High-transparency flame-retardant MABS composite material and preparation method thereof
By preparing a manganese ion polyazole cyclotriphosphazene complex and magnesium hydroxide-coated red phosphorus microcapsules and compounding them with MABS resin, a highly transparent flame-retardant MABS material is formed, which solves the problem of insufficient flame retardant performance of MABS material and achieves a balance between high transparency and high fire resistance.
Patent Information
- Application Number
- CN202511075571.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-01
- Publication Date
- 2025-10-17
AI Technical Summary
MABS materials have poor flame retardant properties and pose a fire hazard, which limits their application in fields with high safety requirements for flame retardant properties.
A manganese ion polyazole cyclotriphosphazene complex and magnesium hydroxide-coated red phosphorus microcapsules are prepared, and the microcapsules are stirred and mixed with MABS resin, a compatibilizer, a lubricant and an antioxidant, and then melt-blended and extruded to form a highly transparent flame-retardant MABS composite material.
The flame retardant properties of MABS materials are significantly improved while maintaining high transparency, meeting the requirements of high transparency and high fire resistance.
Smart Images
Figure CN120795518A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of high polymer materials, and particularly relates to a high-transparent flame-retardant MABS composite material and a preparation method thereof. BACKGROUND
[0002] Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) is widely used in the fields of electronic appliances, automotive interiors, medical devices, optical devices, etc. due to its chemical resistance of acrylonitrile, toughness of butadiene, processability of styrene and high transparency of methyl methacrylate. However, MABS has poor flame retardant performance and belongs to flammable material, which has fire hazards in use and is accompanied by melt dripping when burning, thereby limiting its application in the fields with high safety requirements on flame retardant performance.
[0003] Therefore, it is of great significance to develop a high-transparent flame-retardant MABS composite material and a preparation method thereof. SUMMARY
[0004] In order to overcome the above technical problems, the present application aims to provide a high-transparent flame-retardant MABS composite material and a preparation method thereof, which solves the problem of poor flame retardant performance of the existing MABS, fire hazards in use, and limitation of its application in the fields with high safety requirements on flame retardant performance.
[0005] The object of the present application can be achieved by the following technical solutions.
[0006] A high-transparent flame-retardant MABS composite material comprises the following components by weight:
[0007] MABS resin 80-90 parts, manganese ion multi-nitrogen azole ring triphosphazene complex 2-10 parts, magnesium hydroxide coated red phosphorus microcapsule 1.2-3.6 parts, compatibilizer 3-5 parts, lubricant 0.6-1.2 parts and antioxidant 0.2-0.4 parts;
[0008] The manganese ion multi-nitrogen azole ring triphosphazene complex is prepared by the following steps:
[0009] Step s11: 5-amino tetrazole, triethylamine and anhydrous acetonitrile are added into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a reflux condenser, and nitrogen is introduced for protection, and then the reaction is stirred at a temperature of 0-5℃ and a stirring speed of 200-300r / min for 20-30min, and then hexachlorocyclotriphosphazene is added and the reaction is stirred for 20-30min, and then the temperature is increased to 20-25℃ and the reaction is stirred for 1-2h, and then the temperature is increased to reflux and the reaction is stirred for 20-30h, and then the reaction product is cooled to room temperature, and then vacuum filtration is performed, and then the filtrate is rotary evaporated to remove the solvent, and then it is added into ice water and left to precipitate, and then vacuum filtration is performed, and then the filter cake is washed with hydrochloric acid and anhydrous ethanol for 2-3 times, and then it is recrystallized with ethyl acetate, and then it is placed in a vacuum drying box and dried at a temperature of 60-65℃ for 6-7h to obtain a polyazolyl cyclotriphosphazene compound.
[0010] Step s12: the polyazolyl cyclotriphosphazene compound, manganese chloride and deionized water are added into a hydrothermal reactor, and then the reaction is carried out at a temperature of 150-160℃ for 20-30h, and then the reaction product is cooled to room temperature, and then vacuum filtration is performed, and then the filter cake is washed with anhydrous ethanol for 2-3 times, and then it is placed in a vacuum drying box and dried at a temperature of 80-85℃ for 2-3h to obtain a manganese ion polyazolyl cyclotriphosphazene complex.
[0011] As a further scheme of the present application, the amount ratio of the 5-amino tetrazole, triethylamine, anhydrous acetonitrile and hexachlorocyclotriphosphazene in step s11 is 66-72mmol:80-85mmol:70-80mL:10mmol.
