Triazine ring compounds, preparation methods, and triazine ring phosphorus-containing flame retardants and applications

Abstract

The present invention relates to the technical field of phosphorus-nitrogen synergistic flame retardant materials, and particularly relates to triazine ring compounds, preparation methods, triazine ring phosphorus-containing flame retardants and applications. The chemical structure of the triazine ring compound simultaneously has a phosphorus-containing group and a nitrogen-containing group. During the combustion process, the phosphorus-containing group forms P· radicals and PO· radicals, which quench H· and HO· radicals in the gas phase, having a gas-phase flame retardant effect. At the same time, the phosphorus-containing group is further oxidized to form phosphoric acid, promoting the formation of a dense carbon layer in the polymer matrix, achieving the effect of condensed-phase flame retardancy; the nitrogen-containing group can form non-combustible components such as ammonia and nitrogen oxides during the combustion process, effectively reducing the concentration of oxygen and combustible gases in the combustion area, achieving the purpose of gas-phase flame retardancy; the phosphorus-containing group and the nitrogen-containing group can exert the phosphorus-nitrogen synergistic flame retardant effect, thereby achieving the purpose of high-efficiency flame retardancy.

Description

Technical Field

[0001] The present invention relates to the technical field of phosphorus-nitrogen synergistic flame retardant materials, and particularly to triazine ring compounds, preparation methods, phosphorus-containing triazine ring flame retardants and applications thereof. Background Art

[0002] Polymer materials are widely used in many fields of modern life, bringing great convenience to people's production and life. However, their relatively high fire hazard also poses a certain threat to people's lives and property safety. Therefore, the flame retardant technology of polymer materials has become one of the hot research fields at home and abroad in recent decades. At present, common halogen-free flame retardant systems mainly include phosphorus-based flame retardants, nitrogen-based flame retardants, silicon-based flame retardants, boron-based flame retardants, etc. In order to improve the flame retardant efficiency and make up for the deficiencies of single flame retardants, using multiple flame retardants to form a synergistic system is one of the current research hotspots of halogen-free flame retardants in the world, in order to balance the relationship between the dosage, performance and cost of flame retardants and meet the growing requirements of environmental protection and safety (Journal of Analytical and Applied Pyrolysis 2007, 78, 371-377). Phosphorus-nitrogen synergistic flame retardants are one of the most common synergistic flame retardant systems, with the advantages of flame retardancy, heat insulation, oxygen isolation, and less smoke generation (Journal of Applied Polymer Science 2004, 92, 410-417; Industrial & Engineering Chemistry Research 2016, 55, 10813-10822; Polymer-Plastics Technology and Engineering 2017, 56, 1118-1127; Cellulose 2021, 28, 1781–1793). 1,3,5-(tripiperazine)-triazine contains rich nitrogen elements, and the aromatic ring structure is beneficial to improving the thermal stability of the carbon layer. In addition, the 1,3,5-(tripiperazine)-triazine structure contains N-H functional groups, which can form a P-N structure after being substituted by some phosphorus-containing compounds. However, there are few reports on such compounds. 1,3,5-(tripiperazine)-triazine-based phosphorus-containing flame retardants contain rich phosphorus and nitrogen elements, can exert the phosphorus-nitrogen synergistic flame retardant effect, and are expected to become a new type of halogen-free, environmentally friendly, safe and efficient phosphorus-based flame retardant. Summary of the Invention

[0003] The chemical structure of the triazine ring compound provided by the present invention contains both phosphorus atoms and nitrogen atoms at the same time, can exert the phosphorus-nitrogen synergistic flame retardant effect, and improve the flame retardant efficiency; and can adjust the hydrophilic-lipophilicity of the triazine ring compound by regulating the types of its phosphorus-containing functional groups, and is suitable for the flame retardant treatment of different polymer matrices.

