Phenoxy triazine sulfonate flame retardant as well as preparation method and application thereof

Abstract

The invention discloses a phenoxy triazine sulfonate flame retardant as well as a preparation method and application thereof, relates to the field of sulfonate flame retardants, and aims to solve the problems that an existing sulfonate flame retardant is relatively high in water solubility, short in timeliness and easy to separate out. The preparation method of the phenoxy triazine sulfonate flame retardant comprises the following steps: 1, mixing cyanuric chloride and a solvent, and stirring until cyanuric chloride and the solvent are dissolved; 2, dissolving a bisphenol organic matter and an acid-binding agent in water, and dropwise adding to obtain an intermediate 1; 3, dissolving p-hydroxybenzene sulfonate and an acid-binding agent in water, dropwise adding to obtain an intermediate 2 when the dropwise adding amount reaches half, continuously dropwise adding, heating, and carrying out reflux reaction; and 4, stopping heating, cooling, carrying out suction filtration, washing and drying to obtain the phenoxy triazine sulfonate flame retardant. The flame retardant provided by the invention has water insolubility, has better compatibility with PC, has less influence on transparency and haze, and is not easy to separate out in a PC matrix. The flame retardant is used for flame retardance of bisphenol A polycarbonate.

Description

Technical Field

[0001] This invention relates to the field of sulfonate flame retardants, specifically a phenoxytriazine sulfonate flame retardant, its preparation method, and its application. Background Technology

[0002] Polycarbonate (PC), as a general-purpose engineering plastic, is widely used due to its high impact strength and high transparency. Compared with other engineering plastics, PC itself has a certain flame retardancy, reaching the UL-94 V2 level. However, it is clearly insufficient for applications requiring higher flame retardancy ratings, such as electronic components and indoor furniture. Therefore, it needs to be modified to achieve the UL-94 V0 flame retardancy level.

[0003] Currently, the flame retardant systems used in PCs mainly include halogen-based, phosphate ester-based, organosilicon-based, and sulfonate-based systems. Among them, halogen-based flame retardants have been largely banned due to their failure to meet environmental protection requirements, and halogen-free flame retardants are the mainstream direction for future market development.

[0004] The phosphate ester flame retardant market is dominated by bisphenol A (diphenyl phosphate), which has a relatively small impact on the transparency of PC, but its flame retardant efficiency is low and the dosage is large, generally requiring more than 10wt% and compounding with an anti-dripping agent (PTFE), otherwise it will drip and ignite absorbent cotton. Furthermore, it has a significant impact on the mechanical properties of PC, making it not a good choice. Organosilicon flame retardants, used alone, have poor flame retardant effects on PC and need to be compounded with other flame retardants. They also significantly affect the transparency and mechanical properties of PC and are more expensive, making them difficult to use on a large scale in actual production and daily life as the main flame retardant for PC at present.

[0005] With more and more countries issuing PFAS bans, the use of fluorinated flame retardants and anti-dripping agents is restricted. Currently, sulfonate flame retardants are very promising for flame-retardant PCs because they can achieve ideal flame-retardant effects with very low addition amounts and have little impact on the mechanical properties of PCs. The mainstream sulfonate flame retardants on the market are potassium diphenyl sulfonate (KSS) and potassium perfluorobutyl sulfonate (PPFBS). However, only KSS is a truly halogen-free sulfonate flame retardant. However, it is highly water-soluble and easily precipitates in humid environments, resulting in a short flame-retardant duration, making it difficult to meet the requirement of maintaining long-term flame retardancy in humid environments. Furthermore, its unit price is relatively high. Summary of the Invention

[0006] The present invention aims to solve the problems of existing sulfonate flame retardants having high water solubility, short effective period, and easy precipitation, and provides a phenoxytriazine sulfonate flame retardant, its preparation method, and its application.

[0007] This invention provides a phenoxytriazine sulfonate flame retardant, the structure of which is as follows:

[0008]

[0009] Where n≥1, X is , , , or .

