A flame retardant and antibacterial triazine intermediate and its application

Abstract

The invention relates to the technical field of cyanuric chloride, and discloses a flame retardant and antibacterial triazine intermediate and application thereof. The invention uses 4-aminophenol, dicyandiamide, diethylenetriamine, formaldehyde, cyanuric chloride and the like as raw materials, and undergoes addition reaction, Mannich reaction and substitution reaction to obtain an intermediate product 3. 3,5-divinylaniline and DOPO are subjected to addition reaction to obtain bis-DOPO aniline, and finally the intermediate product 3 and bis-DOPO aniline are used as raw materials, and two substitution reactions are performed to obtain a flame retardant and antibacterial triazine intermediate. The flame retardant and antibacterial triazine intermediate prepared by the invention has a novel structure and good symmetry. The flame retardant and antibacterial triazine intermediate is applied to coatings to improve the flame retardant property, antibacterial property and thermal stability of the coatings.

Description

Technical Field

[0001] The invention relates to the technical field of cyanuric chloride, in particular to a flame retardant and antibacterial triazine intermediate and application thereof. Background Art

[0002] Keeping the environment pollution-free is a practical way to prevent bacteria and viruses from infecting humans, and using antibacterial coatings is one of the most effective ways to achieve a pollution-free environment. However, the flame retardant properties of traditional coatings are not good. Therefore, it is crucial to improve the antibacterial and flame retardant properties of coatings.

[0003] Cyanuric chloride is a fine chemical product with a large output. It is a common chemical intermediate with high reactivity and thermal stability. It is widely used in dyes, finishing agents, and coatings. Biguanide compounds can change the normal material and energy metabolism of organisms by interacting with certain specific groups in organisms. They have strong antibacterial and bactericidal abilities and are widely used in agriculture, medicine, and other fields. 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is a common flame retardant intermediate and is widely used because of its excellent flame retardant properties.

[0004] For example, the patent application publication number CN113583239A discloses a triazine-based nitrogen-phosphorus flame retardant, a flame-retardant water-based acrylic coating and a preparation method thereof. The acrylic coating prepared by the invention has good flame retardant properties, but does not improve the antibacterial properties and thermal stability of the coating. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a flame retardant and antibacterial triazine intermediate and its application. The prepared triazine intermediate is applied to coatings to improve the antibacterial properties, flame retardant properties and thermal stability of the coatings.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A flame retardant and antibacterial triazine intermediate, the structure of which is shown below:

[0008] ;

[0009] The preparation method of the flame retardant and antibacterial triazine intermediate is as follows:

[0010] The intermediate product 3 is added to deionized water, and bis-DOPO aniline is added thereto, and the reaction is carried out at 40-50°C for 2-4 hours, and then the temperature is raised to 80-90°C, and the reaction is continued for 20-30 hours. After the reaction is completed, the product is filtered, washed with deionized water, and dried to obtain a flame retardant antibacterial triazine intermediate, and the reaction formula is:

[0011] .

[0012] Furthermore, the molar ratio of the intermediate product 3 to the bis-DOPO aniline is 1:2.5-3.

[0013] Furthermore, the preparation method of the intermediate product 3 is:

[0014] (1) 4-aminophenol is added to deionized water, and hydrochloric acid with a mass fraction of 30-36% is added thereto, and the mixture is stirred to dissolve. Then dicyandiamide is added thereto, and the mixture is reacted at 70-90° C. for 5-8 hours. After the reaction is completed, the mixture is concentrated, acetone is added thereto for precipitation, the mixture is filtered, recrystallized, and dried to obtain an intermediate product 1, whose reaction formula is:

[0015] ;

[0016] (2) Add diethylenetriamine to toluene solvent, then add 37% formaldehyde aqueous solution, control the temperature to 5-10°C, stir and mix for 20-40 minutes, then add intermediate product 1, react at 80-95°C for 20-24 hours. After the reaction is completed, filter and take the filtrate, wash with sodium hydroxide aqueous solution and deionized water in turn, distill under reduced pressure, and dry to obtain intermediate product 2, whose reaction formula is:

[0017] ;

[0018] (3) Add cyanuric chloride to deionized water, stir and mix evenly, then add intermediate product 2 and sodium carbonate, react at 0-5°C for 2-5h. After the reaction is completed, filter, wash with deionized water, and dry to obtain intermediate product 3, whose reaction formula is: .