[0004] To achieve the above object, the present invention adopts the following technical solutions:

[0005] A triazine ring compound, the structure of which is shown in Formula I:

[0006]

[0007] Wherein: in Formula I, each R is a group containing P=O.

[0008] Further, the three Rs in Formula I are independently selected from:

[0009]

[0010] Further, a preparation method of the triazine ring compound includes the following steps:

[0011] S1. Take a phosphorus-containing compound, triethylamine and 1,3,5-(tripiperazine)-triazine and dissolve them in dichloromethane;

[0012] S2. Stir and cool the mixture in step S1, and the cooling temperature ranges from -5°C to +5°C;

[0013] S3. Dropwise add carbon tetrachloride to the mixture in step S2, and maintain the reaction temperature between -20°C and 35°C during the dropping process;

[0014] S4. Stir and heat the mixture obtained in step S3 to room temperature;

[0015] S5. Filter the reactant obtained in step S4 to obtain a precipitate;

[0016] S6. Wash the precipitate obtained in step S5;

[0017] S7. Dry the material obtained after washing in step S6 to a constant weight to obtain the triazine ring compound.

[0018] Further, the molar ratio of 1,3,5-(tripiperazine)-triazine, the phosphorus-containing compound, triethylamine and carbon tetrachloride is 1.0:(2.5 - 4.5):(2.5 - 5.0):(2.5 - 5.0).

[0019] Further, the molar ratio of 1,3,5-(tripiperazine)-triazine, the phosphorus-containing compound, triethylamine and carbon tetrachloride is 1.0:(3.0 - 3.3):(3.0 - 3.5):(3.0 - 3.5).

[0020] Further, the phosphorus-containing compound is one or a mixture of several of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide, phosphorous acid, diphenyl phosphite, dibenzyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, and diisobutyl phosphite.

[0021] Further, in step S6, the precipitate is washed with water and / or acetone.

[0022] Further, step S7 uses vacuum drying.

[0023] Further, in step S2, the cooling temperature ranges from -3°C to +3°C, and in step S3, the reaction temperature is maintained between -5°C and +25°C during the dropping process.

[0024] Further, in step S2, the cooling temperature is 0°C, and in step S3, the reaction temperature is maintained at 15°C during the dropping process.

[0025] Further, in step S3, the dropping time of carbon tetrachloride is controlled within 0.5 to 2 hours, and after dropping carbon tetrachloride, in step S4, the reaction time of heating to room temperature and continuously stirring is 2 to 24 hours.

[0026] The triazine ring-containing phosphorus flame retardant containing a triazine ring compound uses the triazine ring compound of claim 1 or 2 as a flame retardant component.

[0027] The application of a triazine ring compound or a triazine ring-containing phosphorus flame retardant, wherein the triazine ring compound or the triazine ring-containing phosphorus flame retardant is formulated into an aqueous or ethanol solution, and then a cotton fabric is impregnated in the above solution and taken out until it reaches a constant weight to obtain a flame-retardant textile.

[0028] The application of a triazine ring compound or a triazine ring-containing phosphorus flame retardant, wherein the triazine ring compound or the triazine ring-containing phosphorus flame retardant is added to an epoxy resin to produce a flame-retardant epoxy resin.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1. In the chemical structure of the triazine ring compound provided by the present invention, there are both a phosphorus-containing group and a nitrogen-containing group. The phosphorus-containing group forms P· radicals and PO· radicals during the combustion process, quenches H· and HO· radicals in the gas phase, and has a gas-phase flame retardant effect. At the same time, the phosphorus-containing group is further oxidized to form phosphoric acid, promoting the formation of a dense carbon layer in the polymer matrix, achieving the effect of condensed-phase flame retardancy; the nitrogen-containing group can form non-combustible components such as ammonia and nitrogen oxides during the combustion process, effectively reducing the concentration of oxygen and combustible gases in the combustion area, achieving the purpose of gas-phase flame retardancy; the phosphorus-containing group and the nitrogen-containing group can exert a phosphorus-nitrogen synergistic flame retardant effect, thereby achieving the purpose of high-efficiency flame retardancy.