[0010] This invention provides a method for preparing phenoxytriazine sulfonate flame retardants, comprising the following steps:

[0011] Step 1: Add cyanuric chloride to the reaction vessel, then add solvent, and stir thoroughly at 0-10℃ until the cyanuric chloride dissolves;

[0012] Step 2: Dissolve the bisphenol organic compound and the acid-binding agent in water to prepare dropping solution I. Add the solution dropwise using a constant pressure dropping funnel, controlling the dropping rate and keeping the system temperature between 0-5℃ and the pH not exceeding 10. After the addition is complete, intermediate 1 is obtained.

[0013] Step 3: Dissolve p-hydroxybenzenesulfonate and the acid-binding agent in water to prepare dropping solution II, and transfer it into a constant pressure dropping funnel. Start dropping at a temperature of 0-5℃, and raise the temperature to 30℃ while dropping. When half of the amount has been added, intermediate 2 is obtained. Then continue dropping and raise the temperature to 80-100℃. The pH should not exceed 10 during the entire dropping process. After the dropping is completed, reflux for 3-5 hours.

[0014] Step 4: Then stop heating, cool the reactants to room temperature, filter, wash with distilled water 3-5 times, and dry to obtain phenoxytriazine sulfonate flame retardant.

[0015] Furthermore, in step one, the mass ratio of cyanuric chloride to solvent is 1:(0.5-10).

[0016] Furthermore, the solvent mentioned in step one is one or more of water, tetrahydrofuran, acetone, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Ethylene glycol dimethyl ether and diethylene glycol dimethyl ether are preferred solvents.

[0017] Furthermore, in step two, the molar ratio of bisphenol organic compound to acid-binding agent is 1:2.

[0018] Furthermore, the bisphenol organic compound mentioned in step two is one or more of bisphenol A, bisphenol S, hydroquinone, resorcinol, and 4,4'-biphenyl.

[0019] Furthermore, the molar ratio of bisphenol organic compound to cyanuric chloride is m:(m+1), where 1≤m≤30.

[0020] Furthermore, the acid-binding agent mentioned in steps two and three is an alkali metal hydroxide, specifically potassium hydroxide or sodium hydroxide.

[0021] Furthermore, in step three, the molar ratio of p-hydroxybenzenesulfonate to the acid-binding agent is 1:1.

[0022] Furthermore, the molar ratio of p-hydroxybenzenesulfonate to cyanuric chloride is (m+3):(m+1), where 1≤m≤30.

[0023] Furthermore, the p-hydroxybenzenesulfonate mentioned in step three is one or both of potassium and sodium salts. The potassium salt is potassium p-hydroxybenzenesulfonate, and the sodium salt is sodium p-hydroxybenzenesulfonate.

[0024] This invention also provides the application of phenoxytriazine sulfonate flame retardants in the flame retardancy of bisphenol A type polycarbonate.

[0025] The beneficial effects of this invention are:

[0026] Compared to conventional sulfonate flame retardants, the phenoxytriazine sulfonate flame retardant of the present invention is water-insoluble. The phenoxytriazine sulfonate molecular chain structure of the present invention contains a bisphenol A group or a bisphenol S group and a triazine ring. Due to the hydrophobicity and π-π stacking of these groups, it is insoluble in water, but forms easily dispersible clustered particles in water. Therefore, the phenoxytriazine sulfonate flame retardant of the present invention does not precipitate.

[0027] The phenoxytriazine sulfonate flame retardant of the present invention incorporates the structure of bisphenol organic compounds, which makes it more compatible with PC, has less impact on transparency and haze, is less likely to precipitate in the PC matrix, and can achieve long-term effectiveness.

[0028] The raw materials required for the synthesis of the phenoxytriazine sulfonate flame retardant of the present invention are readily available, the synthesis process is simple, easy to operate, and easy to promote.