[0019] Furthermore, the molar ratio of 4-aminophenol to dicyandiamide is 1:1-1.5.

[0020] Furthermore, the molar ratio of diethylenetriamine to the intermediate product 1 is 1:2-2.5.

[0021] Furthermore, the molar ratio of cyanuric chloride, intermediate product 2, and sodium carbonate is 1:0.8-1:1.4-1.6.

[0022] Furthermore, the preparation method of the bis-DOPO aniline is:

[0023] 3,5-divinylaniline and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) are added to a toluene solvent, stirred and mixed evenly, and reacted at 80-90°C for 24-48 hours. After the reaction is completed, xylene is added thereto, stirred and allowed to stand for stratification, and the liquid is separated. The lower layer of liquid is taken, washed with xylene, and dried to obtain aniline containing di-DOPO, and the reaction formula is: .

[0024] Furthermore, the molar ratio of 3,5-divinylaniline to DOPO is 1:2-2.5.

[0025] Furthermore, the flame retardant and antibacterial triazine intermediates are used in coatings.

[0026] Reaction mechanism: The present invention uses 4-aminophenol and dicyandiamide as raw materials for addition reaction to obtain intermediate product 1, which is then reacted with diethylenetriamine and formaldehyde through a Mannich reaction to obtain intermediate product 2, and the secondary amino group in intermediate product 2 is used to undergo a substitution reaction with the first chlorine atom of cyanuric chloride to obtain intermediate product 3. 3,5-divinylaniline is used to undergo an addition reaction with DOPO to obtain bis-DOPO aniline, and finally, intermediate product 3 and bis-DOPO aniline are used as raw materials and subjected to two substitution reactions to obtain a flame-retardant antibacterial triazine intermediate.

[0027] Compared with the prior art, the present invention provides the following beneficial effects:

[0028] The flame retardant and antibacterial triazine intermediate prepared by the present invention has a novel structure and a good symmetrical structure, wherein it contains two biguanide structures and four DOPO structures, and therefore, it has good flame retardant and antibacterial properties. In addition, the flame retardant and antibacterial triazine intermediate prepared by the present invention contains a benzene ring rigid structure, which is a good heat-resistant structure, and the benzoxazine structure contained therein can be open-ring cross-linked to form a cross-linked network structure when heated to further improve the thermal stability of the flame retardant and antibacterial triazine intermediate. The present invention applies it to coatings to improve the thermal stability, flame retardancy and antibacterial properties of the coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is the structural formula of flame retardant and antibacterial triazine intermediate;

[0030] Figure 2 It is the carbon spectrum of flame retardant and antibacterial triazine intermediates; Figure 2In the NMR carbon spectrum of , two groups of peaks appear in the high field region. The peak at the chemical shift of 29.94 ppm is the methylene carbon signal (C-2) connected to the benzene ring, and the peak at the chemical shift of 36.03 ppm is the methylene carbon signal (C-1) connected to the P atom; the three groups of peaks with chemical shifts between 51-49 ppm in the mid-field region are the methylene carbon signals (C-3, 4, 5) connected to the N atom, and the peak at the chemical shift of about 76 ppm is the methylene carbon signal (C-6) connected to both the N and O atoms; the carbon signal of the C=N double bond (C-7) in the structure is located between 158 and 155 ppm in the low field region; the two groups of peaks at the low field region chemical shifts of 159.47 and 152.66 ppm are the olefinic carbon signals of the C=N double bond and connected to another N atom (C-8, 9); the remaining chemical shifts are between 151 and 106 The carbon signal peaks between ppm are the aromatic carbon signals on the benzene ring in the structure. DETAILED DESCRIPTION

[0031] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the following specific description is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention. Embodiment 1

[0032] (1) Add 30 mmol of 4-aminophenol to 100 mL of deionized water, add 35% by mass hydrochloric acid thereto, stir to dissolve, then add 45 mmol of dicyandiamide thereto, react at 80°C for 8 h. After the reaction is completed, concentrate, add acetone thereto for precipitation, filter, recrystallize, and dry to obtain intermediate 1.