[0031] 2. The phosphorus content and the number of aromatic rings in the chemical structure of the triazine ring compound provided by the present invention can be regulated, so that the hydrophilic-lipophilic balance of the product can be regulated, and it has good compatibility with the matrix, and is suitable for the flame retardant treatment of different polymer matrices.

[0032] 3. During the dropping process in step S3, carbon tetrachloride has participated in the reaction, but not completely. The dropping rate is controlled to prevent the temperature from rising too fast; in step S4, it is the process of further reaction after the dropping of carbon tetrachloride is completed. Description of the Drawings

[0033] Figure 1 Curves of heat release rate of epoxy resin, flame retardant epoxy resin-2, and flame retardant epoxy resin-6;

[0034] Figure 2 , Figure 1 Partial enlarged view within the time range of 0 - 200 s;

[0035] Figure 3 Curves of total heat release of epoxy resin, flame retardant epoxy resin-2, and flame retardant epoxy resin-6;

[0036] Figure 4 , Figure 3 Partial enlarged view within the time range of 200 - 700 s;

[0037] Figure 5 Comparison diagram of transparency between epoxy resin and flame retardant epoxy resin-2;

[0038] Figure 6 Real-time photos of vertical burning test of unflame-retarded cotton fabric and flame-retarded cotton fabric. Specific Embodiments

[0039] Example 1:

[0040] Dissolve 3.3 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 3.5 mol of triethylamine, and 1.0 mol of 1,3,5-(tripiperazine)-triazine in 2 L of dichloromethane, stir and cool to 0 °C. Then, gradually add 3.5 mol of carbon tetrachloride dropwise, and maintain the reaction temperature at 15 °C during the dropping process. Stir while dropping, control the dropping time of carbon tetrachloride to 0.5 hour, and after the dropping of carbon tetrachloride is completed, heat to room temperature and continue stirring for 2 hours. Subsequently, filter the reaction mixture and collect the precipitate. Wash the precipitate with 1 L of water 3 times and 500 ml of acetone 2 times in sequence, and then dry it under vacuum to constant weight to obtain the target product a, whose chemical structure is shown as follows:

[0041]

[0042] The target product a was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy ( 1 1H-NMR), and its chemical structure was confirmed as follows: FT-IR (KBr, cm -1 ): 2958 (-CH2-), 1685, 1458 (C aryl =C aryl ), 1530 (C=N), 1235 (P=O), 1115 (C-N), 762 (P–O–Ph). 1 1H-NMR (400 MHz, CDCl3, ppm): 2.81 (t, 12H), 3.68 (t, 12H), 6.97~7.86 (m, 24H).

[0043] Example 2:

[0044] 3.0 mol of diphenylphosphine oxide, 3.3 mol of triethylamine, and 1.0 mol of 3,5-(tripiperazine)-triazine were dissolved in 2 L of dichloromethane, stirred, and cooled to -5 °C. Then, 3.3 mol of carbon tetrachloride was added dropwise, and the reaction temperature was maintained at 10 °C during the addition. Stirring was carried out simultaneously during the addition, and the addition time of carbon tetrachloride was controlled to be 2 hours. After the addition of carbon tetrachloride, the mixture was heated to room temperature and continuously stirred for 24 hours. Subsequently, the reaction mixture was filtered and the precipitate was collected. The precipitate was washed successively with 1 L of water three times and 500 ml of acetone twice, and then dried under vacuum to constant weight to obtain the target product b, whose chemical structure is shown below:

[0045]

[0046] The target product b was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy ( 1 1H-NMR), and its chemical structure was confirmed as follows: FT-IR (KBr, cm -1 ): 2962 (-CH2-), 1655, 1460 (C aryl =C aryl ), 1520 (C=N), 1215 (P=O), 1115 (C-N). 1 1H-NMR (400 MHz, CDCl3, ppm): 2.75 (t, 12H), 3.54 (t, 12H), 7.45~7.82 (m, 30H).

