Bromine antimony compound flame retardant, its preparation method and application
By synthesizing organic bromoantimony compounds, the problems of antimony trioxide flame retardants affecting transparency and black smoke were solved, and bromoantimony compounds with excellent flame retardant properties were prepared, which are suitable for flammable materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGDONG SHUNDE TONGCHENG NEW MATERIALS TECH CO LTD
- Filing Date
- 2026-01-27
- Publication Date
- 2026-05-29
AI Technical Summary
Existing antimony trioxide flame retardants affect the transparency of products and produce black smoke during use, and must be used in conjunction with halogen and phosphorus flame retardants, which limits their application.
By synthesizing organic bromoantimony compounds, reacting bromine-containing compounds with phosphoryl chloride to form oligomers, and then capping with antimony trichloride to form bromoantimony salts, bromoantimony compound flame retardants were prepared by controlling the reaction conditions and purification process.
It achieves excellent flame retardant properties, good thermal stability, is suitable for flammable materials, reduces black smoke production, and improves the transparency of products.
Smart Images
Figure CN121592032B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of flame retardant materials technology, and in particular to a bromine-antimony compound flame retardant, its preparation method, and its application. Background Technology
[0002] Antimony-based organic and inorganic compounds are widely used flame retardants, with antimony trioxide being the most prevalent and widely applied in plastics, synthetic fibers, and paints. However, antimony trioxide itself lacks flame retardancy and only achieves good results when used in combination with flame retardants containing halogens and phosphorus. Adding excessive amounts of antimony trioxide to products can affect their transparency and produce large amounts of black smoke during combustion, limiting its application. Therefore, synthesizing organobromine-antimony compounds containing both organic bromine and flame-retardant elements in the same molecule is crucial for addressing these issues and is urgently needed. Summary of the Invention
[0003] The purpose of this invention is to provide a bromine-antimony compound flame retardant, its preparation method, and its application. The bromine-antimony compound flame retardant proposed in this invention has excellent flame retardant effect.
[0004] This invention is achieved through the following technical solutions:
[0005] This invention protects a bromine-antimony compound flame retardant, with the structural formula shown in Formula I:
[0006] ;
[0007] Wherein: R1 is selected from phenyl or phenoxy, and R3 is selected from propane or sulfonyl.
[0008] This invention also protects a method for preparing the above-mentioned bromoantimony compound flame retardant, comprising the following steps:
[0009] (1) A bromine-containing compound and phosphoryl chloride are reacted in an organic solvent under heating conditions. After the reaction is completed, the organic solvent is evaporated to dryness to obtain an oligomer.
[0010] (2) Antimony trichloride was added to the oligomer obtained in step (1) for end-capping polymerization to obtain antimony bromide salt;
[0011] (3) The bromo-antimony salt is filtered, washed, and dried to obtain the bromo-antimony compound flame retardant.
[0012] This invention uses a bifunctional monomer containing a bromine compound and phosphoryl dichloride as raw materials to form a polymer backbone containing a phosphate ester with specific functional groups through a condensation reaction (deHCl). In the end-capping stage, the active phenol-OH group at the end of the polymer undergoes nucleophilic substitution or coordination reaction with SbCl3 to form an Sb-O- bond, thereby introducing antimony and achieving functional end-capping.
[0013] In the reaction process of preparing bromine-antimony compound flame retardants, SbCl3 molecules are difficult to approach and react effectively with these end groups, resulting in low end-capping rate and incomplete reaction. The degree of polycondensation reaction between bromine-containing compounds and phosphoryl dichloride affects the subsequent end-capping effect. This invention mainly controls the proportion of oligomers generated by controlling the reaction time, temperature or the dropping rate of phosphoryl chloride. The degree of polymerization of the polymer in the reaction system is determined by monitoring the molecular weight of LCMS [M+1]+. Antimony trichloride is then used for end-capping polymerization. The byproduct SbCl3 that may appear in this reaction is easily hydrolyzed to generate impurities such as SbOCl, and may also be oxidized. Therefore, anhydrous and oxygen-free solvents are used in the reaction process, and the raw materials and system are thoroughly dried. Post-treatment purification is carried out to remove impurities, and alkaline washing and other operations are performed to remove excess end-capping agent.