[0033] (2) Add 50 mmol of diethylenetriamine to 100 mL of toluene solvent, then add 37% formaldehyde aqueous solution, control the temperature to 10°C, stir and mix for 30 min, then add 120 mmol of intermediate 1, react at 95°C for 24 h. After the reaction is completed, filter and take the filtrate, wash with 3 mol / L sodium hydroxide solution and deionized water in turn, distill under reduced pressure, and dry to obtain intermediate 2.

[0034] (3) Add 0.2 mol of cyanuric chloride to 150 mL of deionized water, stir and mix well, then add 0.2 mol of intermediate product 2 and 0.28 mol of sodium carbonate, react at 0°C for 5 h. After the reaction is completed, filter, wash with deionized water, and dry to obtain intermediate product 3.

[0035] (4) Add 0.3 mol of 3,5-divinylaniline and 0.75 mol of DOPO to 100 mL of toluene solvent, stir and mix evenly, and react at 90°C for 48 hours. After the reaction is completed, add xylene, stir and stand to separate the layers, separate the layers, take the lower layer, wash with xylene, and dry to obtain aniline containing di-DOPO.

[0036] (5) 0.2 mol of the intermediate product 3 was added to 150 mL of deionized water, to which 0.55 mol of di-DOPO aniline was added, and the reaction was carried out at 50 °C for 2 h. The temperature was then raised to 85 °C and the reaction was continued for 24 h. After the reaction was completed, the mixture was filtered, washed with deionized water, and dried to obtain a flame retardant and antibacterial triazine intermediate with a yield of 72.4%. Embodiment 2

[0037] (1) 30 mmol of 4-aminophenol was added to 100 mL of deionized water, and 30% by mass of hydrochloric acid was added thereto, and the mixture was stirred to dissolve. Then 35 mmol of dicyandiamide was added thereto, and the mixture was reacted at 90° C. for 5 h. After the reaction was completed, the mixture was concentrated, acetone was added thereto for precipitation, the mixture was filtered, recrystallized, and dried to obtain an intermediate product 1.

[0038] (2) Add 50 mmol of diethylenetriamine to 100 mL of toluene solvent, then add 37% formaldehyde aqueous solution, control the temperature to 5°C, stir and mix for 40 min, then add 125 mmol of intermediate 1, react at 95°C for 22 h. After the reaction is completed, filter and take the filtrate, wash with 3 mol / L sodium hydroxide solution and deionized water in turn, distill under reduced pressure, and dry to obtain intermediate 2.

[0039] (3) Add 0.2 mol of cyanuric chloride to 150 mL of deionized water, stir and mix well, then add 0.16 mol of intermediate 2 and 0.32 mol of sodium carbonate, react at 5°C for 4 h. After the reaction is completed, filter, wash with deionized water, and dry to obtain intermediate 3.

[0040] (4) Add 0.3 mol of 3,5-divinylaniline and 0.6 mol of DOPO to 100 mL of toluene solvent, stir and mix evenly, and react at 90°C for 24 h. After the reaction, add xylene, stir and stand to separate the layers, separate the layers, take the lower layer, wash with xylene, and dry to obtain aniline containing di-DOPO.

[0041] (5) 0.2 mol of the intermediate product 3 was added to 150 mL of deionized water, to which 0.5 mol of di-DOPO aniline was added, and the reaction was carried out at 40 °C for 4 h. The temperature was then raised to 90 °C and the reaction was continued for 20 h. After the reaction was completed, the mixture was filtered, washed with deionized water, and dried to obtain a flame retardant and antibacterial triazine intermediate with a yield of 70.7%. Embodiment 3

[0042] (1) Add 30 mmol of 4-aminophenol to 100 mL of deionized water, add 36% by mass hydrochloric acid thereto, stir to dissolve, then add 30 mmol of dicyandiamide thereto, react at 70°C for 6 h. After the reaction is completed, concentrate, add acetone to precipitate, filter, recrystallize, and dry to obtain intermediate 1.

[0043] (2) Add 50 mmol of diethylenetriamine to 100 mL of toluene solvent, then add 37% formaldehyde aqueous solution, control the temperature to 5°C, stir and mix for 20 min, then add 100 mmol of intermediate 1, react at 80°C for 20 h. After the reaction is completed, filter and take the filtrate, wash with 3 mol / L sodium hydroxide solution and deionized water in turn, distill under reduced pressure, and dry to obtain intermediate 2.