[0047] Example 3:

[0048] Dissolve 3.0 mol of diethyl phosphite, 3.0 mol of triethylamine, and 1.0 mol of 1,3,5-(tripiperazine)-triazine in 2 L of dichloromethane, stir, and cool to -3 °C. Then, add 3.0 mol of carbon tetrachloride dropwise while maintaining the reaction temperature at 25 °C during the addition. Stir while adding, control the carbon tetrachloride addition time within 1 hour, and after adding carbon tetrachloride, heat to room temperature and continue stirring for 12 hours. Subsequently, filter the reaction mixture and collect the precipitate. Wash the precipitate with 1 L of water three times and 500 ml of acetone twice, and then dry it under vacuum to constant weight to obtain the target product c, whose chemical structure is shown below:

[0049]

[0050] The target product c was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy ( 1 1H-NMR), and its chemical structure was confirmed as follows: FT-IR (KBr, cm -1 ): 2985 (-CH3), 2960 (-CH2-), 1663, 1465 (C aryl =C aryl ), 1528 (C=N), 1225 (P=O), 1110 (C-N), 990 (P-O-C). 1 1H-NMR (400 MHz, CDCl3, ppm): 1.20 (m, 18H), 2.78 (t, 12H), 3.17 (t, 12H), 4.51 (m, 12H).

[0051] Example 4:

[0052] Dissolve 3.3 mol of phosphorous acid, 3.5 mol of triethylamine, and 1.0 mol of 1,3,5-(tripiperazine)-triazine in 2 L of dichloromethane, stir, and cool to 3 °C. Then, add 3.5 mol of carbon tetrachloride dropwise while maintaining the reaction temperature at 25 °C during the addition. Stir while adding, control the carbon tetrachloride addition time within 1.5 hours, and after adding carbon tetrachloride, heat to room temperature and continue stirring for 10 hours. Subsequently, filter the reaction mixture and collect the precipitate. Wash the precipitate with 500 ml of acetone five times, and then dry it under vacuum to constant weight to obtain the target product d, whose chemical structure is shown below:

[0053]

[0054] The target product d was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy ( 1 1H-NMR), and its chemical structure was confirmed as follows: FT-IR (KBr, cm -1): 3425 (-OH), 2962 (-CH2-), 1643, 1459 (C aryl = C aryl ), 1530 (C = N), 1239 (P = O), 1110 (C-N). 1 H-NMR (400 MHz, CDCl3, ppm): 2.79 (t, 12H), 3.20 (t, 12H), 4.80 (m, 6H).

[0055] Example 5:

[0056] In this example, a flame-retardant epoxy resin was prepared according to the formulation in Table 1:

[0057] Table 1 Formulation of Flame-Retardant Epoxy Resin

[0058]

[0059] Note: The epoxy resin is a commercial bisphenol A epoxy resin (grade: E-44), and the curing agent is 4,4'-diaminodiphenylmethane.

[0060] Accurately weigh the epoxy resin, curing agent, and flame retardant. First, mix the epoxy resin and the flame retardant at 80 °C for 1 hour, then add the curing agent and continue to mix for 30 minutes. Immediately pour it into a mold, and the curing conditions are curing at 100 °C for 2 hours + curing at 150 °C for 2 hours + curing at 180 °C for 2 hours. Naturally cool to room temperature to obtain a flame-retardant epoxy resin sample. Test the oxygen index and vertical burning performance of the sample according to GBT 2406.2-2009 and ASTM D 3801-10 respectively. The results are shown in Table 2:

[0061] Table 2 Oxygen Index and Vertical Burning Test Results of Flame-Retardant Epoxy Resin