[0029] Due to the introduction of sulfonate groups and triazine rings, the flame retardant of the present invention also has the effect of rapid expansion into char. Therefore, the sulfonate flame retardant involved in the present invention exhibits excellent flame retardant properties and water resistance without precipitation in PC materials, providing a new solution for the preparation of fluorine-free flame retardant PC materials. Attached Figure Description

[0030] Figure 1 This is the thermogravimetric curve of flame retardant I (n=1);

[0031] Figure 2 This is the thermogravimetric curve of flame retardant I (n=10);

[0032] Figure 3 This is the thermogravimetric curve of flame retardant I (n=30);

[0033] Figure 4 This is the thermogravimetric curve of flame retardant II (n=1);

[0034] Figure 5 This is the thermogravimetric curve of flame retardant II (n=10);

[0035] Figure 6 This is the thermogravimetric curve of flame retardant II (n=30);

[0036] Figure 7 It is the infrared spectrum of flame retardant I (n=1);

[0037] Figure 8 It is the infrared spectrum of flame retardant I (n=10);

[0038] Figure 9 It is the infrared spectrum of flame retardant I (n=30);

[0039] Figure 10 It is the infrared spectrum of flame retardant II (n=1);

[0040] Figure 11 It is the infrared spectrum of flame retardant II (n=10);

[0041] Figure 12 This is the infrared spectrum of flame retardant II (n=30). Detailed Implementation

[0042] The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

[0043] Specific Implementation Method 1: The phenoxytriazine sulfonate flame retardant of this implementation method has the following structure:

[0044]

[0045] Where n≥1, X is , , , or .

[0046] Specific Implementation Method Two: The preparation method of the phenoxytriazine sulfonate flame retardant in this implementation method includes the following steps:

[0047] Step 1: Add cyanuric chloride to the reaction vessel, then add solvent, and stir thoroughly at 0-10℃ until the cyanuric chloride dissolves;

[0048] Step 2: Dissolve the bisphenol organic compound and the acid-binding agent in water to prepare dropping solution I. Add the solution dropwise using a constant pressure dropping funnel, controlling the dropping rate and maintaining the system temperature at 0-5℃ and pH not exceeding 10. After the addition is complete, intermediate 1 is obtained. Taking bisphenol A as an example, the chemical reaction process is as follows:

[0049]

[0050] Step 3: Dissolve p-hydroxybenzenesulfonate and the acid-binding agent in water to prepare dropping solution II, and transfer it into a constant pressure dropping funnel. Start dropping at a temperature of 0-5℃, and raise the temperature to 30℃ while dropping. When half of the amount has been added, intermediate 2 is obtained. Then continue dropping and raise the temperature to 80-100℃. The pH should not exceed 10 during the entire dropping process. After the dropping is completed, reflux for 3-5 hours.

[0051] Taking potassium p-hydroxybenzenesulfonate as an example, its chemical reaction process is as follows:

[0052]

[0053] Step 4: Then stop heating, cool the reactants to room temperature, filter, wash with distilled water 3-5 times, and dry to obtain phenoxytriazine sulfonate flame retardant.

[0054] Specific Implementation Method 3: In step one of this implementation method, the mass ratio of cyanuric chloride to solvent is 1:(0.5-10). Other steps and parameters are the same as in Specific Implementation Method 2.

[0055] Specific Implementation Method Four: The solvent mentioned in step one of this implementation method is one or more of water, tetrahydrofuran, acetone, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Other steps and parameters are the same as in Specific Implementation Method Two or Three.

[0056] In this embodiment, the preferred solvents are ethylene glycol dimethyl ether and diethylene glycol dimethyl ether.

[0057] Specific Implementation Method 5: In step two of this implementation method, the molar ratio of bisphenol organic compound to acid-binding agent is 1:2. Other steps and parameters are the same as in one of Specific Implementation Methods 2 to 4.

[0058] Specific Implementation Method Six: The bisphenol organic compound mentioned in step two of this implementation method is one or more of bisphenol A, bisphenol S, hydroquinone, resorcinol, and 4,4'-biphenyl. Other steps and parameters are the same as in any one of Specific Implementation Methods Two to Five.

[0059] Specific Implementation Method Seven: In this implementation method, the molar ratio of bisphenol organic compound to cyanuric chloride is m:(m+1), where 1≤m≤30. Other steps and parameters are the same as in Specific Implementation Methods Two to Six.

[0060] Specific Implementation Method Eight: The acid-binding agent mentioned in steps two and three of this implementation method is an alkali metal hydroxide. Other steps and parameters are the same as in any of Specific Implementation Methods Two to Seven.

