A titanium carbide-based biomass flame retardant and a preparation method thereof
By loading polydopamine and casein onto the surface of titanium carbide and introducing phytic acid, a TiC@PDA@CAS@PA composite material was formed, which solved the problem of poor dispersion of titanium carbide in polymers and achieved high-efficiency flame retardancy and improved mechanical properties.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HUBEI KEPUDA OPTIC-ELECTRIC MATERIAL CO LTD
- Filing Date
- 2023-07-28
- Publication Date
- 2026-07-07
AI Technical Summary
Existing inorganic flame retardants such as TiC have poor dispersibility in polymers, resulting in limited flame retardant effects and reduced mechanical properties.
By loading polydopamine and casein onto the surface of titanium carbide and introducing phytic acid, a TiC@PDA@CAS@PA composite material is formed. The dispersibility and flame retardant properties are enhanced by using a mass ratio of dopamine hydrochloride to TiC of 1:0.5-2.0, a mass ratio of TiC@PDA to casein of 1:1-3, and a mass ratio of TiC@PDA@CAS to phytic acid of 1:0.2-0.8.
It significantly improves the limiting oxygen index of the polymer, enhances the flame retardant effect, and maintains or improves the mechanical properties. It also exhibits good dispersibility with no obvious agglomerates or particles.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of flame retardant materials technology, and specifically relates to a biomass flame retardant based on titanium carbide and its preparation method. Background Technology
[0002] Currently, the preparation of additive flame retardants is largely based on research on inorganic materials. While inorganic materials possess many excellent properties, such as thermal stability, chemical stability, corrosion resistance, and abrasion resistance, simply adding them often deteriorates the performance of the matrix material. Numerous studies have shown that while the addition of additive flame retardants can improve flame retardant performance, it has a greater "negative impact" on mechanical properties. Taking TiC as an example, TiC is an inorganic material, while the matrix (such as resin or plastic) to which TiC needs to be added is an organic material. The polarity of TiC differs greatly from that of organic materials; direct mixing will cause agglomeration, failing to achieve the flame retardant effect and instead reducing mechanical properties.
[0003] The flammability and mechanical properties of composite materials are closely related to the degree of dispersion of nano-additives in the matrix. Well-dispersed nanocomposites exhibit excellent flame retardancy and good mechanical properties. Surface modification is a common method to enhance the dispersibility of inorganic flame retardants in coatings. Organic modification can greatly improve the compatibility between inorganic flame retardants and polymers. Developing organic-inorganic composite flame retardants is a promising area of research.
[0004] Titanium carbide is a two-dimensional inorganic non-metallic material, a typical transition metal carbide, possessing advantages such as high melting point, high hardness, high thermal oxidation resistance, stable chemical properties, good corrosion resistance, and thermal conductivity. In recent years, research on titanium carbide in the field of flame retardancy has attracted widespread attention from scholars, and due to its unique properties, it has broad application prospects in polymers. However, the flame retardant effect of titanium carbide alone on polymers is limited, and its poor dispersibility also negatively impacts the mechanical properties of polymers, hindering its widespread application. Summary of the Invention
[0005] To address the aforementioned problems, this invention provides a biomass flame retardant based on titanium carbide and its preparation method. By loading polydopamine onto the surface of titanium carbide, a large number of active groups are introduced, which is beneficial for subsequent loading and improves the flame retardant performance of the composite. Phytic acid contains phosphorus, which has gas-phase flame retardant properties, and the long molecular chains of casein can improve the thermal stability of the composite, acting as a condensed-phase flame retardant. Modification imparts good dispersibility of titanium carbide in polymer matrices, expanding its application in the flame retardant field. The technical solution is as follows:
[0006] On one hand, embodiments of the present invention provide a biomass flame retardant based on titanium carbide, which is made of TiC, dopamine hydrochloride (PDA), casein (CAS), and phytic acid (PA). Dopamine hydrochloride first modifies TiC to obtain TiC@PDA, then grafts casein to obtain TiC@PDA@CAS, and finally grafts phytic acid to obtain TiC@PDA@CAS@PA. The mass ratio of dopamine hydrochloride to TiC is 1:0.5-2.0, the mass ratio of TiC@PDA to casein is 1:1-3, and the mass ratio of TiC@PDA@CAS to phytic acid is 1:0.2-0.8.