[0062] Oxygen index (%) Results of UL-94 vertical burning test Epoxy resin 22.0 No rating Flame-retardant epoxy resin-1 28.5 V-2 rating Flame-retardant epoxy resin-2 30.0 V-0 rating Flame-retardant epoxy resin-3 31.0 V-0 rating Flame-retardant epoxy resin-4 31.5 V-0 rating Flame-retardant epoxy resin-5 28.0 No rating Flame-retardant epoxy resin-6 27.0 No rating

[0063] From the flame-retardant test results of each sample in Table 2, it can be seen that the oxygen index of the untreated epoxy resin is 22.0%, and there is no rating in the UL-94 vertical burning test. The oxygen index of the flame-retardant epoxy resin-5 with 5 wt% DOPO added is increased to 28.0%, but there is no rating in the UL-94 vertical burning test. The oxygen index of the flame-retardant epoxy resin-6 with 5 wt% 1,3,5-(tripiperazine)-triazine added is increased to 27.0%, but there is still no rating in the UL-94 vertical burning test. In contrast, the oxygen index of the flame-retardant epoxy resin with 5 wt% of flame retardant a, flame retardant b, and flame retardant c added is increased to more than 30.0%, and it can pass the UL-94 vertical burning test at the V-0 level, demonstrating the advantage of high flame-retardant efficiency.

[0064] Figure 1The heat release rate curves of epoxy resin, flame-retardant epoxy resin-2, and flame-retardant epoxy resin-6 obtained by cone calorimeter testing. The peak heat release rate of the unflame-retarded epoxy resin is approximately 1045 kW / m 2 , and the peak heat release rate of the flame-retardant epoxy resin-2 with 5 wt% of flame retardant a added drops to 771 kW / m 2 , a decrease of 26.2%, and its flame retardant efficiency is better than that of flame-retardant epoxy resin-6.

[0065] Figure 2 is Figure 1 The partial enlarged view within the time range of 0 - 200 s. It can be found that for the flame-retardant epoxy resin-6 compared to the unflame-retarded epoxy resin, the peak time of the heat release rate appears at approximately 125 s, and the peak heat release rate of the flame-retardant epoxy resin-6 is approximately 1034 kW / m 2 , the peak time is 102 s, and the peak time of the heat release rate of the flame-retardant epoxy resin-2 with 5 wt% of flame retardant a added is 103 s, and its peak appearance time is also delayed compared to the flame-retardant epoxy resin-6.

[0066] Figure 3 The total heat release curves of epoxy resin, flame-retardant epoxy resin-2, and flame-retardant epoxy resin-6 obtained by cone calorimeter testing. The total heat release curve of the unflame-retarded epoxy resin reaches the peak faster (110.1 MJ / m 2 ); in contrast, the total heat release of the flame-retardant epoxy resin-2 with 5 wt% of flame retardant a added increases slowly and has a lower peak (87.8 MJ / m 2 ), and it is also lower than the total heat release of the flame-retardant epoxy resin-6 with the same amount of flame retardant added (105.4 MJ / m 2 ).

[0067] Figure 4 is Figure 3 The partial enlarged view within the time range of 200 - 700 s. It can be found that the total heat release of the flame-retardant epoxy resin-2 decreases significantly compared to the epoxy resin and the flame-retardant epoxy resin-6.

[0068] Figure 5 The comparison diagram of the transparency of epoxy resin and flame-retardant epoxy resin-2. Compared with the epoxy resin, the flame-retardant epoxy resin-2 still has good transparency, indicating good compatibility between the flame retardant a and the epoxy resin.

[0069] Example 6: Results of the vertical burning test of flame-retardant cotton fabric

[0070] The target product d of the flame retardant was formulated into a 10 wt% aqueous solution, and then the cotton fabric was impregnated in the above solution for 10 minutes. After taking it out, it was placed in an oven at 60 °C and dried to a constant weight to obtain a flame-retardant cotton fabric (weight gain: 3.5%). The vertical burning performance of the sample was tested according to ASTM D6413-08, and the results are as Figure 6 shown.

