A chemical warfare agent simulation degradation composite material based on a porphyrin functional component and a preparation method thereof

Abstract

The present application relates to a kind of chemical war agent simulation degradation composite material based on porphyrin functional component and preparation method thereof, belong to chemical protection material and functional composite material technical field.The stable composite network structure is constructed by introducing porphyrin organic molecules into metal organic framework material and combining organosilicon silsesquioxane, and the firm immobilization of functional component on the surface of matrix material is realized.The composite material can produce catalytic degradation effect on chemical war agent simulation, has structural stability and functional durability, and is suitable for protective fabric and related chemical protection material field.The preparation process of the present application is simple, has good application prospect and popularization value.

Description

Technical Field

[0001] This invention belongs to the technical field of chemical protective materials and functional composite materials, specifically relating to a chemical warfare agent simulating degradation composite material based on porphyrin functional components, as well as the preparation method and application of the composite material. In particular, it relates to a functional protective material for catalytic degradation of chemical warfare agent simulants by synergistically immobilizing porphyrin functional components on the surface of a fabric matrix through organosilicon silsesquioxane and metal-organic framework materials. Background Technology

[0002] Chemical warfare agents and similar toxic chemicals are characterized by high toxicity, rapid action, and severe environmental hazards, posing a significant threat to personnel health and safety in military protection, emergency rescue, and public safety. Existing protective materials primarily rely on physical barriers or adsorption to protect against chemical warfare agents, such as activated carbon fibers, adsorbent fillers, and coating materials. However, these materials are prone to adsorption saturation during practical use, making continuous handling of chemical warfare agents difficult. Furthermore, they are susceptible to secondary pollution under complex environmental conditions, failing to meet the requirements for long-term, stable protection.

[0003] To achieve proactive treatment of chemical warfare agents, researchers have recently attempted to introduce catalytically active functional components for the degradation of chemical warfare agents or their analogues. However, liquid-phase catalytic systems or enzyme catalytic systems generally suffer from poor stability, limited application conditions, and difficulty in integrating with flexible protective materials. While some inorganic catalytic materials possess certain degradation capabilities, their bonding strength with matrix materials such as fabrics is insufficient, leading to easy detachment or deactivation, making long-term use in protective materials difficult.

[0004] Porphyrins and their derivatives, due to their unique conjugated structures and catalytic activities, have shown potential application value in the field of toxic chemical degradation. However, in existing technologies, porphyrins are mostly present in free molecule or simple supported forms, which suffers from problems such as easy loss, difficulty in immobilization, and insufficient durability, limiting their practical application in protective materials. Therefore, how to stably introduce porphyrin functional components into protective material systems and achieve continuous degradation of chemical warfare agent simulants while ensuring structural stability remains a pressing technical problem to be solved in this field. Summary of the Invention

[0005] The technical problem solved by this invention is to overcome the shortcomings of the prior art and propose a chemical warfare agent-simulated degradation composite material based on porphyrin functional components.