[0007] The raw materials selected for this invention are all bio-based materials, which are green and environmentally friendly. They also contain a large number of active groups, and the components are bonded together by forming a large number of hydrogen bonds.
[0008] The introduction of casein into the system of this invention, during combustion, forms char residue that effectively isolates oxygen and facilitates heat transfer, promoting the formation of a dense char layer and enhancing the protection of the substrate by the polymer or coating. Phosphorus is a novel flame-retardant element that can quench hydrogen free radicals and interrupt the combustion reaction. Phytic acid contains a large amount of phosphorus. On the one hand, the phosphorus-containing free radicals generated by the decomposition of phytic acid can capture hydrogen and hydroxyl free radicals generated during combustion; on the other hand, phytic acid also contributes to the formation of the char layer. Phytic acid can undergo grafting reactions with both dopamine and casein.
[0009] This patent involves organically compounding inorganic TiC, allowing it to disperse in resins or plastics to enhance flame retardant properties. Simultaneously, by compounding with specific organic compounds, the issue of reduced mechanical properties associated with adding flame retardants can be avoided.
[0010] Preferably, the mass ratio of dopamine hydrochloride to TiC is 1:0.8-1.5; more preferably, the mass ratio of dopamine hydrochloride to TiC is 1:0.8-1.2; and most preferably, the mass ratio of dopamine hydrochloride to TiC is 1:1.
[0011] Preferably, the mass ratio of TiC@PDA to casein is 1:1.5-2.5; more preferably, the mass ratio of TiC@PDA to casein is 1:2.
[0012] Preferably, the mass ratio of TiC@PDA@CAS to phytic acid is 1:0.5.
[0013] The preparation process of TiC@PDA is as follows: TiC and Tris buffer are added to deionized water, ultrasonically dispersed, and the pH is adjusted to 8-10. Dopamine hydrochloride is then added according to the specified ratio, and the mixture is stirred at 20-40℃ for 10-20 hours to obtain TiC@PDA. The concentration of tris(hydroxymethyl)aminomethane in the Tris buffer solution is 0.04-0.08 g / mL, and the mass-to-volume ratio (g / mL) of TiC to Tris buffer solution is 1:10-20.
[0014] The preparation process of TiC@PDA@CAS is as follows: Casein is added to a first solvent, heated and stirred to dissolve, and then TiC@PDA is added according to the specified ratio. The mixture is stirred and reacted at 50-70℃ and pH=8-10 for 0.5-2.0 h to obtain TiC@PDA@CAS. The first solvent is selected from one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, potassium carbonate solution, and potassium bicarbonate solution.
[0015] The preparation process of TiC@PDA@CAS@PA is as follows: TiC@PDA@CAS is added to a second solvent, ultrasonically dispersed, and then phytic acid is added according to the formula. The mixture is stirred and reacted at 25-40℃ for 0.5-2.0h to obtain TiC@PDA@CAS@PA. The second solvent is selected from one or more of deionized water or ethanol.
[0016] On the other hand, this invention also provides a method for preparing the aforementioned titanium carbide-based biomass flame retardant, the method comprising:
[0017] (1) Add TiC and Tris buffer to deionized water, disperse by sonication and adjust the pH to 8-10, then add dopamine hydrochloride according to the ratio, and stir the reaction at 20-40℃ to obtain TiC@PDA. The concentration of tris(hydroxymethyl)aminomethane in the Tris buffer solution is 0.04-0.08 g / mL, and the mass-volume ratio (g / mL) of TiC to Tris buffer solution is 1:10-20.
[0018] (2) Casein is added to the first solvent, heated and stirred to dissolve, and then TiC@PDA is added according to the ratio. The reaction is carried out under stirring at 50-70℃ and pH=8-10 to obtain TiC@PDA@CAS. The first solvent is selected from one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, potassium carbonate solution and potassium bicarbonate solution.
[0019] (3) Add TiC@PDA@CAS to the second solvent, disperse ultrasonically, then add phytic acid according to the ratio, and stir the reaction at 25-40℃ to obtain TiC@PDA@CAS@PA. The second solvent is selected from one or more of deionized water or ethanol.