[0012] As a further scheme of the present application, the molar concentration of the hydrochloric acid in step s11 is 1-1.5mol / L.
[0013] As a further scheme of the present application, the amount ratio of the polyazolyl cyclotriphosphazene compound, manganese chloride and deionized water in step s12 is 10mmol:0.9-2.5g:120-150mL.
[0014] As a further scheme of the present application, the magnesium hydroxide coated red phosphorus microcapsule is prepared by the following steps:
[0015] Step s21: red phosphorus powder, polyvinylpyrrolidone K85 and deionized water are added to a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and stirred at a temperature of 20-25℃ and a stirring rate of 200-300r / min for 20-30min, then adjusted to pH 8-10 with ammonia water, and then added dropwise magnesium chloride solution while stirring, controlling the dropping rate at 1-3 drops / s, and continued to stir for 3-5h after the addition was completed, the reaction product was vacuum filtered after the reaction was completed, the filter cake was washed with distilled water for 2-3 times, and then placed in a vacuum drying oven and dried at a temperature of 90-95℃ for 2-3h to obtain magnesium hydroxide coated red phosphorus;
[0016] Step s22: magnesium hydroxide coated red phosphorus, ethyl cellulose, emulsifier and anhydrous ethanol are added to a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and stirred at a temperature of 20-25℃ and a stirring rate of 200-300r / min for 10-20min, then heated to 60-65℃ and continued to stir for 30-50min, then cooled to 20-25℃ and added dropwise deionized water while stirring, controlling the dropping rate at 1-3 drops / s, and continued to stir for 20-30min after the addition was completed, the reaction product was vacuum filtered after the reaction was completed, the filter cake was placed in a vacuum drying oven and dried at a temperature of 80-85℃ for 3-4h to obtain magnesium hydroxide coated red phosphorus microcapsules.
[0017] As a further scheme of the present application, the red phosphorus powder, polyvinylpyrrolidone K85, deionized water and magnesium chloride solution in step s21 are 1g: 0.08-0.12g: 20-25mL: 50-60mL.
[0018] As a further scheme of the present application, the average particle size of the red phosphorus powder in step s21 is 200nm; the mass fraction of the ammonia water is 25-27%; and the mass fraction of the magnesium chloride solution is 6-8%.
[0019] As a further scheme of the present application, the amount ratio of the magnesium hydroxide coated red phosphorus, ethyl cellulose, emulsifier, anhydrous ethanol and deionized water in step s22 is 1g: 0.2-0.8g: 0.3-0.5g: 30-40mL: 50-60mL.
[0020] As a further scheme of the present application, the ethyl cellulose in step s22 is ethyl cellulose M70; and the emulsifier is emulsifier OP-10.
[0021] As a further scheme of the present application, a preparation method of a high-transparency flame-retardant MABS composite material comprises the following steps:
[0022] Step one: according to the weight parts, MABS resin 80-90 parts, manganese ion polyazole ring triphosphazene complex 2-10 parts, magnesium hydroxide coated red phosphorus microcapsule 1.2-3.6 parts, compatibilizer 3-5 parts, lubricant 0.6-1.2 parts and antioxidant 0.2-0.4 parts are weighed, ready for use;
[0023] Step two: MABS resin, manganese ion polyazole ring triphosphazene complex, magnesium hydroxide coated red phosphorus microcapsule, compatibilizer, lubricant and antioxidant are added into a high-speed mixer, stirred and mixed at a temperature of 60-80℃ and a stirring rate of 800-1000r / min for 20-30min, then added into a twin-screw extruder, melt blended and extruded at a temperature of 180-220℃ and a screw speed of 100-150r / min, then cooled and granulated to obtain high transparent flame-retardant MABS composite material.
[0024] As a further scheme of the present application, the MABS resin is PA-758.
[0025] As a further scheme of the present application, the compatibilizer is ABS-g-MAH M400A.
[0026] As a further scheme of the present application, the lubricant is zinc stearate.
[0027] As a further scheme of the present application, the antioxidant is antioxidant 1010.
