A bimetallic flame retardant modifier and preparation method thereof
By adding metal zinc or cobalt to melamine phytate salt and preparing bimetallic flame retardant modifier, the problem of insufficient flame retardant performance of existing flame retardant is solved, and a better flame retardant effect is achieved.
Patent Information
- Application Number
- CN202311080491.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-08-25
- Publication Date
- 2025-04-11
- Estimated Expiration
- 2043-08-25
AI Technical Summary
The flame retardant performance of existing metal ion/complex flame retardants has not yet achieved the best results, especially among bio-based flame retardants, where there is a need to improve flame retardant performance.
Bimetal flame retardant modifiers were prepared by incorporating metal zinc or cobalt into melamine phytate salt and reacting under specific conditions. The method includes dissolving the zinc precursor and the cobalt precursor in water, adding dropwise to the melamine phytate megluamine salt dispersion, performing suction filtration and drying after reaction, and obtaining a solid flame retardant.
The bimetal flame retardant modifier significantly improves the flame retardant performance, and is more effective than the modification of a single metal, which can effectively suppress combustion and extend combustion time.
Abstract
Description
Technical Field
[0001] The invention relates to the field of flame retardants, and in particular to a bimetallic flame retardant modifier and a preparation method thereof. Background Art
[0002] Flame retardants refer to materials that can inhibit or delay combustion but are not easy to burn themselves. They are widely used in wood, clothing, petroleum, chemical industry, metallurgy, shipbuilding, fire protection and national defense. According to the method of use, flame retardants can be divided into additive flame retardants and reactive flame retardants. According to the chemical composition, flame retardants can be divided into organic flame retardants and inorganic flame retardants.
[0003] Metal ion / complex flame retardants are one of the commonly used flame retardants in the prior art. For example, some scholars have obtained metal ion-modified bio-based flame retardants by adding metal Cu, Mn or Ni to bio-based flame retardants. However, the flame retardant properties of the bio-based flame retardant need to be improved. Therefore, it is necessary to design a flame retardant with better flame retardant properties. Summary of the invention
[0004] In view of the problems existing in the prior art, the present invention aims to provide a method for preparing a bimetallic flame retardant modifier.
[0005] The present invention provides a method for preparing a bimetallic flame retardant modifier, and the method for preparing the bimetallic flame retardant modifier comprises the following steps:
[0006] 10-12g of melamine phytate meglumine salt is uniformly dispersed in 150-180mL of deionized water and heated to 45-48°C to obtain a melamine phytate meglumine salt dispersion, 0.2-0.6g of a zinc precursor and 0.2-0.6g of a cobalt precursor are dissolved in deionized water to obtain a metal salt solution, the metal salt solution is dropwise added to the melamine phytate meglumine salt dispersion, reacted at 45-48°C for 4-5h, then filtered and washed with deionized water several times, and dried at 60-65°C to obtain a solid flame retardant.
[0007] Preferably, the zinc precursor is zinc acetate.
[0008] Preferably, the cobalt precursor is cobalt acetate.
[0009] Preferably, the number of washings with deionized water is 10 times.
[0010] Preferably, the drying temperature is 60°C.
[0011] Preferably, the reaction time is 4 hours.
[0012] Preferably, the heating temperature is 45°C.
[0013] Furthermore, the present invention also provides a bimetallic flame retardant modifier, which is prepared by the above method.
[0014] In order to obtain a flame retardant modifier with excellent performance, the present invention adds metal zinc or cobalt to melamine phytate meglumine salt. Studies have shown that melamine phytate meglumine salt modified with metal zinc or cobalt has excellent flame retardant properties, and when the two metals are modified at the same time, the effect is better than that of using a single metal. DETAILED DESCRIPTION
[0015] The technical effects of the present invention are verified below through specific examples, but the embodiments of the present invention are not limited thereto.
[0016] The preparation process of phytic acid melamine salt and melamine phytic acid meglumine salt in the present invention refers to the prior art, and the specific method is:
[0017] The preparation method of phytic acid melamine salt is as follows: 7.56 g of melamine and 130 mL of distilled water are heated to 80° C. to obtain a melamine solution, 13.2 g of a phytic acid aqueous solution with a concentration of 50% is mixed with 50 mL of deionized water to obtain a phytic acid solution, the phytic acid solution is added dropwise to the melamine solution, and after the addition is completed, the mixture is reacted at 80° C. for 3.5 hours, cooled to room temperature, filtered, washed with deionized water 10 times, and dried at 60° C. to obtain solid phytic acid melamine salt.
[0018] Preparation method of melamine phytate meglumine salt: 1.95g meglumine is dissolved in 20mL deionized water, and fully stirred to obtain a meglumine aqueous solution, 10g phytate melamine salt is added to 130mL deionized water, and fully stirred to make it evenly dispersed, and then the meglumine aqueous solution is added dropwise, and then the temperature is raised to 85°C, and the reaction is performed for 3h. Finally, it is cooled to room temperature and filtered, and washed with deionized water 10 times, and dried at 60°C to obtain solid melamine phytate meglumine salt.
[0019] Example 1
[0020] Take 10g of melamine phytate meglumine salt and disperse it evenly in 150mL of deionized water and heat it to 45°C to obtain a melamine phytate meglumine salt dispersion, take 0.2g of zinc acetate and 0.2g of cobalt acetate and dissolve them in 30mL of deionized water to obtain a metal salt solution, add the metal salt solution dropwise into the melamine phytate meglumine salt dispersion, react at 45°C for 4h, then filter and wash with deionized water 10 times, and dry at 60°C to obtain a solid flame retardant.