[0014] The synthesis equation for bromine-antimony compound flame retardants is shown in Formula II:
[0015] ;
[0016] Preferably, the organic solvent in step (1) is selected from one or more of tetrahydrofuran, dioxane and ethanol, and the bromine-containing compound is selected from one of tetrabromobisphenol A and tetrabromobisphenol S; the molar ratio of the bromine-containing compound to phosphoryl chloride is 1.2~1.3:1, and the mass ratio of the total mass of the bromine-containing compound and phosphoryl chloride to the mass of the organic solvent is 1:2~5.
[0017] Further preferred, the mass ratio of the total mass of the bromine-containing compound and phosphoryl chloride to the mass of the organic solvent is 1:2~3.
[0018] Preferably, the phosphoryl chloride in step (1) is phenylphosphoryl dichloride or phenoxyphosphoryl dichloride.
[0019] Preferably, the reaction temperature in step (1) is 55℃~190℃, and the reaction time (the total time of adding the dropping time of phosphoryl chloride to the reaction time) is 9~24 hours.
[0020] Further optimization involves adding the bromine-containing compound to the organic solvent in step (1), adjusting the temperature to 35℃~45℃, slowly adding phosphoryl chloride dropwise while stirring, adjusting the temperature to 75℃~100℃ after the phosphoryl chloride is added, and continuing the reaction. The total time for the addition of phosphoryl chloride and the reaction time is 24 hours. After the reaction is completed, the organic solvent is evaporated to dryness to obtain the oligomer.
[0021] Preferably, step (2) is as follows: the oligomer obtained in step (1) is dissolved in tetrahydrofuran to obtain a tetrahydrofuran solution of the oligomer, and then antimony trichloride is dissolved in tetrahydrofuran to obtain a tetrahydrofuran suspension of antimony trichloride. The tetrahydrofuran suspension of antimony trichloride is slowly added dropwise to the tetrahydrofuran solution of the oligomer at 55℃~65℃. After the addition is completed, the reaction is continued at a constant temperature for 3~4 hours to obtain antimony bromine salt.
[0022] Further optimization involves a reaction temperature of 60°C and a reaction time of 3-4 hours.
[0023] Further preferred, in step (2), the molar ratio of the bromine-containing compound to antimony trichloride is 1:0.3~1.
[0024] Further optimization is made by using a molar ratio of bromine-containing compound to antimony trichloride in step (2) of 1:0.30~0.45.
[0025] Preferably, the mass fraction of the oligomer in the tetrahydrofuran solution of the oligomer in step (2) is 20% to 50%, and the mass fraction of antimony trichloride in the tetrahydrofuran suspension of antimony trichloride is 20% to 50%.
[0026] Step (3) The specific steps are as follows: filter to remove the alkali in the liquid, wash with a 5% sodium bicarbonate or potassium carbonate solution until it is slightly alkaline, then wash with deionized water until it is neutral, and put it in an oven (95℃) to dry.
[0027] The present invention also protects a flame-retardant polypropylene, comprising, by weight parts: 74.2 to 76.2 parts of homopolymer polypropylene or copolymer polypropylene, 23 to 25 parts of the bromine-antimony compound flame retardant, and 0.8 parts of additives.
[0028] Preferably, the additives include antioxidants, lubricants, and anti-drip agents, with the mass ratio of antioxidants, lubricants, and anti-drip agents being 2:3:3.
[0029] Compared with existing technologies, the advantages of this invention are: by using antimony trichloride to cap organic bromine compounds, this invention synthesizes an organic bromine-antimony compound in which bromine and antimony, a flame retardant additive element, are in the same molecular structure. This bromine-antimony compound exhibits excellent flame retardant properties as a flame retardant. Attached Figure Description
[0030] Figure 1 The TGA curve of the bromine-antimony compound flame retardant obtained in Example 1 is shown. Detailed Implementation
[0031] The present invention will be further described in detail below with reference to the embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are considered to be commercially available through conventional markets. In the following application examples, the anti-dripping agent was purchased from Nanjing Tianshi, L635.