[0020] Specifically, in step (1), ultrasonic dispersion is performed for 20-60 minutes, and stirring reaction is performed for 10-20 hours. Preferably, in step (1), ultrasonic dispersion is performed for 30 minutes, stirring reaction temperature is 30°C, and reaction time is 16 hours.
[0021] Preferably, in step (1), the pH is adjusted to 8.5.
[0022] Preferably, in step (1), the concentration of tris(hydroxymethyl)aminomethane in the Tris buffer solution is 0.05-0.07 g / mL; more preferably, the concentration of tris(hydroxymethyl)aminomethane in the Tris buffer solution is 0.064 g / mL.
[0023] In step (1), the mass-volume ratio (g / mL) of TiC to deionized water is 1:75-120; preferably, the mass-volume ratio (g / mL) of TiC to deionized water is 1:100.
[0024] Further, in step (1), after the reaction is complete, solid-liquid separation is performed by centrifugation, followed by washing with deionized water 2-5 times, and finally vacuum drying at 60-100℃ for 16-24h to obtain TiC@PDA. The centrifugation speed is 3000-5000 r / min. Preferably, the drying temperature is 80℃ and the drying time is 24h.
[0025] Specifically, in step (2), the reaction is stirred for 0.5-2.0 h. Preferably, in step (2), the reaction temperature is 60 °C and the reaction time is 1 h.
[0026] Preferably, in step (2), the pH is adjusted to 9.
[0027] Preferably, in step (2), the first solvent is a sodium bicarbonate solution.
[0028] In step (2), the mass-to-volume ratio (g / mL) of casein to the first solvent is 1:10-20.
[0029] Further, in step (2), after the reaction is complete, solid-liquid separation is performed by centrifugation, followed by washing with ethanol 2-5 times, and finally vacuum drying at 60-80℃ for 10-24h to obtain TiC@PDA@CAS. The centrifugation speed is 5000-8000 r / min. Preferably, the drying temperature is 70℃ and the drying time is 24h.
[0030] Specifically, in step (3), ultrasonic dispersion is performed for 20-60 min, and the reaction is stirred for 0.5-2.0 h. Preferably, in step (3), ultrasonic dispersion is performed for 30 min, the reaction temperature is room temperature, and the reaction time is 1 h.
[0031] Preferably, in step (3), the second solvent is deionized water.
[0032] In step (3), the mass-volume ratio (g / mL) of TiC@PDA@CAS to the second solvent is 1:30-80.
[0033] Further, in step (3), after the reaction is complete, solid-liquid separation is performed by centrifugation, followed by washing with ethanol until neutral, and finally vacuum drying at 60-80℃ for 10-24h to obtain TiC@PDA@CAS@PA. The centrifugation speed is 5000-8000 r / min. Preferably, the drying temperature is 80℃ and the drying time is 24h.
[0034] Preferably, the preparation method of the titanium carbide-based biomass flame retardant provided by the present invention includes the following steps:
[0035] (1) TiC and Tris buffer were added to deionized water, ultrasonically dispersed for 30 min, and the pH was adjusted to 8.5. Dopamine hydrochloride was then added, and the mixture was stirred at 30 °C for 16 h. After the reaction was completed, solid-liquid separation was performed by centrifugation, followed by washing with deionized water. Finally, TiC@PDA was obtained by vacuum drying at 80 °C for 24 h. The concentration of tris(hydroxymethyl)aminomethane in the Tris buffer solution was 0.064 g / mL, the mass-to-volume ratio of TiC to Tris buffer solution (g:mL) was 1:12.5, the mass ratio of dopamine hydrochloride to TiC was 1:1, and the mass-to-volume ratio of TiC to deionized water (g / mL) was 1:100.
[0036] (2) Casein was added to sodium bicarbonate solution and heated and stirred for 30 min. Then TiC@PDA was added, and the mixture was stirred and reacted at 60 °C and pH=9 for 1 h. After the reaction was completed, solid-liquid separation was performed by centrifugation, followed by washing with ethanol. Finally, TiC@PDA@CAS was obtained by vacuum drying at 70 °C for 24 h. The mass ratio of TiC@PDA to casein was 1:2, and the mass-volume ratio (g / mL) of casein to sodium bicarbonate solution was 1:18.