[0044] (3) Add 0.2 mol of cyanuric chloride to 150 mL of deionized water, stir and mix well, then add 0.18 mol of intermediate 2 and 0.3 mol of sodium carbonate, react at 5°C for 5 h. After the reaction is completed, filter, wash with deionized water, and dry to obtain intermediate 3.

[0045] (4) Add 0.3 mol of 3,5-divinylaniline and 0.75 mol of DOPO to 100 mL of toluene solvent, stir and mix evenly, and react at 80°C for 48 hours. After the reaction is completed, add xylene, stir and stand to separate the layers, separate the layers, take the lower layer, wash with xylene, and dry to obtain aniline containing di-DOPO.

[0046] (5) 0.2 mol of the intermediate product 3 was added to 150 mL of deionized water, to which 0.6 mol of di-DOPO aniline was added, and the reaction was carried out at 45 °C for 3 h. The temperature was then raised to 80 °C and the reaction was continued for 30 h. After the reaction was completed, the mixture was filtered, washed with deionized water, and dried to obtain a flame retardant and antibacterial triazine intermediate with a yield of 74.2%. Embodiment 4

[0047] To 100 parts by weight of acrylic emulsion, add 29 parts by weight of ethylene glycol, 0.5 parts by weight of carboxymethyl cellulose, 0.5 parts by weight of NXZ defoamer, 2 parts by weight of 1124 dispersant and 2 parts by weight of the flame retardant and antibacterial triazine intermediate prepared in Example 1, stir and mix evenly, apply on a polytetrafluoroethylene plate, control the coating thickness to 1 mm, dry at room temperature for 12 hours, and then place in an oven at 80°C to dry for 24 hours to obtain a coating. Embodiment 5

[0048] To 100 parts by weight of acrylic emulsion, add 29 parts by weight of ethylene glycol, 0.5 parts by weight of carboxymethyl cellulose, 0.5 parts by weight of NXZ defoamer, 2 parts by weight of 1124 dispersant and 2 parts by weight of the flame retardant and antibacterial triazine intermediate prepared in Example 2, stir and mix evenly, apply on a polytetrafluoroethylene plate, control the coating thickness to 1 mm, dry at room temperature for 12 hours, and then place in an oven at 80°C to dry for 24 hours to obtain a coating. Embodiment 6

[0049] To 100 parts by weight of acrylic emulsion, add 29 parts by weight of ethylene glycol, 0.5 parts by weight of carboxymethyl cellulose, 0.5 parts by weight of NXZ defoamer, 2 parts by weight of 1124 dispersant and 2 parts by weight of the flame retardant and antibacterial triazine intermediate prepared in Example 3, stir and mix evenly, apply on a polytetrafluoroethylene plate, control the coating thickness to 1 mm, dry at room temperature for 12 hours, and then place in an oven at 80°C to dry for 24 hours to obtain a coating. Embodiment 7

[0050] The difference between this embodiment and embodiment 4 is that the amount of the flame retardant and antibacterial triazine intermediate used is 4 parts by weight. Embodiment 8

[0051] The difference between this embodiment and embodiment 4 is that the amount of the flame retardant and antibacterial triazine intermediate used is 6 parts by weight. Embodiment 9

[0052] The difference between this embodiment and embodiment 4 is that the amount of the flame retardant and antibacterial triazine intermediate used is 8 parts by weight.

[0053] Comparative Example 1

[0054] The difference between this comparative example and Example 4 is that it does not contain the flame retardant antibacterial triazine intermediate.

[0055] Flame retardant performance test: Use an oxygen index tester to test the limiting oxygen index of the coating.

[0056] Table 1:

[0057]

[0058] As can be seen from the table, the limiting oxygen index of Examples 4-6 is greater than that of Comparative Example 1. This is because Examples 4-6 contain flame retardant antibacterial triazine intermediates, which are added to the coating to increase the flame retardant properties of the coating. As can be seen from Examples 4 and 7-9, as the amount of flame retardant antibacterial triazine intermediates increases, the flame retardant properties increase.

[0059] Thermal stability performance test: Use a thermal gravimetric analyzer to test the thermal stability of the coating. In a nitrogen atmosphere, the temperature range is 30-600°C and the heating rate is 10°C / min.