[0032] Example 1
[0033] ;
[0034] In a 500 mL reaction flask, 28.8 g of tetrabromobisphenol A and 110 g of tetrahydrofuran were added. The temperature was adjusted to 40 °C, and 8.6 g of phenylphosphine dichloride was slowly added while stirring. After the addition was complete, the temperature was adjusted to 75 °C, and the reaction was continued. The total reaction time, including the addition time, was 24 hours. After the reaction was completed, the tetrahydrofuran was evaporated to obtain tetrabromobisphenol A phenylphosphine oligomer.
[0035] 33.0 g of the oligomer was dissolved in tetrahydrofuran to obtain a tetrahydrofuran solution with a mass fraction of 30% for the oligomer. 5.4 g of antimony trichloride was dissolved in tetrahydrofuran to prepare a tetrahydrofuran suspension with a mass fraction of 30% for antimony trichloride. This antimony trichloride tetrahydrofuran suspension was added dropwise to the tetrahydrofuran solution of the oligomer, and the reaction was continued at a constant temperature of 60°C for 3 hours to obtain antimony bromide. The alkali in the liquid was removed by filtration, and then washed with a 5% sodium bicarbonate solution until slightly alkaline, followed by washing with deionized water until neutral. The solution was then dried in an oven (95°C) to obtain a pale yellow solid. 1 H NMR (500 MHz, Chloroform-d) δ 7.97-8.02 (m, 7H), 7.93 – 7.87 (m, 2H), 7.67 – 7.60 (m, 5H), 7.60 – 7.56 (m, 6H), 7.56 – 7.52 (m, 3H), 7.51 (d, J = 7.0 Hz, 1H), 7.43 (s,18H), 7.36 (s, 2H), 1.65 (s, 30H). 13C NMR (125 MHz, Chloroform-d) δ 150.63,146.39, 146.35, 145.83, 145.73, 144.97, 132.75, 132.68, 132.53, 132.40,131.27, 130.87, 130.83, 128.61, 128.46, 127.22, 124.99, 117.41, 117.26,113.74, 42.44, 42.39, 30.82. LC-MS[M+H] + =3568.1.
[0036] Thermogravimetric analysis (TGA) of the bromine-antimony compound prepared in Example 1 is shown in [reference needed]. Figure 1 The thermogravimetric analysis (TGA) curves show two distinct stages: thermal stability up to 230°C, followed by significant thermal decomposition and weight loss (approximately 8%) between 230°C and 350°C; and only a 10% weight loss within the 350°C to 450°C range. This TGA analysis indicates that the thermal decomposition temperature of antimony bromine compounds closely matches that of commonly used engineering plastics (300°C to 400°C), suggesting their potential application as flame retardants in these flammable materials.
[0037] Example 2
[0038] ;
[0039] In a 250 mL reaction flask, 31.1 g of tetrabromobisphenol A and 100.0 g of dioxane were added as solvent. The temperature was adjusted to 40 °C, and 9.3 g of phenoxyphosphoryl dichloride was slowly added while stirring. After the addition was complete, the temperature was kept constant at 100 °C and the reaction continued. The total time for the addition and the reaction was 24 hours. The tetrabromobisphenol A oligomer was obtained by evaporation.
[0040] 35.0 g of the oligomer was dissolved in tetrahydrofuran to obtain a 30% tetrahydrofuran solution of the oligomer. 4.0 g of antimony trichloride was dissolved in tetrahydrofuran to prepare a 30% tetrahydrofuran suspension of antimony trichloride. The tetrahydrofuran suspension of antimony trichloride was slowly added dropwise to the tetrahydrofuran solution of the oligomer. After the addition was complete, the reaction was continued at a constant temperature of 60°C for 4 hours to obtain antimony bromide. Excess alkali in the system was removed by filtration. Then, the solution was washed with a 5% potassium carbonate solution until slightly alkaline, followed by washing with deionized water until neutral. The resulting solid was then dried overnight in an oven (95°C) to obtain a pale yellow solid. 1 H NMR (500 MHz, Chloroform- d) δ 7.42 (s, 18H), 7.38 – 7.28 (m, 12H), 7.18-7.24 (m, 15H), 1.65 (s, 30H). 13 C NMR (125 MHz, Chloroform-d)δ 151.75, 150.63, 150.46, 147.54, 146.48, 146.46, 146.32, 145.90, 145.73,131.27, 130.99, 130.97, 129.76, 125.78, 125.74, 120.20, 120.17, 117.33,117.29, 113.74, 42.35, 42.33, 42.30, 30.82. LC-MS[M+H] + =3647.4.
