin organic framework structure. The iron-magnesium bimetalloporphyrin is spindle-shaped ( Figure 3 e), this is because the coordination of the iron-magnesium bimetallic further destroys the π-π bond interaction of the benzene ring of vanillin porphyrin. Compared with the iron-magnesium bimetallic porphyrin, the metal porphyrin organic framework derivative P3 is uniformly doped with nano-PANI microspheres ( Figure 3 f), indicating that PANI microspheres have been successfully loaded onto the surface of the metalloporphyrin organic framework structure.

[0081] See attached Figure 4 , is the heat release rate (HRR) image of EP, EP / P1, EP / P2 and EP / P3 measured by cone calorimetry. The peak heat release rate (PHRR) of pure EP is 1329.3kW / m 2 When the metal porphyrin organic framework derivatives were added, the PHRR of the polymer decreased significantly. The PHRRs of EP / P1, EP / P2 and EP / P3 were 689.4, 907.3 and 923.3 kW / m, respectively. 2, which were reduced by 48.1%, 31.7% and 20.5% respectively compared with pure EP.

[0082] See attached Figure 5 , is the total heat release rate (THR) graph of EP, EP / P1, EP / P2 and EP / P3 measured using cone calorimetry. The THR of pure EP is 93.91 MJ / m 2 When the metal porphyrin organic framework derivatives were added, the THR of the polymers decreased significantly. The PHRRs of EP / P1, EP / P2 and EP / P3 were 67.9, 73.8 and 74.4 MJ / m 2 , which were reduced by 25.8%, 21.4% and 20.8% respectively compared with pure EP.

[0083] See attached Figure 6 , is the smoke release rate (SPR) image of EP, EP / P1, EP / P2 and EP / P3 measured by cone calorimetry. The SPR of pure EP is 0.46m 2 / s. When the metal porphyrin organic framework derivatives were added, the SPR of the polymers decreased significantly. The PHRRs of EP / P1, EP / P2 and EP / P3 were 0.22, 0.38 and 0.39 m / s, respectively. 2 / s, which were reduced by 52.2%, 17.4% and 15.2% respectively compared with pure EP.

[0084] See attached Figure 7 , is a graph of the total smoke release (TSP) of EP, EP / P1, EP / P2, and EP / P3 measured using a cone calorimeter test. The TSP of pure EP is 41.6m 2 When the metal porphyrin organic framework derivatives were added, the TSP of the polymers decreased significantly. The TSP of EP / P1, EP / P2 and EP / P3 were 23.6, 32.3 and 36.0 m 2 , which were reduced by 43.3%, 22.4% and 13.5% respectively compared with pure EP.

[0085] See attached Figure 8 , which is the CO2 release rate (PCO2P) image of EP, EP / P1, EP / P2 and EP / P3 measured by cone calorimetry. The PCO2P of pure EP is 0.91 g / s. When the metal porphyrin organic framework derivative is added, the PCO2P of the polymer is significantly reduced. The PHRR of EP / P1, EP / P2 and EP / P3 are 0.45, 0.60 and 0.61 g / s, respectively, which are 50.5%, 34.1% and 33.0% lower than that of pure EP.

[0086] See attached Fig. 9, which is the CO release rate (PCOP) image of EP, EP / P1, EP / P2 and EP / P3 measured by cone calorimetry. The PCOP of pure EP is 0.106 g / s. When the metal porphyrin organic framework derivative is added, the PCOP of the polymer is significantly reduced. The PHRR of EP / P1, EP / P2 and EP / P3 are 0.051, 0.028 and 0.035 g / s, respectively, which are 51.9%, 73.6% and 67.0% lower than that of 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: The derivative is prepared by encapsulating a vanillin porphyrin compound of formula I with nanoparticles, wherein the nanoparticles are silicon dioxide, polyphosphazene or polyaniline, and the vanillin porphyrin compound of formula I has the following structural formula: Wherein, Me is a chelated metal ion.

2. The method for preparing a metalloporphyrin organic framework derivative according to claim 1, characterized in that: include: Step 1: reacting a compound of formula 1 and a compound of formula 2 in a propionic acid solvent to prepare a compound of formula 3; Step 2: dissolving the compound of formula 3, the compound of formula 4 and triethylamine in chloroform, stirring in an ice-water bath, and then transferring to an oven for reaction to obtain a compound of formula 5; Step 3: reacting the compound of formula 5 with a metal salt to obtain a vanillin porphyrin compound of formula I; Step 4: Nanoparticles are coated on the vanillin porphyrin compound of formula I to obtain a metal porphyrin organic framework structure derivative, wherein the nanoparticles are silicon dioxide, polyphosphazene or polyaniline.

3. The method for preparing a metalloporphyrin organic framework derivative according to claim 2, characterized in that: The metal salt is one of FeCl3·6H2O and MgCl2·6H2O or a mixture of the two.

4. The method for preparing a metalloporphyrin organic framework derivative according to claim 2, characterized in that: When the nanoparticles are silicon dioxide, step 4 is specifically: reacting the vanillin porphyrin compound of formula I with hexadecyltrimethylammonium bromide and ethyl orthosilicate under alkaline conditions to obtain the metal porphyrin organic framework structure derivative P1.

5. The method for preparing a metalloporphyrin organic framework derivative according to claim 4, characterized in that: The mass ratio of the vanillin porphyrin compound of formula I: hexadecyltrimethylammonium bromide: ethyl orthosilicate is 2:2.6:1, the pH value is 8-10, the reaction temperature is room temperature, and the reaction time is 16-20 hours.

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

7. The method for preparing a metalloporphyrin organic framework derivative according to claim 6, characterized in that: 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 hours.

8. The method for preparing a metalloporphyrin organic framework derivative according to claim 2, characterized in that: When the nanoparticles are polyaniline, step 4 is specifically: reacting the vanillin porphyrin compound of formula I with aniline and ammonium persulfate in an acidic ice-water bath with stirring to obtain a metal porphyrin organic framework derivative P3.

9. The method for preparing a metalloporphyrin organic framework derivative according to claim 8, characterized in that: The mass ratio of the 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.

10. Use of the metalloporphyrin organic framework derivative according to claim 1 as a flame retardant.

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