[0060] Table 2:

[0061]

[0062] As can be seen from the table, the thermal stability of Examples 4-6 is better than that of Comparative Example 1. This is because the flame retardant and antibacterial triazine intermediates added in Examples 4-6 contain heat-resistant rigid structures and benzoxazine structures, while Comparative Example 1 does not have such structures. Therefore, its thermal stability is not as good as that of Examples 4-6. In addition, it can be seen from Examples 4 and Examples 7-9 that as the amount of the flame retardant and antibacterial triazine intermediate increases, its thermal stability increases.

[0063] Antibacterial performance test: refer to HG / T3950-2007, the test bacteria are Escherichia coli and Staphylococcus aureus.

[0064] Table 3:

[0065]

[0066] As can be seen from the table, the flame retardant and antibacterial triazine intermediate prepared by the present invention can be used in coatings to improve the antibacterial property of the coatings, with the antibacterial rate of Escherichia coli reaching up to 99.40% and the antibacterial rate of Staphylococcus aureus reaching up to 99.16%.

[0067] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A flame retardant and antibacterial triazine intermediate, characterized in that: The structure is as follows: The preparation method of the flame retardant and antibacterial triazine intermediate is as follows: The intermediate product 3 is added to deionized water, and bis-DOPO aniline is added thereto, and the reaction is carried out at 40-50°C for 2-4 hours, and then the temperature is raised to 80-90°C, and the reaction is continued for 20-30 hours. After the reaction is completed, the mixture is filtered, washed with deionized water, and dried to obtain a flame retardant antibacterial triazine intermediate; The preparation method of the intermediate product 3 is: (1) 4-aminophenol is added to deionized water, and hydrochloric acid having a mass fraction of 30-36% is added thereto, and the mixture is stirred to dissolve. Then, dicyandiamide is added thereto, and the mixture is reacted at 70-90° C. for 5-8 hours. After the reaction is completed, the mixture is concentrated, acetone is added thereto for precipitation, the mixture is filtered, recrystallized, and dried to obtain an intermediate product 1, the structure of which is as follows: (2) Add diethylenetriamine to toluene solvent, then add 37% formaldehyde aqueous solution, control the temperature to 5-10° C., stir and mix for 20-40 min, then add intermediate product 1, react at 80-95° C. for 20-24 h. After the reaction is completed, filter, take the filtrate, wash with sodium hydroxide aqueous solution and deionized water in turn, distill under reduced pressure, and dry to obtain intermediate product 2, whose structure is: (3) Add cyanuric chloride to deionized water, stir and mix evenly, then add intermediate product 2 and sodium carbonate, react at 0-5° C. for 2-5 hours. After the reaction is completed, filter, wash with deionized water, and dry to obtain intermediate product 3, whose structure is: The preparation method of the bis-DOPO aniline is as follows: Add 3,5-divinylaniline and DOPO to toluene solvent, stir and mix evenly, react at 80-90°C for 24-48 hours. After the reaction, add xylene, stir and stand to separate the layers, separate the liquid, take the lower layer, wash with xylene, and dry to obtain aniline containing di-DOPO.

2. The flame retardant and antibacterial triazine intermediate according to claim 1, characterized in that: The molar ratio of the intermediate product 3 to the bis-DOPO aniline is 1:2.5-3.

3. The flame retardant and antibacterial triazine intermediate according to claim 1, characterized in that: In the above (1), the molar ratio of 4-aminophenol to dicyandiamide is 1:1-1.

5.

4. The flame retardant and antibacterial triazine intermediate according to claim 1, characterized in that: In the above (2), the molar ratio of diethylenetriamine to the intermediate product 1 is 1:2-2.

5.

5. The flame retardant and antibacterial triazine intermediate according to claim 1, characterized in that: In the above (3), the molar ratio of cyanuric chloride, intermediate product 2 and sodium carbonate is 1:0.8-1:1.4-1.

6.

6. The flame retardant and antibacterial triazine intermediate according to claim 1, characterized in that: The molar ratio of 3,5-divinylaniline to DOPO is 1:2-2.

5.

7. Use of the flame retardant and antibacterial triazine intermediate as claimed in claim 1 in coatings.

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