[0071] Figure 5 Figures Figure 6 and are real-time photos of the vertical burning tests of the unflame-retarded cotton fabric and the flame-retarded cotton fabric. After the first ignition of the unflame-retarded cotton fabric, the flame spread rapidly, and it burned to the top of the sample in only 30 s, and the residue continued to smolder. In contrast, after the first ignition of the flame-retarded cotton fabric treated with the flame retardant d, it automatically extinguished within 1 s after removing the ignition source, and the char length produced was about 9 cm. Even during the second ignition, it could still self-extinguish when the fire source was removed, indicating that the flame retardant d has a high flame retardancy efficiency for cotton fabrics.

[0072] Example 7:

[0073] A triazine ring-containing phosphorus flame retardant, using the triazine ring compound prepared in any one of Examples 1 to 4 as the flame retardant component.

[0074] Example 8:

[0075] Accurately weigh epoxy resin (bisphenol A epoxy resin, E-44), curing agent (4,4'-diaminodiphenylmethane), the triazine ring compound prepared in any one of Examples 1 to 4, or the triazine ring-containing phosphorus flame retardant of Example 7. First, mix the epoxy resin with the triazine ring compound or the triazine ring-containing phosphorus flame retardant at 80 °C for 1 hour, then add the curing agent, continue to mix for 30 minutes, and immediately pour it into a mold. The curing conditions are curing at 100 °C for 2 hours + curing at 150 °C for 2 hours + curing at 180 °C for 2 hours. Naturally cool to room temperature to obtain a flame-retarded epoxy resin sample.

[0076] Example 9:

[0077] The triazine ring compound prepared in any one of Examples 1 to 3 was formulated into a 10 wt% ethanol solution, and then the cotton fabric was impregnated in the above solution for 10 minutes. After taking it out, it was placed in an oven at 60 °C and dried to a constant weight to obtain a flame-retarded cotton fabric.

[0078] Example 10:

[0079] The triazine ring compound prepared in Example 4 was formulated into a 10 wt% ethanol solution, and then the cotton fabric was impregnated in the above solution for 10 minutes. After taking it out, it was placed in an oven at 60 °C and dried to a constant weight to obtain a flame-retarded cotton fabric.

[0080] Example 11:

[0081] Dissolve 3.0 mol of diphenyl phosphite, 3.2 mol of triethylamine, and 1.0 mol of 3,5-(tripiperazine)-triazine in 2 L of dichloromethane, stir, and cool to -2 °C. Then, add 3.3 mol of carbon tetrachloride dropwise while maintaining the reaction temperature at 15 °C during the addition. Stir while adding, control the carbon tetrachloride addition time within 1 hour, and after the addition of carbon tetrachloride, heat to room temperature and continue stirring for 15 hours. Subsequently, filter the reaction mixture and collect the precipitate. Wash the precipitate successively with 1 L of water three times and 500 ml of acetone twice, and then dry it under vacuum to constant weight to obtain the target product e, whose chemical structure is shown below:

[0082]

[0083] The target product e was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy ( 1 1H-NMR), and its chemical structure was confirmed as follows: FT-IR (KBr, cm -1 -1): 2962 (-CH2-), 1655, 1460 (C aryl =C aryl ), 1520 (C=N), 1223 (P=O), 1115 (C-N). 1 1H-NMR (400 MHz, CDCl3, ppm): 2.78 (t, 12H), 3.17 (t, 12H), 7.21 - 7.40 (m, 30H).