[0006] The technical solution of this invention is: A chemical warfare agent-simulated degradation composite material based on porphyrin functional components, the composite material comprising a matrix material, a metal-organic framework material loaded on the surface of the matrix material, porphyrin functional components, and organosilicon silsesquioxane compounds; wherein the matrix material in the composite material has a mass percentage of 70 wt% to 90 wt%; the raw materials for preparing the composite material include zinc nitrate hexahydrate (Zn(NO3)2·6H2O), 2-methylimidazolium (2-mIM), 4-imidazolium formaldehyde (4-ICA), polyethylene glycol (PEG-4000), tetrakis(4-carboxyphenyl)porphyrin (TCPP), octavinyl polyhedral oligomeric silsesquioxane (POSS), cysteine ​​(HS-CH2-CH2-NH2), and azobisisobutyronitrile (AIBN); With the total mass of the metal-organic framework material, porphyrin functional component, and organosilicon sesquioxane compound loaded on the surface of the matrix material as 100%, the mass percentage of each component is as follows: The above-mentioned method for preparing a chemical warfare agent-simulated degradation composite material based on porphyrin functional components includes the following steps: S1. Powder premixing: Weigh 1.746 g of zinc nitrate hexahydrate, 0.4925 g of 2-methylimidazole, 0.660 g of 4-imidazole formaldehyde and 0.75 g of polyethylene glycol (PEG-4000), place the above raw materials in a mortar and mix and grind to obtain a uniformly mixed premixed powder; S2. Fabric Pretreatment: Select a clean, dry cotton fabric sample and place it in a 250 mL beaker. Add sufficient anhydrous ethanol. Use an ultrasonic cleaner to sonicate the sample for 10 minutes to remove impurities, grease, or other contaminants that may affect material bonding from the fabric surface. After ultrasonic treatment, remove the cotton fabric and place it in an oven at 40 °C until completely dry. S3, MOF precursor hot-press loading: The premixed powder obtained in step S1 is evenly spread on the surface of the pretreated cotton fabric and processed under hot-press conditions to load and construct the metal-organic framework precursor components on the fabric surface; the hot-press conditions are temperature 200 ℃, pressure 100 MPa, and time 10 min. S4. Surface cleaning and drying: The sample obtained in step S3 was cleaned with ethanol to remove unreacted residues, and then vacuum dried at 40 °C to obtain metal-organic framework-loaded fabric. S5. Preparation of aminated organosilicon silsesquioxane: 1.0 g of octavinyl polyhedral oligomeric silsesquioxane was dissolved in 40 mL of anhydrous ethanol, and 1.1 g of cysteamine and 0.01 g of azobisisobutyronitrile were added sequentially. The mixture was reacted at 70-75 °C for 12-24 h under inert gas protection to obtain an aminated organosilicon silsesquioxane reaction solution. S6. Obtaining Aminated Organosilicon Silsesquioxane: The reaction solution from step S5 is subjected to precipitation, separation, washing and drying to obtain the aminated organosilicon silsesquioxane product. S7. Construction of the porphyrin-organosilicon silsesquioxane composite system: Tetra(4-carboxyphenyl)porphyrin and the aminated organosilicon silsesquioxane obtained in step S6 were mixed and compounded in a solvent, and then dried to obtain the porphyrin-organosilicon silsesquioxane composite system. S8. Secondary hot pressing to construct the composite network structure: The metal-organic framework-loaded fabric obtained in step S4 is laid flat, and the porphyrin-organosilicon silsesquioxane composite system obtained in step S7 is introduced onto its surface. A secondary hot pressing treatment is then performed, allowing the porphyrin functional components to synergistically construct the composite network structure through the organosilicon silsesquioxane and the metal-organic framework material. The hot pressing conditions are: temperature 200 ℃, pressure 100 MPa, and time 10 min. S9. Final Cleaning and Drying: The sample obtained in step S8 was cleaned with ethanol to remove free components, and then vacuum dried at 40 °C to obtain a chemical warfare agent-simulated degradation composite material based on porphyrin functional components. The porphyrin functional components account for approximately 4% of the mass of the composite material. Beneficial effects

[0007] Compared with existing technologies, this invention has at least the following beneficial effects: This invention uses porphyrin functional components as the active centers for the simulated degradation of chemical warfare agents, achieving active catalytic degradation of chemical warfare agent mimics, breaking through the traditional protective material protection mode that relies solely on physical barriers or adsorption; by introducing organosilicon silsesquioxanes as linking components, the porphyrin functional components and metal-organic framework materials form a stable composite structure, effectively improving the immobilization stability and durability of the porphyrin functional components in the composite material; the porous structure of the metal-organic framework material provides a good carrying platform for the functional components, which is beneficial for maintaining the accessibility and catalytic activity of the porphyrin functional components; the preparation method of this invention is simple and highly controllable, suitable for constructing chemical warfare agent simulated degradation functional layers on flexible matrix materials such as fabrics, and has good engineering application prospects. Attached Figure Description

[0008] Figure 1 This is a schematic diagram of the overall preparation process of the chemical warfare agent simulated degradation composite material based on porphyrin functional components according to the present invention.

[0009] Figure 2 This is a schematic diagram of the porphyrin-organosilicon sesquioxane-metal-organic framework composite network structure. Detailed Implementation