[0041] Example 3
[0042] ;
[0043] In a 250 mL reaction flask, 31.2 g of tetrabromobisphenol S and 100.0 g of dioxane were added as solvent. The temperature was adjusted to 40 °C, and 8.96 g of phenoxyphosphoryl dichloride was slowly added while stirring. After the addition was complete, the temperature was kept constant at 100 °C and the reaction continued. The total time for the addition and the reaction was 24 hours. The tetrabromobisphenol S oligomer was obtained by evaporation.
[0044] 35.0 g of the oligomer was dissolved in tetrahydrofuran to obtain a 30% tetrahydrofuran solution of the oligomer. 4.0 g of antimony trichloride was dissolved in tetrahydrofuran to prepare a 30% tetrahydrofuran solution of the antimony trichloride oligomer. The tetrahydrofuran suspension of antimony trichloride was slowly added dropwise to the tetrahydrofuran solution of the oligomer. After the addition was complete, the reaction was continued at 60°C for 4 hours to obtain antimony bromide. Excess alkali in the system was removed by filtration. Then, the solution was washed with a 5% potassium carbonate solution until slightly alkaline, followed by washing with deionized water until neutral. The resulting solid was then dried overnight in an oven (95°C) to obtain a pale yellow solid. 1 H NMR (500 MHz, Chloroform- d ) δ 8.05-8.09 (m, 18H), 7.97 (s, 2H), 7.35 – 7.28 (m, 10H), 7.18-7.23 (m, 15H). 13C NMR (125 MHz, Chloroform-d) δ 154.90, 151.75, 150.88, 150.46, 149.62, 136.74, 136.53,131.73, 131.70, 131.63, 129.76, 125.78, 125.74, 120.20, 120.17, 120.16,116.34. LC-MS[M+H] + =3757.7.
[0045] Example 4
[0046] ;
[0047] In a 500 mL reaction flask, 71.7 g of tetrabromobisphenol S and 200.0 g of tetrahydrofuran were added. The temperature was adjusted to 40 °C, and 20.61 g of phenylphosphodichlorophosphate was slowly added while stirring. After the addition was complete, the temperature was adjusted to 75 °C, and the reaction continued. The total reaction time, including the addition time, was 24 hours. After the reaction was completed, the solvent was evaporated to dryness. Tetrabromobisphenol S oligomers were obtained.
[0048] 82.0 g of the oligomer was dissolved in tetrahydrofuran to obtain a 30% tetrahydrofuran solution of the oligomer. 8.8 g of antimony trichloride was also dissolved in tetrahydrofuran to prepare a 30% tetrahydrofuran solution of antimony trichloride. The tetrahydrofuran suspension of antimony trichloride was added dropwise to the tetrahydrofuran solution of the oligomer, and the reaction was continued at a constant temperature of 60°C for 3 hours. The liquid was then filtered to remove the alkali, washed with a 5% sodium bicarbonate solution until slightly alkaline, and then washed with deionized water until neutral. The solution was then dried in an oven (95°C) to obtain a pale yellow solid. 1 H NMR (500 MHz, Chloroform- d ) δ 8.06-8.12 (m, 18H), 8.04 – 7.95 (m, 10H), 7.92 – 7.88 (m, 2H), 7.67 –7.60 (m, 5H), 7.60 – 7.48 (m, 10H). 13C NMR (125 MHz, Chloroform-d) δ 154.90,148.89, 148.41, 136.74, 136.50, 132.75, 132.68, 132.53, 132.40, 131.92,131.73, 131.65, 128.61, 128.46, 127.12, 124.90, 120.07, 119.98, 116.34.LC-MS[M+H] + =3677.8.