[0037] (3) TiC@PDA@CAS was added to deionized water and ultrasonically dispersed for 30 min. Phytic acid was then added, and the mixture was stirred and reacted at room temperature for 1 h. After the reaction was completed, solid-liquid separation was performed by centrifugation, followed by washing with ethanol. Finally, TiC@PDA@CAS@PA was obtained by vacuum drying at 80 °C for 24 h. The mass ratio of TiC@PDA@CAS to phytic acid was 1:0.5, and the mass-volume ratio (g / mL) of TiC@PDA@CAS to deionized water was 1:50.
[0038] The present invention has the following advantages:
[0039] (1) Powdered flame retardant was added to polyurethane and epoxy resin respectively. After dispersion and curing, the powder was sliced for microscopic observation. If TiC was added directly, obvious agglomerates were found. However, when the biomass flame retardant based on titanium carbide was added, there were no obvious agglomerates and the dispersion effect was good.
[0040] (2) After adding the biomass flame retardant based on titanium carbide, the limiting oxygen index of polyurethane is as high as 31%; compared with polyurethane without flame retardant, the limiting oxygen index is increased by about 80%, and compared with polyurethane with TiC added directly, the limiting oxygen index is increased by about 40%.
[0041] (3) After adding this biomass flame retardant based on titanium carbide, the mechanical properties are not significantly changed. Under certain addition amounts, some mechanical properties are even slightly improved. Attached Figure Description
[0042] Figure 1 This is a comparison chart of the mechanical properties of the biomass flame retardant polyurethane produced in Example 1, which is based on titanium carbide. Detailed Implementation
[0043] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings.
[0044] Example 1
[0045] Example 1 provides a method for preparing a biomass flame retardant based on titanium carbide, comprising the following steps:
[0046] (1) Preparation of TiC@PDA functional material: Weigh 3g TiC and 37.5mL Tris buffer and add to 300mL deionized water for ultrasonic dispersion for 30min. Add NaOH aqueous solution or HCl solution to adjust the pH to 9.5. Then add 3g dopamine hydrochloride and stir the reaction at 30℃ for 16h. After the reaction is completed, centrifuge at 5000r / min. Wash the obtained product three times with distilled water and finally dry it in a vacuum oven at 80℃ for 24h to obtain TiC@PDA functional material.
[0047] (2) Preparation of TiC@PDA@CAS composite material: Weigh 5g of casein and add it to sodium bicarbonate solution (pH=9). Stir at 60℃ for 30min, add 2.5g of TiC@PDA functional material, stir and react for 1h. After centrifugation, the product is washed 3 times with ethanol and dried in a vacuum oven at 70℃ for 24h to obtain TiC@PDA@CAS composite material.
[0048] (3) Preparation of TiC@PDA@CAS@PA composite flame retardant: Weigh 2g of TiC@PDA@CAS composite material and add it to 100mL of deionized water. Disperse it by ultrasonication for 30min. Add 1g of phytic acid to the above solution and stir for 1h. After centrifugation and washing until neutral, place it in an 80℃ vacuum oven and dry for 24h to obtain TiC@PDA@CAS@PA composite flame retardant.
[0049] The TiC@PDA@CAS@PA composite flame retardant prepared in Example 1 was weighed and mixed with thermoplastic polyurethane elastomer TPU-75A. The flame retardant contents were 0%, 2%, 3%, 4%, and 5% by mass, respectively. The mixture was melt-blended in a torque rheometer at 170°C. The limiting oxygen index (LOI) of the TiC@PDA@CAS@PA flame-retardant modified TPU was determined according to the national standard GB-T2406.2-2009, and the results are shown in Table 1. The results show that the addition of the TiC@PDA@CAS@PA composite flame retardant significantly improves the LIOI of the TPU. When the addition amount reaches 5%, the LIOI can reach 31%, indicating a significant improvement in flame retardancy.