[0061] The alkali metal hydroxide described in this embodiment is potassium hydroxide or sodium hydroxide.

[0062] Specific Implementation Method Nine: In step three of this implementation method, the molar ratio of p-hydroxybenzenesulfonate and the acid-binding agent is 1:1. Other steps and parameters are the same as in Specific Implementation Methods Two through Eight.

[0063] Specific Embodiment Ten: In this embodiment, the molar ratio of p-hydroxybenzenesulfonate and cyanuric chloride is (m+3):(m+1), where 1≤m≤30. Other steps and parameters are the same as in Specific Embodiments Two to Nine.

[0064] Specific Implementation Method Eleven: The p-hydroxybenzenesulfonate mentioned in step three of this implementation method is one or both of potassium and sodium salts. Other steps and parameters are the same as in Specific Implementation Methods Two through Ten.

[0065] The potassium salt described in this embodiment is potassium p-hydroxybenzenesulfonate, and the sodium salt is sodium p-hydroxybenzenesulfonate.

[0066] Specific Implementation Method Twelve: The application of phenoxytriazine sulfonate flame retardant in the flame retardancy of bisphenol A type polycarbonate.

[0067] The embodiments of the present invention will be described in detail below. The following embodiments are implemented based on the technical solution of the present invention, and detailed implementation schemes and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0068] Example 1:

[0069] The preparation method of the phenoxytriazine sulfonate flame retardant in this embodiment includes the following steps:

[0070] First, place 55.323g of cyanuric chloride (0.3mol) into a four-necked flask equipped with a stirrer, a constant pressure dropping funnel, a reflux tube and a thermometer. Add an ice bath device at the bottom, then pour 500mL of ice water (0℃) into the four-necked flask and stir well.

[0071] 2. Dissolve 34.25g (0.15mol) of bisphenol A and 17.7g (0.3mol) of potassium hydroxide in 200mL of water and stir well to prepare dropping solution I. Then place it in a constant pressure dropping funnel and add it dropwise to a four-necked flask. Control the dropping rate to keep the system temperature at 0℃ and the pH value not exceeding 10. Add at a constant rate for 2 hours. After the addition is complete, intermediate 1 is obtained.

[0072] 3. Dissolve 127.4 g (0.6 mol) of potassium p-hydroxybenzenesulfonate and 35.4 g (0.6 mol) of potassium hydroxide in 400 mL of water and stir well to prepare dropping solution II. Transfer the solution to a constant pressure dropping funnel and start dropping at 0 °C. While dropping, raise the temperature to 30 °C and keep the temperature constant. When half of the amount has been added, intermediate 2 is obtained. Then continue dropping and raise the temperature to 100 °C. Ensure that the pH does not exceed 10 throughout the dropping process. After the dropping is completed, reflux the reaction for 3 h.

[0073] Fourth, stop heating, cool to room temperature, filter, wash three times with distilled water, and then dry in a blower at 110°C for 6 hours to obtain the white target product phenoxytriazine sulfonate flame retardant—Ⅰ (n=1), with a yield of 85%.

[0074] The structure of the phenoxytriazine sulfonate flame retardant prepared in this embodiment is as follows:

[0075]

[0076] Example 2:

[0077] The preparation method of the phenoxytriazine sulfonate flame retardant in this embodiment includes the following steps:

[0078] First, place 55.323g of cyanuric chloride (0.3mol) into a four-necked flask equipped with a stirrer, a constant pressure dropping funnel, a reflux tube and a thermometer, and add an ice bath device below. Then pour 500mL of acetone (0℃) into the four-necked flask and stir until completely dissolved.

[0079] 2. Dissolve 34.25 g (0.15 mol) of bisphenol A and 17.7 g (0.3 mol) of potassium hydroxide in 200 mL of water and stir well to prepare dropping solution I. Place this solution in a constant-pressure dropping funnel and add it dropwise to a four-necked flask. Control the dropping rate to maintain the system temperature at 3°C ​​and the pH value not exceeding 10. Add at a constant rate for 1.5 h. After the addition is complete, intermediate 1 is obtained.