[0049] Application Example 1
[0050] A flame-retardant polypropylene:
[0051] The amounts (mass fractions) of each material are as follows: homopolymer polypropylene (T03, Maoming Petrochemical) 76.2%, bromine antimony compound prepared in Example 1 23%, antioxidant 1010 0.1%, antioxidant 168 0.1%, lubricant EBS 0.3%, and anti-dripping agent 0.3%.
[0052] The preparation method is as follows:
[0053] ① Weigh the above materials according to the proportion and mix them in a high-speed mixer for 2 minutes;
[0054] ② The mixture from step ① is extruded and granulated using a twin-screw extruder at an extrusion temperature of 180℃;
[0055] ③ The granules extruded in step ② are used to prepare test pieces using an injection molding machine. The injection temperature is 200℃, and the test pieces are 125 mm long, 13.0 mm wide, and 1.6 mm thick.
[0056] Application Example 2
[0057] A flame-retardant polypropylene:
[0058] The amounts (mass fractions) of each material are as follows: homopolymer polypropylene (T03, Maoming Petrochemical) 76.2%, bromine antimony compound prepared in Example 2 23%, antioxidant 1010 0.1%, antioxidant 168 0.1%, lubricant EBS 0.3%, and anti-dripping agent 0.3%.
[0059] The preparation method is as follows:
[0060] ① Weigh the above materials according to the proportion and mix them in a high-speed mixer for 2 minutes;
[0061] ② The mixture from step ① is extruded and granulated using a twin-screw extruder at an extrusion temperature of 180℃;
[0062] ③ The granules extruded in step ② are used to prepare test pieces using an injection molding machine. The injection temperature is 200℃, and the test pieces are 125 mm long, 13.0 mm wide, and 1.6 mm thick.
[0063] Application Example 3
[0064] A flame-retardant polypropylene:
[0065] The amounts (mass fractions) of each material are as follows: homopolymer polypropylene (T03, Maoming Petrochemical) 76.2%, bromine-antimony compound prepared in Example 3 23%, antioxidant 1010 0.1%, antioxidant 168 0.1%, lubricant EBS 0.3%, and anti-dripping agent 0.3%.
[0066] The preparation method is as follows:
[0067] ① Weigh the above materials according to the proportion and mix them in a high-speed mixer for 2 minutes;
[0068] ② The mixture from step ① is extruded and granulated using a twin-screw extruder at an extrusion temperature of 180℃;
[0069] ③ The granules extruded in step ② are used to prepare test pieces using an injection molding machine. The injection temperature is 200℃, and the test pieces are 125 mm long, 13.0 mm wide, and 1.6 mm thick.
[0070] Application Example 4
[0071] A flame-retardant polypropylene:
[0072] The amounts (mass fractions) of each material are as follows: homopolymer polypropylene (T03, Maoming Petrochemical) 76.2%, bromine antimony compound prepared in Example 4 23%, antioxidant 1010 0.1%, antioxidant 168 0.1%, lubricant EBS 0.3%, and anti-dripping agent 0.3%.
[0073] The preparation method is as follows:
[0074] ① Weigh the above materials according to the proportion and mix them in a high-speed mixer for 2 minutes;
[0075] ② The mixture from step ① is extruded and granulated using a twin-screw extruder at an extrusion temperature of 180℃;
[0076] ③ The granules extruded in step ② are used to prepare test pieces using an injection molding machine. The injection temperature is 200℃, and the test pieces are 125 mm long, 13.0 mm wide, and 1.6 mm thick.
[0077] Application Example 5
[0078] A flame-retardant polypropylene:
[0079] The amounts (mass fractions) of each material are as follows: copolymer polypropylene (K8009, Guangzhou Petrochemical) 74.2%, bromine antimony compound prepared in Example 1 25%, antioxidant 1010 0.1%, antioxidant 168 0.1%, lubricant EBS 0.3%, and anti-dripping agent 0.3%.