[0050] Table 1
[0051]
[0052] The mechanical properties of TiC@PDA@CAS@PA flame-retardant modified TPU were determined using a universal tensile testing machine. The results are as follows: Figure 1 This indicates that the addition of the TiC@PDA@CAS@PA composite flame retardant has a relatively small impact on the mechanical properties (elongation at break and tensile strength) of TPU-75A. Specifically, the tensile strength of samples 1-5 is all between 8-9 MPa. The tensile strength of sample 2 is lower than that of sample 1, the tensile strength of sample 3 is similar to that of sample 1, and the tensile strength of samples 4 and 5 is slightly higher than that of sample 1. The tensile elongation at break of samples 1-5 is all between 1000%-1200%, and the tensile elongation at break increases sequentially from sample 2, sample 5, sample 4, sample 1, to sample 3.
[0053] Example 2
[0054] Example 2 provides a method for preparing a biomass flame retardant based on titanium carbide, comprising the following steps:
[0055] (1) Preparation of TiC@PDA functional material: Weigh 3g TiC and 45mL Tris buffer and add to 270mL deionized water for ultrasonic dispersion for 30min. Add NaOH aqueous solution or HCl solution to adjust the pH to 8.5. Then add 4.5g dopamine hydrochloride and stir at 25℃ for 20h. After the reaction is completed, centrifuge at 5000r / min. Wash the obtained product three times with distilled water and finally dry it in a vacuum oven at 80℃ for 24h to obtain TiC@PDA functional material.
[0056] (2) Preparation of TiC@PDA@CAS composite material: Weigh 5g of casein and add it to sodium bicarbonate solution (pH=9). Stir at 60℃ for 30min, add 2g of TiC@PDA functional material, stir and react for 1h. After centrifugation, the product is washed 3 times with ethanol and dried in a vacuum oven at 75℃ for 24h to obtain TiC@PDA@CAS composite material.
[0057] (3) Preparation of TiC@PDA@CAS@PA composite flame retardant: Weigh 2g of TiC@PDA@CAS composite material and add it to 80mL of deionized water. Disperse it by ultrasonication for 30min. Add 1.5g of phytic acid to the above solution and stir for 1h. After centrifugation, wash until neutral and dry in a vacuum oven at 80℃ for 24h to obtain TiC@PDA@CAS@PA composite flame retardant.
[0058] The TiC@PDA@CAS@PA composite flame retardant prepared in Example 2 was weighed and mixed with thermoplastic polyurethane elastomer TPU-75A. The flame retardant contents were 0%, 2%, 3%, 4%, and 5% by mass, respectively. The mixture was melt-blended in a torque rheometer at 170°C. The limiting oxygen index (LOI) of the TiC@PDA@CAS@PA flame-retardant modified TPU was determined according to the national standard GB-T2406.2-2009, and the results are shown in Table 2. The results show that the addition of the TiC@PDA@CAS@PA composite flame retardant significantly improves the LIOI of the TPU. When the addition amount reaches 5%, the LIOI can reach 29%, indicating a significant improvement in flame retardancy.
[0059] Table 2
[0060]
[0061] Example 3
[0062] Example 3 provides a method for preparing a biomass flame retardant based on titanium carbide, comprising the following steps:
[0063] (1) Preparation of TiC@PDA functional material: Weigh 3g TiC and 36mL Tris buffer and add to 300mL deionized water for ultrasonic dispersion for 30min. Add NaOH aqueous solution or HCl solution to adjust the pH to 8.5. Then add 2.7g dopamine hydrochloride and stir at 30℃ for 18h. After the reaction is completed, centrifuge at 5000r / min. Wash the obtained product three times with distilled water and finally dry it in a vacuum oven at 80℃ for 24h to obtain TiC@PDA functional material.
[0064] (2) Preparation of TiC@PDA@CAS composite material: Weigh 5g of casein and add it to sodium bicarbonate solution (pH=9.5). Stir at 60℃ for 30min, add 3g of TiC@PDA functional material, stir and react for 1.5h. After centrifugation, the product is washed 3 times with ethanol and dried in a vacuum oven at 70℃ for 24h to obtain TiC@PDA@CAS composite material.
[0065] (3) Preparation of TiC@PDA@CAS@PA composite flame retardant: Weigh 2g of TiC@PDA@CAS composite material and add it to 80mL of deionized water. Disperse it by ultrasonication for 30min. Add 0.8g of phytic acid to the above solution. Stir and react for 2h. After centrifugation, wash until neutral and dry in a vacuum oven at 80℃ for 24h to obtain TiC@PDA@CAS@PA composite flame retardant.