[0080] 3. Dissolve 127.4 g (0.6 mol) of potassium p-hydroxybenzenesulfonate and 35.4 g (0.6 mol) of potassium hydroxide in 400 mL of water and stir well to prepare dropping solution II. Transfer the solution to a constant pressure dropping funnel and start dropping at 0 °C. While dropping, raise the temperature to 30 °C and keep the temperature constant. Control the dropping rate to keep the pH value at 10 to obtain intermediate 2. Then test the pH value. If it exceeds 10, continue to drop while slowly raising the temperature to 70 °C and evaporate the acetone in the system. Then continue to raise the temperature to 100 °C. After the dropping is completed, reflux the reaction for 3 h.

[0081] Fourth, stop heating, cool to room temperature, filter, wash three times with distilled water, and then dry in a blower at 110°C for 6 hours to obtain the white target product, phenoxytriazine sulfonate flame retardant, with a yield of 92.7%.

[0082] The structure of the phenoxytriazine sulfonate flame retardant prepared in this embodiment is as follows:

[0083]

[0084] Example 3:

[0085] The preparation method of the phenoxytriazine sulfonate flame retardant in this embodiment includes the following steps:

[0086] First, place 55.323g of cyanuric chloride (0.3mol) into a four-necked flask equipped with a stirrer, a constant pressure dropping funnel, a reflux tube and a thermometer, and add an ice bath device below. Then, pour 500mL of tetrahydrofuran (0℃) into the four-necked flask and stir until completely dissolved.

[0087] 2. Dissolve 34.25g (0.15mol) of bisphenol A and 17.7g (0.3mol) of potassium hydroxide in 200mL of water and stir well to prepare dropping solution I. Then place it in a constant pressure dropping funnel and add it dropwise to a four-necked flask. Control the dropping rate to keep the system temperature at 0℃ and the pH value not exceeding 10. Add at a constant rate for 1.5h. After the addition is complete, intermediate 1 is obtained.

[0088] 3. Dissolve 127.4 g (0.6 mol) of potassium p-hydroxybenzenesulfonate and 35.4 g (0.6 mol) of potassium hydroxide in 400 mL of water and stir well to prepare dropping solution II. Transfer the solution to a constant pressure dropping funnel and start dropping at 0 °C. While dropping, raise the temperature to 30 °C and keep the temperature constant. Control the dropping rate to keep the pH value at 10 to obtain intermediate 2. Then test the pH value. If it exceeds 10, continue to drop while slowly raising the temperature to 80 °C and evaporate the tetrahydrofuran in the system. Then continue to raise the temperature to 100 °C. After the dropping is completed, reflux the reaction for 3 h.

[0089] Fourth, stop heating, cool to room temperature, filter, wash three times with distilled water, and then dry in a blower at 110°C for 6 hours to obtain the white target product, phenoxytriazine sulfonate flame retardant, with a yield of 82.3%.

[0090] The structure of the phenoxytriazine sulfonate flame retardant prepared in this embodiment is as follows:

[0091]

[0092] Example 4:

[0093] The difference between this embodiment and Example 2 is that the solvent in step one is changed from acetone to ethylene glycol dimethyl ether. All other steps and parameters are the same as in Example 2. The final yield of the target product was 95.6%.

[0094] Example 5:

[0095] The difference between this embodiment and Example 2 is that the solvent in step one is changed from acetone to diethylene glycol dimethyl ether. All other steps and parameters are the same as in Example 2. The final yield of the target product was 97.8%.

[0096] Example 6:

[0097] The difference between this embodiment and Example 1 is that the molar ratio of bisphenol A, cyanuric chloride, and potassium p-hydroxybenzenesulfonate is 10:11:13. Other steps and parameters are the same as in Example 1. A white target product, phenoxytriazine sulfonate flame retardant—Ⅰ (n=10), was obtained, with a final yield of 90.8%.