[0080] The preparation method is as follows:
[0081] ① Weigh the above materials according to the proportion and mix them in a high-speed mixer for 2 minutes;
[0082] ② The mixture from step ① is extruded and granulated using a twin-screw extruder at an extrusion temperature of 180℃;
[0083] ③ The granules extruded in step ② are used to prepare test pieces using an injection molding machine. The injection temperature is 200℃, and the test pieces are 125 mm long, 13.0 mm wide, and 1.6 mm thick.
[0084] Comparative Example 1
[0085] A flame-retardant polypropylene:
[0086] The preparation method of this comparative example is the same as that of application example 1, except that the flame retardant is a mixture of bromine and antimony, including decabromodiphenyl ethane and antimony trioxide, with a mass ratio of 4:1 and an addition amount of 23%.
[0087] Comparative Example 2
[0088] A flame-retardant polypropylene:
[0089] The comparative example is prepared in the same way as application example 5, except that the flame retardant is a mixture of bromine and antimony, including decabromodiphenyl ethane and antimony trioxide, with a mass ratio of 4:1 and an addition amount of 25%.
[0090] The formulation tables for Application Examples 1-5 and Comparative Examples 1-2 are shown in Table 1:
[0091] Table 1
[0092] .
[0093] Flame retardancy tests were conducted on the flame-retardant polypropylene obtained corresponding to Case 1-5 and Comparative Example 1-2. The results are shown in Table 2.
[0094] Table 2
[0095] .
[0096] As can be seen from the table above, this invention synthesizes an organic bromine-antimony compound in which bromine and antimony, the flame retardant additive element, are in the same molecular structure by using antimony trichloride to perform an end-capping reaction on an organic bromine compound. The resulting flame retardant has a good flame retardant effect.
[0097] The above description of the embodiments is only for the purpose of helping to understand the technical solution and core idea of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims
1. A bromine-antimony compound flame retardant, characterized in that, The preparation method of the aforementioned bromine-antimony compound flame retardant includes the following steps: (1) First, add tetrabromobisphenol A to tetrahydrofuran, adjust the temperature to 35℃~45℃, and slowly add phenylphosphodichloride dropwise while stirring. After the phenylphosphodichloride is added, adjust the temperature to 75℃~100℃ and continue the reaction. The total time for the addition of phenylphosphodichloride and the reaction time is 24 hours. After the reaction is completed, evaporate the tetrahydrofuran to obtain the oligomer. The molar ratio of tetrabromobisphenol A to phenylphosphodichloride is 1.2~1.3:1, and the total mass ratio of tetrabromobisphenol A and phenylphosphodichloride to the mass ratio of tetrahydrofuran is 1:2~3. (2) The oligomer obtained in step (1) is dissolved in tetrahydrofuran to obtain a tetrahydrofuran solution of the oligomer. Antimony trichloride is then dissolved in tetrahydrofuran to obtain a tetrahydrofuran suspension of antimony trichloride. The tetrahydrofuran suspension of antimony trichloride is slowly added dropwise to the tetrahydrofuran solution of the oligomer at 55℃~65℃. After the addition is complete, the reaction is continued at a constant temperature for 3~4 hours to obtain antimony bromine salt. The molar ratio of tetrabromobisphenol A to antimony trichloride is 1:0.30~0.
45. (3) The bromoantimony salt is washed, filtered and dried to obtain the bromoantimony compound flame retardant.
2. The bromine-antimony compound flame retardant according to claim 1, characterized in that, The mass fraction of oligomers in the tetrahydrofuran solution of the oligomers mentioned in step (2) is 20% to 50%, and the mass fraction of antimony trichloride in the tetrahydrofuran suspension of antimony trichloride is 20% to 50%.
3. A flame-retardant polypropylene, characterized in that, The product comprises, by mass parts, the following components: 74.2 to 76.2 parts of homopolymer polypropylene or copolymer polypropylene, 23 to 25 parts of the bromine-antimony compound flame retardant as described in claim 1, and 0.8 parts of additives.
4. The flame-retardant polypropylene according to claim 3, characterized in that, The additives include antioxidants, lubricants, and anti-dripping agents, with a mass ratio of 2:3:3.