[0084] Example 12:

[0085] Dissolve 3.1 mol of dibenzyl phosphite, 3.3 mol of triethylamine, and 1.0 mol of 3,5-(tripiperazine)-triazine in 2 L of dichloromethane, stir, and cool to -3 °C. Then, add 3.5 mol of carbon tetrachloride dropwise while maintaining the reaction temperature at 10 °C during the addition. Stir while adding, control the carbon tetrachloride addition time within 1.5 hours, and after the addition of carbon tetrachloride, heat to room temperature and continue stirring for 12 hours. Subsequently, filter the reaction mixture and collect the precipitate. Wash the precipitate successively with 1 L of water three times and 500 ml of acetone twice, and then dry it under vacuum to constant weight to obtain the target product f, whose chemical structure is shown below:

[0086]

[0087] The target product f was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy ( 1 1H-NMR), and its chemical structure was confirmed as follows: FT-IR (KBr, cm -1): 2962 (-CH2-), 1655, 1460 (C aryl =C aryl ), 1522 (C=N), 1230 (P=O), 1110 (C-N). 1 1H-NMR (400 MHz, CDCl3, ppm): 2.76 (t, 12H), 3.18 (t, 12H), 5.29 (m, 12H), 7.32 - 7.47 (m, 30H).

[0088] Example 13:

[0089] Dissolve 3.2 mol of dimethyl phosphite, 3.2 mol of triethylamine, and 1.0 mol of 3,5-(tripiperazine)-triazine in 2 L of dichloromethane, stir and cool to -3 °C. Then add 3.5 mol of carbon tetrachloride dropwise, and keep the reaction temperature at 18 °C during the dropping process. Stir while dropping, control the dropping time of carbon tetrachloride to 0.8 hours, and after dropping carbon tetrachloride, heat to room temperature and continue stirring for 12 hours. Subsequently, filter the reaction mixture and collect the precipitate. Wash the precipitate with 1 L of water three times and 500 ml of acetone twice in sequence, and then dry it in vacuo to constant weight to obtain the target product g, whose chemical structure is as follows:

[0090]

[0091] The target product g was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectrum ( 1 1H-NMR), and its chemical structure was confirmed as follows: FT-IR (KBr, cm -1 ): 2980 (-CH3), 2968 (-CH2-), 1525 (C=N), 1211 (P=O), 1115 (C-N). 1 1H-NMR (400 MHz, CDCl3, ppm): 2.78 (t, 12H), 3.20 (t, 12H), 3.78 (m, 18H).

[0092] Example 14:

[0093] Dissolve 3.1 mol of dibutyl phosphite, 3.3 mol of triethylamine and 1.0 mol of 3,5-(tripiperazine)-triazine in 2 L of dichloromethane, stir and cool to -1 °C. Then add 3.5 mol of carbon tetrachloride dropwise, and keep the reaction temperature at 10 °C during the dropping process. Stir while dropping, control the dropping time of carbon tetrachloride at 1.0 hour, and after the addition of carbon tetrachloride, heat to room temperature and continue stirring for 15 hours. Subsequently, filter the reaction mixture and collect the precipitate. Wash the precipitate successively with 1 L of water 3 times and 500 ml of acetone 2 times, and then dry it in vacuo to constant weight to obtain the target product h, whose chemical structure is shown below:

[0094]

[0095] The target product h was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy ( 1 1H-NMR), and its chemical structure was confirmed as follows: FT-IR (KBr, cm -1 -1): 2982 (-CH3), 2962 (-CH2-), 1520 (C=N), 1215 (P=O), 1115 (C-N). 1 1H-NMR (400 MHz, CDCl3, ppm): 0.95 (m, 18H), 1.43 (m, 12H), 1.76 (m, 12H), 2.77 (t, 12H), 3.18 (t, 12H), 4.08 (m, 12H).