[0098] The structure of the phenoxytriazine sulfonate flame retardant prepared in this embodiment is as follows:

[0099]

[0100] Example 7:

[0101] The difference between this embodiment and Example 1 is that the molar ratio of bisphenol A, cyanuric chloride, and potassium p-hydroxybenzenesulfonate is 30:31:33. Other steps and parameters are the same as in Example 1. A white target product, phenoxytriazine sulfonate flame retardant—Ⅰ (n=30), was obtained, with a final yield of 96%.

[0102] The structure of the phenoxytriazine sulfonate flame retardant prepared in this embodiment is as follows:

[0103]

[0104] Example 8:

[0105] The preparation method of the sulfonate flame retardant in this embodiment includes the following steps:

[0106] First, place 55.323g of cyanuric chloride (0.3mol) into a four-necked flask equipped with a stirrer, a constant pressure dropping funnel, a reflux tube and a thermometer. Add an ice bath device at the bottom, then pour 100mL of ice water (0℃) into the four-necked flask and stir well.

[0107] 2. Dissolve 38g (0.15mol) of bisphenol S and 17.7g (0.3mol) of potassium hydroxide in 200mL of water and stir well to prepare dropping solution I. Then place it in a constant pressure dropping funnel and add it dropwise to a four-necked flask. Control the dropping rate to keep the system temperature at 5℃ and the pH value not exceeding 10. Add at a constant rate for 2 hours. After the addition is complete, intermediate 1 is obtained.

[0108] 3. Dissolve 127.4 g (0.6 mol) of potassium p-hydroxybenzenesulfonate and 35.4 g (0.6 mol) of potassium hydroxide in 400 mL of water and stir well to prepare dropping solution II. Transfer the solution to a constant pressure dropping funnel and start dropping at 0 °C. While dropping, raise the temperature to 30 °C and keep the temperature constant. When half of the amount has been added, intermediate 2 is obtained. Then continue dropping and raise the temperature to 100 °C. Ensure that the pH does not exceed 10 throughout the dropping process. After the dropping is completed, reflux the reaction for 5 h.

[0109] Fourth, stop heating, cool to room temperature, filter, wash three times with distilled water, and then dry in a blower at 110°C for 6 hours to obtain the white target product phenoxytriazine sulfonate flame retardant II (n=1), with a yield of 95%.

[0110] The structure of the phenoxytriazine sulfonate flame retardant prepared in this embodiment is as follows:

[0111]

[0112] Example 9:

[0113] The difference between this embodiment and Example 8 is that the molar ratio of bisphenol S, cyanuric chloride, and potassium p-hydroxybenzenesulfonate is 10:11:13. Other steps and parameters are the same as in Example 8. A white target product, phenoxytriazine sulfonate flame retardant—II (n=10), was obtained, with a final yield of 96%.

[0114] The structure of the phenoxytriazine sulfonate flame retardant prepared in this embodiment is as follows:

[0115]

[0116] Example 10:

[0117] The difference between this embodiment and Example 8 is that the molar ratio of bisphenol S, cyanuric chloride, and potassium p-hydroxybenzenesulfonate is 30:31:33. Other steps and parameters are the same as in Example 8. A white target product, phenoxytriazine sulfonate flame retardant II (n=30), was obtained, with a final yield of 96%.

[0118] The structure of the phenoxytriazine sulfonate flame retardant prepared in this embodiment is as follows:

[0119]

[0120] The flame retardants prepared in Examples 1 and 6-10 above were subjected to the following analysis and testing:

[0121] (I) Thermogravimetric analysis (TGA) test of phenoxytriazine sulfonate flame retardant

[0122] Thermogravimetric analysis (TGA) was performed on flame retardants I (n=1), I (n=10), I (n=30) and II (n=1), II (n=10), II (n=30), respectively. The test results are as follows: Figures 1-6 As shown, the initial decomposition temperatures of flame retardants I (n=1), I (n=10), and I (n=30) are 394.5℃, 402.6℃, and 408.3℃, respectively. A pattern emerges: the thermal stability of the product increases with increasing chain length. The initial decomposition temperatures of flame retardants II (n=1), II (n=10), and II (n=30) are 360.9℃, 362.7℃, and 367.2℃, respectively, also exhibiting good thermal stability. The flame retardant compounds of this invention can meet the processing temperature requirements of most polymer materials.