[0021] Example 2
[0022] Take 10g of melamine phytate meglumine salt and evenly disperse it in 150mL of deionized water and heat it to 45°C to obtain a melamine phytate meglumine salt dispersion, take 0.3g of zinc acetate and 0.3g of cobalt acetate and dissolve them in 30mL of deionized water to obtain a metal salt solution, add the metal salt solution dropwise into the melamine phytate meglumine salt dispersion, react at 45°C for 4h, then filter and wash with deionized water 10 times, and dry at 60°C to obtain a solid flame retardant.
[0023] Example 3
[0024] Take 10g of melamine phytate meglumine salt and disperse it evenly in 150mL of deionized water and heat it to 45°C to obtain a melamine phytate meglumine salt dispersion, take 0.41g of zinc acetate and 0.27g of cobalt acetate and dissolve them in 30mL of deionized water to obtain a metal salt solution, add the metal salt solution dropwise into the melamine phytate meglumine salt dispersion, react at 45°C for 4h, then filter and wash with deionized water 10 times, and dry at 60°C to obtain a solid flame retardant.
[0025] Example 4
[0026] Take 10g of melamine phytate meglumine salt and disperse it evenly in 150mL of deionized water and heat it to 45°C to obtain a melamine phytate meglumine salt dispersion, take 0.27g of zinc acetate and 0.41g of cobalt acetate and dissolve them in 30mL of deionized water to obtain a metal salt solution, add the metal salt solution dropwise into the melamine phytate meglumine salt dispersion, react at 45°C for 4h, then filter and wash with deionized water 10 times, and dry at 60°C to obtain a solid flame retardant.
[0027] Example 5
[0028] Take 10g of melamine phytate meglumine salt and disperse it evenly in 150mL of deionized water and heat it to 45°C to obtain a melamine phytate meglumine salt dispersion, take 0.6g of zinc acetate and 0.6g of cobalt acetate and dissolve them in 30mL of deionized water to obtain a metal salt solution, add the metal salt solution dropwise into the melamine phytate meglumine salt dispersion, react at 45°C for 4h, then filter and wash with deionized water 10 times, and dry at 60°C to obtain a solid flame retardant.
[0029] Comparative Example 1
[0030] Take 10g of melamine phytate meglumine salt and disperse it evenly in 150mL of deionized water and heat it to 45°C to obtain a melamine phytate meglumine salt dispersion, take 0.68g of zinc acetate and dissolve it in 30mL of deionized water to obtain a metal salt solution, add the metal salt solution dropwise into the melamine phytate meglumine salt dispersion, react at 45°C for 4h, then filter and wash with deionized water 10 times, and dry at 60°C to obtain a solid flame retardant.
[0031] Comparative Example 2
[0032] Take 10g of melamine phytate meglumine salt and disperse it evenly in 150mL of deionized water and heat it to 45°C to obtain a melamine phytate meglumine salt dispersion, take 0.68g of cobalt acetate and dissolve it in 30mL of deionized water to obtain a metal salt solution, add the metal salt solution dropwise into the melamine phytate meglumine salt dispersion, react at 45°C for 4h, then filter and wash with deionized water 10 times, and dry at 60°C to obtain a solid flame retardant.
[0033] Hereinafter, the flame retardants in Examples 1-5 and Comparative Examples 1-2 were added to PU to evaluate the relevant properties of the flame retardants, and PU without flame retardants was used as a control group. Among them, relative to the total mass of the flame-retardant PU, the solid flame retardant accounted for 12wt%. In order to ensure the comparability of each group of tests, 5 parallel tests were conducted for each group of tests to obtain the average value, and it was ensured that the only difference between each group of tests was the absence of flame retardants.
[0034] Table 1
[0035] serial number <![CDATA[Peak heat release rate / W·m -2 > <![CDATA[Total heat release / MJ·m -2 > Residual carbon / % Example 1 875.0 141.3 4.28 Example 2 843.5 119.2 7.33 Example 3 782.5 89.1 10.25 Example 4 802.4 105.4 8.67 Example 5 796.4 98.3 9.01 Comparative Example 1 872.6 137.5 4.65 Comparative Example 2 863.1 124.3 5.23 Control group 903.2 158.3 2.19
[0036] It can be seen from Table 1 that melamine phytate meglumine salt modified by metal zinc or cobalt has excellent flame retardant properties, and when the two metals are modified at the same time, the effect is better than using a single metal.
[0037] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A method for preparing a bimetallic flame retardant modifier, characterized in that: The preparation method of the bimetallic flame retardant modifier comprises the following steps: 10-12g of melamine phytate meglumine salt is uniformly dispersed in 150-180mL of deionized water and heated to 45-48°C to obtain a melamine phytate meglumine salt dispersion, 0.2-0.6g of a zinc precursor and 0.2-0.6g of a cobalt precursor are dissolved in deionized water to obtain a metal salt solution, the metal salt solution is dropwise added to the melamine phytate meglumine salt dispersion, reacted at 45-48°C for 4-5h, then filtered and washed with deionized water for several times, and dried at 60-65°C to obtain a solid flame retardant; the zinc precursor is zinc acetate, and the cobalt precursor is cobalt acetate.
2. A method for preparing the bimetallic flame retardant modifier according to claim 1, characterized in that: The number of washings with deionized water was 10 times.
3. A method for preparing the bimetallic flame retardant modifier according to claim 1, characterized in that: The drying temperature is 60°C.
4. A method for preparing the bimetallic flame retardant modifier according to claim 1, characterized in that: The reaction time is 4h.
5. A method for preparing the bimetallic flame retardant modifier according to claim 1, characterized in that: The heating temperature is 45°C.
6. A bimetallic flame retardant modifier, characterized in that: The bimetallic flame retardant modifier is prepared by the method described in any one of claims 1-5.