[0066] The TiC@PDA@CAS@PA composite flame retardant prepared in Example 3 was weighed and mixed with thermoplastic polyurethane elastomer TPU-75A. The flame retardant contents were 0%, 2%, 3%, 4%, and 5% by mass, respectively. The mixture was melt-blended in a torque rheometer at 170°C. The limiting oxygen index (LOI) of the TiC@PDA@CAS@PA flame-retardant modified TPU was determined according to the national standard GB-T2406.2-2009, and the results are shown in Table 3. The results show that the addition of the TiC@PDA@CAS@PA composite flame retardant significantly improves the LIO index of the TPU. When the addition amount reaches 5%, the LIO index can reach 29%, indicating a significant improvement in flame retardancy.
[0067] Table 3
[0068]
[0069] Comparative Example 1
[0070] Using the test method of Example 1, the flame retardant was TiC, and the addition amount was 5%.
[0071] Comparative Example 2
[0072] Using the test method of Example 1, the flame retardant is TiC, and the amount added is equal to the amount of TiC used in the 5% flame retardant addition in the example.
[0073] Comparative Example 3
[0074] The test method of Example 1 is basically the same as that of the flame retardant preparation method in Example 1. The difference is that the order of steps (2) and (3) is exchanged and the amount added is equal to the amount of TiC in the 5% flame retardant addition in the example, calculated as TiC.
[0075] Comparative Example 4
[0076] The test method of Example 1 is basically the same as that of the flame retardant preparation method of Example 1. The difference is that only step (1) is used, and the amount of TiC added is equal to the amount of TiC in the 5% flame retardant addition in the example.
[0077] Comparative Example 5
[0078] The flame retardant was prepared using the same test method as in Example 1, except that it only included steps (1) and (2), and the amount of TiC added was equal to the amount of TiC used in the 5% flame retardant addition in the examples. The comparison results between Example 1 and Comparative Examples 1-5 are shown in Table 4.
[0079] Table 4
[0080]
[0081] As can be seen from Table 4, directly using TiC as a flame retardant has a mediocre flame retardant effect and will significantly reduce the product's breaking strength and elongation at break.
[0082] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A biomass flame retardant based on titanium carbide, characterized in that, It is made of TiC, dopamine hydrochloride, casein and phytic acid. Dopamine hydrochloride first modifies TiC to obtain TiC@PDA, then grafts casein to obtain TiC@PDA@CAS, and finally grafts phytic acid to obtain TiC@PDA@CAS@PA. The mass ratio of dopamine hydrochloride to TiC is 1:0.5-2.0, the mass ratio of TiC@PDA to casein is 1:1-3, and the mass ratio of TiC@PDA@CAS to phytic acid is 1:0.2-0.
8.
2. The biomass flame retardant based on titanium carbide according to claim 1, characterized in that, The mass ratio of dopamine hydrochloride to TiC is 1:1, the mass ratio of TiC@PDA to casein is 1:2, and the mass ratio of TiC@PDA@CAS to phytic acid is 1:0.
5.
3. The biomass flame retardant based on titanium carbide according to claim 1, characterized in that, The preparation process of TiC@PDA is as follows: TiC and Tris buffer are added to deionized water, ultrasonically dispersed and the pH is adjusted to 8-10. Dopamine hydrochloride is then added according to the ratio, and the mixture is stirred and reacted at 20-40℃ for 10-20h to obtain TiC@PDA. The concentration of tris(hydroxymethyl)aminomethane in the Tris buffer solution is 0.04-0.08 g / mL, and the mass-to-volume ratio of TiC to Tris buffer solution is 1:10-20 g / mL.
4. The biomass flame retardant based on titanium carbide according to claim 1, characterized in that, The preparation process of TiC@PDA@CAS is as follows: casein is added to the first solvent, heated and stirred to dissolve, and then TiC@PDA is added according to the ratio. The mixture is stirred and reacted at 50-70℃ and pH=8-10 for 0.5-2.0h to obtain TiC@PDA@CAS. The first solvent is selected from one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, potassium carbonate solution and potassium bicarbonate solution.