[0123] (II) Structural characterization of phenoxytriazine sulfonate flame retardants

[0124] Figure 7 The infrared spectrum of flame retardant I (n=1) is shown below. Figure 7 It can be known that 2920cm -1 The absorption peak at 1130 cm⁻¹ corresponds to the CH stretching vibration on the benzene ring. -1 The peak at 1630 cm⁻¹ represents the -CH₃ bending vibration of bisphenol A. -1 With 1365cm -1 The peak at 1507 cm⁻¹ represents the stretching vibration of the triazine ring. -1 and 1460cm -1 The absorption peak at 1038 cm⁻¹ represents the skeletal vibrational absorption peak of the benzene ring. -1 With 1012cm -1 The position is sulfonate ion (-SO3). - The stretching vibration peaks of flame retardant I (n=10) and flame retardant I (n=30) are respectively... Figure 8 and Figure 9 .like Figure 10 As shown, 2918cm -1 The peak at 1631 cm⁻¹ corresponds to the absorption peak of the CH stretching vibration on the benzene ring. -1 With 1365cm -1 The absorption peak at 1490 cm⁻¹ is the stretching vibration absorption peak of the triazine ring. -1The absorption peak at 1012 cm⁻¹ represents the skeletal vibrational absorption peak of the benzene ring. -1 With 1038cm -1 The position is sulfonate ion (-SO3). - The stretching vibration absorption peak of 1125 cm⁻¹. -1 With 1151cm -1 The absorption peak at this position is the stretching vibration peak of the -(SO2)- group. The infrared spectra of flame retardant II (n=10) and flame retardant II (n=30) are respectively... Figure 11 and Figure 12 .

[0125] (III) Performance of Flame-Retardant Polycarbonate (PC) Materials

[0126] (1) Sample preparation

[0127] The synthesized phenoxytriazine sulfonate flame retardant was thoroughly mixed with PC at a certain mass ratio using a high-speed mixer. The mixture was then heated and melt-blended for 15 minutes using a torque rheometer. The temperatures of each heating zone were 250℃, 250℃, and 250℃, respectively, at a rotation speed of 50 r / min. After mixing, the material was removed and placed on a flat vulcanizing machine for hot pressing at 250℃ and 10 MPa pressure. The resulting material was then cut into standard strips, which were used to produce flame-retardant PC for performance testing.

[0128] (2) Flame retardant performance test of PC composite material

[0129] The flame retardant properties of the flame-retardant PC material were characterized by vertical burning (UL-94) and limiting oxygen index (LOI) tests. Pure PC is relatively easy to ignite in air, dripping and carrying fire, with an LOI value of 27% and a UL-94 rating of V2. When the synthesized sulfonate flame retardant was added to the PC material, its flame retardant properties were significantly improved. Tests showed that when the flame retardant prepared in Examples 1-7 was added at a concentration of 0.05%, the UL-94 flame retardant V0 rating was achieved, with an LOI as high as 38%. Similarly, when the flame retardant prepared in Examples 8-10 was added at a concentration of 0.1%, the UL-94 flame retardant V0 rating was achieved, with an LOI as high as 38%. The test results indicate that the synthesized phenoxytriazine sulfonate flame retardant has excellent flame retardant effects on PC.

[0130] (3) Optical performance testing of flame-retardant PC materials

[0131] Besides its superior impact strength, PC, as an engineering plastic, also boasts excellent transparency. The impact of flame retardants on the optical properties of PC is a crucial indicator. Under laboratory conditions, the optical properties of PC were tested as follows: pure PC had a light transmittance of 89.7% and a haze of 5.34%. However, when flame retardant I (n=1) was added at amounts of 0.05%, 0.1%, 0.5%, and 0.8%, the light transmittance was 89.8%, 89.6%, 88.3%, and 87.5%, respectively, and the haze was 5.29%, 5.41%, 6.42%, and 8.82%, respectively. It can be seen that lower addition amounts have little impact on transparency, thus meeting both flame retardant requirements and other necessary conditions. When the addition amounts of flame retardant II (n=1) were 0.05%, 0.1%, 0.5%, and 0.8%, respectively, their transparency was 88.5%, 88.2%, 87.3%, and 85.2%, and their haze was 6.36%, 6.87%, 8.23%, and 11.26%, respectively. The PC materials blended with it had lower transparency and haze than those blended with flame retardant I (n=1). This may be because flame retardant I incorporates bisphenol A into its structure, giving it better compatibility with PC and resulting in higher transparency.