[0010] The present invention will be further described below with reference to the accompanying drawings and embodiments. A chemical warfare agent-simulating degradation composite material based on porphyrin functional components, the composite material comprising a matrix material, a metal-organic framework material supported on the surface of the matrix material, porphyrin functional components, and organosilicon sesquioxane compounds; wherein the mass percentage of the matrix material in the composite material is 70 wt% to 90 wt%. The raw materials of the composite material include zinc nitrate hexahydrate Zn(NO3)2·6H2O, 2-methylimidazolium 2-mIM, 4-imidazolium formaldehyde 4-ICA, polyethylene glycol PEG, porphyrin functional components, octavinyl polyhedral oligomeric silsesquioxane POSS, cysteine ​​HS-CH2-CH2-NH2, and azobisisobutyronitrile AIBN; Based on the total mass of the aforementioned metal-organic framework material, porphyrin functional component, and organosilicon sesquioxane compound as 100%, the mass percentage of each component is as follows: Zinc nitrate hexahydrate 28%-36% 2-Methylimidazole 6%-12% 4-Imidazole formaldehyde 8%-14% PEG 1%-4% Porphyrin functional components 1%-8% Octaviovinyl POSS 18%-26% cysteine 18%-28% Azobisisobutyronitrile 0.1%-0.6% 。 In a preferred embodiment, the mass percentage of each component is as follows: Zinc nitrate hexahydrate 32%-36% 2-Methylimidazole 9%-12% 4-Imidazole formaldehyde 11%-14% PEG 3%-4% Porphyrin functional components 5%-8% Octaviovinyl POSS 18%-22% cysteine 18%-23% Azobisisobutyronitrile 0.1%-0.3% 。 In a preferred embodiment, the mass percentage of each component is as follows: Zinc nitrate hexahydrate 28%-32% 2-Methylimidazole 6%-9% 4-Imidazole formaldehyde 8%-11% PEG 1%-3% Porphyrin functional components 1%-5% Octaviovinyl POSS 22%-26% cysteine 23%-28% Azobisisobutyronitrile 0.3%-0.6% 。 In a preferred embodiment, the porphyrin functional component is tetrakis(4-carboxyphenyl)porphyrin TCPP or its metallized derivative. In a preferred embodiment, the matrix material is cotton fabric. The polyethylene glycol (PEG) is polyethylene glycol PEG4000.

[0011] A method for preparing the chemical warfare agent simulated degradation composite material, the method comprising the following steps: The first step is to weigh zinc nitrate hexahydrate, 2-methylimidazole, 4-imidazole formaldehyde and PEG according to the predetermined mass ratio, put them into a mortar and grind and mix them to obtain a uniformly mixed premixed powder. The second step is to perform ultrasonic cleaning and drying of the substrate material with ethanol. The third step is to evenly spread the premixed powder on the surface of the pretreated matrix material, cover it with aluminum foil, and press it with a hot press to achieve the loading of metal-organic framework material on the surface of the matrix material. The fourth step involves soaking the matrix material obtained in the third step in ethanol and manually cleaning it to remove unreacted residues, followed by vacuum drying to obtain the metal-organic framework supported matrix material. Fifth step: Octadecyl POSS is mixed with cysteine ​​and azobisisobutyronitrile in anhydrous ethanol solution and reacted in an oil bath under nitrogen protection to synthesize the amination POSS reaction solution. Step 6: The reaction solution obtained in step 5 is subjected to precipitation, separation, washing, and drying to obtain the amination-modified POSS product. Step 7: Mix the porphyrin functional component with the aminated POSS obtained in step 5, and form a porphyrin functional component-POSS composite system by solution compounding and drying curing. Step 8: The porphyrin functional component-POSS composite system is introduced into the material obtained in step 4, and a porphyrin functional component-organosilicon sesquioxane-metal-organic framework composite network structure is constructed by secondary hot pressing to obtain the target composite material.

[0012] In a preferred embodiment, in the first step, the mass amounts of zinc nitrate hexahydrate, 2-methylimidazole, 4-imidazolium formaldehyde, and PEG are 1.746 g, 0.4925 g, 0.660 g, and 0.75 g, respectively. In the fifth step, the amount of octavinyl POSS is 1.0 g, the amount of cysteine ​​is 1.1 g, the amount of azobisisobutyronitrile is 0.01 g, and the amount of anhydrous ethanol in the reaction system is 40 mL.

[0013] In a preferred embodiment, in the fifth step, the nitrogen flow rate is 50 mL / min, the nitrogen introduction time is 30 min, the reaction temperature is controlled at 70-75 ℃, and the reaction time is 12-24 h. In the third and eighth steps, the hot-pressing conditions are a temperature of 200 ℃, a pressure of 100 MPa, and a time of 10 min.

[0014] The application of the above-mentioned chemical warfare agent simulant degradation composite material in protective fabrics or chemical protective materials for the degradation of chemical warfare agents or their simulants.