5. The biomass flame retardant based on titanium carbide according to claim 1, characterized in that, The preparation process of TiC@PDA@CAS@PA is as follows: TiC@PDA@CAS is added to a second solvent, ultrasonically dispersed, and then phytic acid is added according to the ratio. The mixture is stirred and reacted at 20-40℃ for 0.5-2.0h to obtain TiC@PDA@CAS@PA. The second solvent is selected from one or more of deionized water or ethanol.
6. The method for preparing the biomass flame retardant based on titanium carbide as described in any one of claims 1-5, characterized in that, The method includes: (1) Add TiC and Tris buffer to deionized water, disperse by sonication and adjust pH to 8-10, then add dopamine hydrochloride according to the ratio, and stir the reaction at 20-40℃ to obtain TiC@PDA; the concentration of tris(hydroxymethyl)aminomethane in the Tris buffer solution is 0.04-0.08 g / mL, and the mass-volume ratio of TiC to Tris buffer solution is 1:10-20 g / mL; (2) Add casein to the first solvent, heat and stir to dissolve, then add TiC@PDA according to the ratio, and stir to react at 50-70℃ and pH=8-10 to obtain TiC@PDA@CAS; the first solvent is selected from one or more of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, potassium carbonate solution and potassium bicarbonate solution; (3) Add TiC@PDA@CAS to the second solvent, disperse by ultrasonication, then add phytic acid according to the ratio, and stir the reaction at 20-40℃ to obtain TiC@PDA@CAS@PA; the second solvent is selected from one or more of deionized water or ethanol.
7. The method according to claim 6, characterized in that, In step (1), ultrasonic dispersion is performed for 20-60 min, and stirring reaction is performed for 10-20 h; in step (2), stirring reaction is performed for 0.5-2.0 h; in step (3), ultrasonic dispersion is performed for 20-60 min, and stirring reaction is performed for 0.5-2.0 h.
8. The method according to claim 6, characterized in that, In step (1), after the reaction is completed, solid-liquid separation is performed by centrifugation, followed by washing with deionized water, and finally vacuum drying at 60-100℃ for 16-24h to obtain TiC@PDA; in step (2), after the reaction is completed, solid-liquid separation is performed by centrifugation, followed by washing with ethanol, and finally vacuum drying at 60-80℃ for 10-24h to obtain TiC@PDA@CAS; in step (3), after the reaction is completed, solid-liquid separation is performed by centrifugation, followed by washing with ethanol, and finally vacuum drying at 60-80℃ for 10-24h to obtain TiC@PDA@CAS@PA.
9. The method according to claim 6, characterized in that, The method includes: (1) TiC and Tris buffer were added to deionized water, ultrasonically dispersed for 30 min and the pH was adjusted to 8.
5. Dopamine hydrochloride was then added and the mixture was stirred at 30 °C for 16 h. After the reaction was completed, solid-liquid separation was performed by centrifugation, followed by washing with deionized water. Finally, TiC@PDA was obtained by vacuum drying at 80 °C for 24 h. The concentration of tris(hydroxymethyl)aminomethane in the Tris buffer solution was 0.064 g / mL, the mass-to-volume ratio of TiC to Tris buffer solution was 1:12.5 g:mL, and the mass ratio of dopamine hydrochloride to TiC was 1:
1. (2) Casein was added to sodium bicarbonate solution, heated and stirred for 30 min, then TiC@PDA was added, and the mixture was stirred and reacted at 60 °C and pH=9 for 1 h. After the reaction was completed, solid-liquid separation was performed by centrifugation, followed by washing with ethanol, and finally vacuum drying at 70 °C for 24 h to obtain TiC@PDA@CAS; the mass ratio of TiC@PDA to casein was 1:
2. (3) Add TiC@PDA@CAS to deionized water, disperse ultrasonically for 30 min, then add phytic acid, stir and react at room temperature for 1 h. After the reaction is completed, separate the solid and liquid by centrifugation, wash with ethanol, and finally vacuum dry at 80℃ for 24 h to obtain TiC@PDA@CAS@PA; the mass ratio of TiC@PDA@CAS to phytic acid is 1:0.5.