[0096] Example 15:

[0097] Dissolve 3.1 mol of diisobutyl phosphite, 3.5 mol of triethylamine and 1.0 mol of 3,5-(tripiperazine)-triazine in 2 L of dichloromethane, stir and cool to -4 °C. Then add 3.5 mol of carbon tetrachloride dropwise, and keep the reaction temperature at 8 °C during the dropping process. Stir while dropping, control the dropping time of carbon tetrachloride at 1.5 hours, and after the addition of carbon tetrachloride, heat to room temperature and continue stirring for 15 hours. Subsequently, filter the reaction mixture and collect the precipitate. Wash the precipitate successively with 1 L of water 3 times and 500 ml of acetone 2 times, and then dry it in vacuo to constant weight to obtain the target product i, whose chemical structure is shown below:

[0098]

[0099] The target product i was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectroscopy ( 1 1H-NMR), and its chemical structure was confirmed as follows: FT-IR (KBr, cm -1): 2978 (-CH3), 2955 (-CH2-), 1513 (C=N), 1210 (P=O), 1112 (C-N). 1 H-NMR (400 MHz, CDCl3, ppm): 0.91 (m, 36H), 1.32 (m, 6H), 2.78 (t, 12H), 3.21 (t, 12H), 3.95 (m, 12H).

Claims

1. Triazine ring compounds, characterized in that: The structure is as shown in Formula I: Wherein: the three Rs in Formula I are each independently selected from:

2. The preparation method of the triazine ring compound according to claim 1, characterized in that It includes the following steps: S1. Take a phosphorus-containing compound, triethylamine and 1,3,5-(tripiperazine)-triazine and dissolve them in dichloromethane; S2. Stir and cool the mixture in step S1, and the cooling temperature is between -5°C and +5°C; S3. Dropwise add carbon tetrachloride to the mixture in step S2, and maintain the reaction temperature between -20°C and +35°C during the dropping process; S4. Stir and heat the mixture obtained in step S3 to room temperature; S5. Filter the reactant obtained in step S4 to obtain a precipitate; S6. Wash the precipitate obtained in step S5; S7. Dry the material obtained after washing in step S6 to constant weight to obtain a triazine ring compound; The phosphorus-containing compound in step S1 is one or a mixture of several of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diisobutyl phosphite.

3. The preparation method of the triazine ring compound according to claim 2, characterized in that: The molar ratio of 1,3,5-(tripiperazine)-triazine, phosphorus-containing compound, triethylamine and carbon tetrachloride is 1.0:(3.0 - 3.3):(3.0 - 3.5):(3.0 - 3.5).

4. The preparation method of the triazine ring compound according to claim 2, wherein: In step S6, the precipitate is washed with water and / or acetone.

5. The preparation method of the triazine ring compound according to claim 2, wherein: Step S7 uses vacuum drying.

6. The preparation method of the triazine ring compound according to claim 2, characterized in that: In step S2, the cooling temperature is between -3°C and +3°C, and in step S3, the reaction temperature is maintained between -5°C and +25°C during the dropping process.

7. The preparation method of the triazine ring compound according to claim 6, characterized in that: In step S2, the cooling temperature is 0°C, and in step S3, the reaction temperature is maintained at 15°C during the dropping process.

8. The preparation method of the triazine ring compound according to claim 2, wherein: In step S3, the dropping time of carbon tetrachloride is controlled within 0.5 - 2 hours, and after dropping carbon tetrachloride, the reaction time of continuous stirring after heating to room temperature in step S4 is 2 - 24 hours.

9. A triazine ring-containing phosphorus-containing flame retardant comprising the triazine ring compound of claim 1, characterized in that: Use the triazine ring compound of claim 1 as a flame retardant component.

10. According to the application of the triazine ring compound of claim 1 and the phosphorus-containing flame retardant containing triazine ring of claim 9, it is characterized in that: The triazine ring compound or triazine ring phosphorus-containing flame retardant is formulated into a solution of water or ethanol, and then the cotton fabric is impregnated in the above solution and taken out until it reaches constant weight to obtain a flame retardant textile.

11. Use of the triazine ring compound according to claim 1 or the phosphorus-containing flame retardant containing a triazine ring according to claim 9, characterized in that: Add the triazine ring compound or triazine ring phosphorus-containing flame retardant to epoxy resin to produce flame retardant epoxy resin.

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