[0015] Example 1 A method for preparing a chemical warfare agent-simulated degradation composite material based on porphyrin functional components includes the following steps: 1.746 g of zinc nitrate hexahydrate, 0.4925 g of 2-methylimidazole, 0.660 g of 4-imidazolium formaldehyde, and 0.75 g of polyethylene glycol (PEG-4000) were weighed and thoroughly ground in a mortar to obtain a uniform premixed powder. Cotton fabric was ultrasonically cleaned and dried in anhydrous ethanol. The premixed powder was then evenly spread on the surface of the cotton fabric and subjected to hot-pressing treatment at 200 °C and 100 MPa for 10 min to allow the metal-organic framework material to be constructed and loaded in situ on the fabric surface. The sample was then cleaned with ethanol and vacuum dried at 40 °C to obtain a metal-organic framework-loaded fabric. Separately, 1.0 g of octavinyl polyhedral oligomeric silsesquioxane, 1.1 g of cysteine, and 0.01 g of azobisisobutyronitrile were dissolved in 40 mL of anhydrous ethanol and reacted at 70-75 °C for 12-24 h under nitrogen protection to prepare an aminated organosilicon silsesquioxane reaction solution. After the reaction was completed, the product was obtained by precipitation, separation, washing, and drying. Weigh 0.24 g of tetra(4-carboxyphenyl)porphyrin, and combine it with the above-obtained aminated organosilicon sesquioxane in solution. After drying, a porphyrin-organosilicon sesquioxane composite system is obtained. The porphyrin-organosilicon silsesquioxane composite system was uniformly spread on the surface of the metal-organic framework-loaded fabric, and a secondary hot-pressing treatment was performed at 200 °C and 100 MPa for 10 min, so that the porphyrin functional component could synergistically construct a composite network structure with the organosilicon silsesquioxane and the metal-organic framework material to obtain the target composite material. The matrix material in the composite material has a mass percentage of 80 wt%. The resulting composite material was used in a chemical warfare agent simulation degradation experiment, and the results showed that the material could effectively promote the degradation of chemical warfare agent simulants.

[0016] Comparative Example 1 (without porphyrin functional components) The preparation method of Comparative Example 1 was the same as that of Example 1, except that no porphyrin functional component was introduced. That is, after constructing the metal-organic framework material on the fabric matrix surface and functionalizing the organosilicon silsesquioxane, the porphyrin functional component was not introduced into the composite system, and the resulting material was directly subjected to a secondary hot-pressing treatment. When the resulting material was used to treat chemical warfare agent simulants, it did not exhibit significant catalytic degradation, indicating that the porphyrin functional component plays an important role as an active center for the degradation of chemical warfare agents in the composite material.

[0017] Comparative Example 2 (without the introduction of organosilicon sesquioxane linker) The preparation method of Comparative Example 2 was the same as that of Example 1, except that the organosilicone silsesquioxane was not introduced as a linking component. That is, after constructing the metal-organic framework material and loading the fabric, the porphyrin functional component was directly introduced into the material system without composite linking treatment using organosilicone silsesquioxane. The resulting material exhibited poor immobilization stability of the porphyrin functional component, which was prone to loss during use, leading to unstable degradation of chemical warfare agent simulants. This indicates that organosilicone silsesquioxane plays a crucial linking role in constructing a stable composite structure.

[0018] Comparative Example 3 (No metal-organic framework material was constructed on the fabric surface) The preparation method of Comparative Example 3 was identical to that of Example 1, except that a metal-organic framework material was not constructed on the surface of the matrix material. That is, only the porphyrin-organosilicone sesquioxane composite system was introduced onto the surface of the fabric matrix, without providing a metal-organic framework material as a porous load-bearing structure. Due to the lack of structural support and synergistic effect of the metal-organic framework material, the resulting material showed limited effectiveness in treating chemical warfare agent simulants, illustrating the importance of metal-organic framework materials as a load-bearing platform and synergistic structure in composite materials.

[0019] In summary, the above are merely preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A chemical warfare agent-simulated degradation composite material based on porphyrin functional components, characterized in that: The composite material comprises a matrix material, a metal-organic framework material supported on the surface of the matrix material, a porphyrin functional component, and an organosilicon sesquioxane compound; wherein the matrix material in the composite material has a mass percentage of 70 wt% to 90 wt%. The raw materials of the composite material include zinc nitrate hexahydrate Zn(NO3)2·6H2O, 2-methylimidazolium 2-mIM, 4-imidazolium formaldehyde 4-ICA, polyethylene glycol PEG, porphyrin functional components, octavinyl polyhedral oligomeric silsesquioxane POSS, cysteine ​​HS-CH2-CH2-NH2, and azobisisobutyronitrile AIBN; Based on the total mass of the aforementioned metal-organic framework material, porphyrin functional component, and organosilicon sesquioxane compound as 100%, the mass percentage of each component is as follows: Zinc nitrate hexahydrate 28%-36% 2-Methylimidazole 6%-12% 4-Imidazole formaldehyde 8%-14% PEG 1%-4% Porphyrin functional components 1%-8% Octavinyl POSS 18%-26% Cysteine ​​18%-28% Azobisisobutyronitrile (AIORT) 0.1%-0.6%.