[0132] (4) Water resistance test of flame-retardant PC material

[0133] The water resistance test involved immersing the test sample in a water bath containing 70°C deionized water for 168 hours, with the deionized water replaced every 24 hours. After the immersion test, the sample was removed and dried in a 120°C oven. After drying, the surface was observed for any precipitates or white bloom, and the water-treated sample was obtained. The experimental results showed that when the addition amounts of flame retardant I (n=1) were 0.05% and 0.1%, respectively, the surface of the water-treated flame-retardant PC samples showed no precipitates or white bloom, and both passed the UL-94 V-0 rating. Compared to untreated flame-retardant PC, its oxygen index remained at 37%, and its light transmittance and haze showed almost no change.

Claims

1. A phenoxytriazine sulfonate flame retardant, characterized in that, The structure of this flame retardant is as follows: Where n≥1, X is , , , or .

2. The method for preparing the phenoxytriazine sulfonate flame retardant as described in claim 1, characterized in that, The preparation method includes the following steps: Step 1: Add cyanuric chloride to the reaction vessel, then add solvent, and stir thoroughly at 0-10℃ until the cyanuric chloride dissolves; Step 2: Dissolve the bisphenol organic compound and the acid-binding agent in water to prepare dropping solution I. Add the solution dropwise using a constant pressure dropping funnel, controlling the dropping rate and keeping the system temperature between 0-5℃ and the pH not exceeding 10. After the addition is complete, intermediate 1 is obtained. Step 3: Dissolve p-hydroxybenzenesulfonate and the acid-binding agent in water to prepare dropping solution II, and transfer it into a constant pressure dropping funnel. Start dropping at a temperature of 0-5℃, and raise the temperature to 30℃ while dropping. When half of the amount has been added, intermediate 2 is obtained. Then continue dropping and raise the temperature to 80-100℃. The pH should not exceed 10 during the entire dropping process. After the dropping is completed, reflux for 3-5 hours. Step 4: Then stop heating, cool the reactants to room temperature, filter, wash with distilled water 3-5 times, and dry to obtain phenoxytriazine sulfonate flame retardant.

3. The method for preparing the phenoxytriazine sulfonate flame retardant according to claim 2, characterized in that, In step one, the mass ratio of cyanuric chloride to solvent is 1:(0.5-10).

4. The method for preparing the phenoxytriazine sulfonate flame retardant according to claim 2, characterized in that, In step two, the molar ratio of bisphenol organic compound to acid-binding agent is 1:

2.

5. The method for preparing the phenoxytriazine sulfonate flame retardant according to claim 2, characterized in that, The bisphenol organic compound mentioned in step two is one or more of bisphenol A, bisphenol S, hydroquinone, resorcinol, and 4,4'-biphenyl.

6. The method for preparing the phenoxytriazine sulfonate flame retardant according to claim 2, characterized in that, The molar ratio of bisphenol organic compound to cyanuric chloride is m:(m+1), where 1≤m≤30.

7. The method for preparing the phenoxytriazine sulfonate flame retardant according to claim 2, characterized in that, In step three, the molar ratio of p-hydroxybenzenesulfonate to the acid-binding agent is 1:

1.

8. The method for preparing the phenoxytriazine sulfonate flame retardant according to claim 2, characterized in that, The molar ratio of p-hydroxybenzenesulfonate to cyanuric chloride is (m+3):(m+1), where 1≤m≤30.

9. The method for preparing the phenoxytriazine sulfonate flame retardant according to claim 2, characterized in that, The p-hydroxybenzenesulfonate mentioned in step three is one or both of potassium and sodium salts.

10. The application of the phenoxytriazine sulfonate flame retardant as described in claim 1 in the flame retardancy of bisphenol A type polycarbonate.

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