2. The chemical warfare agent simulated degradation composite material according to claim 1, characterized in that, The mass percentage of each component is as follows: Zinc nitrate hexahydrate 32%-36% 2-Methylimidazole 9%-12% 4-Imidazole formaldehyde 11%-14% PEG 3%-4% Porphyrin functional components 5%-8% Octadecyl POSS 18%-22% Cysteine ​​18%-23% Azobisisobutyronitrile (AIBN) 0.1%-0.3%.

3. The chemical warfare agent simulated degradation composite material according to claim 1, characterized in that, The mass percentage of each component is as follows: Zinc nitrate hexahydrate 28%-32% 2-Methylimidazole 6%-9% 4-Imidazole formaldehyde 8%-11% PEG 1%-3% Porphyrin functional components 1%-5% Octadecyl POSS 22%-26% Cysteine ​​23%-28% Azobisisobutyronitrile (AIBN) 0.3%-0.6%.

4. The chemical warfare agent simulated degradation composite material according to claim 1, 2 or 3, characterized in that, The porphyrin functional component is tetra(4-carboxyphenyl)porphyrin TCPP or its metallized derivative.

5. A method for preparing a chemical warfare agent simulated degradation composite material as described in claim 1, 2, or 3, characterized in that, The method includes the following steps: The first step is to weigh zinc nitrate hexahydrate, 2-methylimidazole, 4-imidazole formaldehyde and PEG according to the predetermined mass ratio, put them into a mortar and grind and mix them to obtain a uniformly mixed premixed powder. The second step is to perform ultrasonic cleaning and drying of the substrate material with ethanol. The third step is to evenly spread the premixed powder on the surface of the pretreated matrix material, cover it with aluminum foil, and press it with a hot press to achieve the loading of metal-organic framework material on the surface of the matrix material. The fourth step involves soaking the matrix material obtained in the third step in ethanol and manually cleaning it to remove unreacted residues, followed by vacuum drying to obtain the metal-organic framework supported matrix material. Fifth step: Octadecyl POSS is mixed with cysteine ​​and azobisisobutyronitrile in anhydrous ethanol solution and reacted in an oil bath under nitrogen protection to synthesize the amination POSS reaction solution. The sixth step involves precipitating, separating, washing, and drying the reaction solution obtained in the fifth step to obtain the amination-modified POSS product. Step 7: Mix the porphyrin functional component with the aminated POSS obtained in step 5, and form a porphyrin functional component-POSS composite system by solution compounding and drying curing. Step 8: The porphyrin functional component-POSS composite system is introduced into the material obtained in step 4, and a porphyrin functional component-organosilicon sesquioxane-metal-organic framework composite network structure is constructed by secondary hot pressing to obtain the target composite material.

6. The preparation method according to claim 5, characterized in that, In the first step, the masses of zinc nitrate hexahydrate, 2-methylimidazole, 4-imidazole formaldehyde, and PEG were 1.746 g, 0.4925 g, 0.660 g, and 0.75 g, respectively.

7. The preparation method according to claim 5, characterized in that, In the fifth step, the amount of octavinyl POSS used is 1.0 g, the amount of cysteine ​​used is 1.1 g, the amount of azobisisobutyronitrile used is 0.01 g, and the amount of anhydrous ethanol used in the reaction system is 40 mL.

8. The preparation method according to claim 5, characterized in that, In the fifth step, the nitrogen flow rate is 50 mL / min, the nitrogen flow time is 30 min, the reaction temperature is controlled at 70-75 ℃, and the reaction time is 12-24 h.

9. The preparation method according to claim 5, characterized in that, In the third and eighth steps, the hot pressing conditions are: temperature 200 ℃, pressure 100 MPa, and time 10 min.

10. The application of a chemical warfare agent simulant degradation composite material as described in claim 1, 2, 3 or 4 in protective fabrics or chemical protective materials for the degradation of chemical warfare agents or their simulants.

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