[0028] The beneficial effects of the present application are:
[0029] The high transparent flame-retardant MABS composite material and its preparation method of the present application, by stirring and mixing MABS resin, manganese ion polyazole ring triphosphazene complex, magnesium hydroxide coated red phosphorus microcapsule, compatibilizer, lubricant and antioxidant, then melt blending and extruding, and then cooling and granulating, high transparent flame-retardant MABS composite material is obtained; the preparation method takes MABS resin as the main raw material, MABS resin gives the material high transparency and good mechanical strength, manganese ion polyazole ring triphosphazene complex, magnesium hydroxide coated red phosphorus microcapsule are added, through different flame-retardant mechanisms, reasonable synergistic cooperation can significantly improve the flame-retardant performance of MABS resin, so that the prepared composite material not only maintains high transparency, but also has good flame-retardant performance, so as to ensure that the composite material can meet the requirements of high transparency and high fire resistance at the same time in actual use.
[0030] In the process of preparing high transparent flame-retardant MABS composite material, firstly, a manganese ion polytetrazole cyclotriphosphazene complex is prepared. The polytetrazole cyclotriphosphazene compound containing a large number of cyclic structures, nitrogen elements and phosphorus elements is formed by the reaction between the amino group on 5-amino tetrazole and the chlorine atom on hexachlorocyclotriphosphazene. Then, the complex is formed by self-assembly of the manganese metal ion and the large number of coordination nitrogen atoms on the polytetrazole cyclotriphosphazene compound, and the manganese ion polytetrazole cyclotriphosphazene complex is obtained. The cyclic structure contained in the molecular structure of the manganese ion polytetrazole cyclotriphosphazene complex endows it with excellent thermal stability. The phosphorus element in the molecular structure can be thermally decomposed into phosphoric acid or polyphosphoric acid in the combustion process, which promotes the formation of carbon layer as a dehydrating agent to effectively isolate oxygen. In addition, the phosphorus-containing free radicals generated by thermal decomposition can capture hydrogen radicals and hydroxyl radicals in the combustion process to terminate the chain reaction and inhibit combustion. The nitrogen element in the molecular structure can produce nitrogen-containing gas in the combustion process, which can dilute the concentration of oxygen and combustible gas and reduce the combustion rate. The presence of manganese ions in the molecular structure can catalyze the formation of carbon layer, promote the formation of dense carbon layer on the surface of the polymer, and further isolate the transmission of oxygen and heat to prevent further decomposition and combustion of the polymer, thereby improving the flame-retardant performance of the material.
[0031] In the process of preparing high transparent flame-retardant MABS composite material, a magnesium hydroxide coated red phosphorus microcapsule is also prepared. The magnesium hydroxide coated red phosphorus is obtained by precipitating magnesium hydroxide on the surface of red phosphorus powder as the core. Then, the magnesium hydroxide coated red phosphorus is coated with ethyl cellulose to obtain the magnesium hydroxide coated red phosphorus microcapsule. Red phosphorus can promote the dehydration and carbonization of polymers to form carbon layer by decomposing phosphoric acid and metaphosphoric acid in the combustion process. Magnesium hydroxide can reduce the surface temperature of the material by decomposing and absorbing heat at high temperature, and the released water vapor can dilute the concentration of oxygen and combustible gas. The compatibility of red phosphorus and magnesium hydroxide with the MABS resin matrix can be improved after coating with ethyl cellulose, which can reduce their agglomeration in the matrix and maintain the high transparency of the material. In addition, the coating can prevent the oxidation and moisture absorption of red phosphorus, thereby ensuring the stability and flame-retardant efficiency of the magnesium hydroxide coated red phosphorus microcapsule. BRIEF DESCRIPTION OF DRAWINGS
[0032] The application will be further described below with reference to the accompanying drawings.
[0033] Figure 1 The figure is a schematic diagram of the limiting oxygen index and ignition temperature test results of the high transparent flame-retardant MABS composite material of examples 1-3 and comparative examples 1-4 in the application. DETAILED DESCRIPTION
[0034] With reference to the drawings and the embodiments of the present application, the technical solutions in the embodiments of the present application will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all the other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.
[0035] Embodiment 1
[0036] The embodiment is a preparation method of a high-transparency flame-retardant MABS composite material, including the following steps.
[0037] Step S1: 66 mmol of 5-amino tetrazole, 80 mmol of triethylamine and 70 mL of anhydrous acetonitrile are added into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a reflux condenser, nitrogen is introduced for protection, stirring is carried out at a temperature of 0℃ and a stirring speed of 200 r / min for 20 min, then 10 mmol of hexachlorocyclotriphosphazene is added and stirring is continued for 20 min, then the temperature is increased to 20℃ and stirring is continued for 1 h, then the temperature is increased to reflux and stirring is continued for 20 h, after the reaction is completed, the reaction product is cooled to room temperature, then vacuum filtration is carried out, the filtrate is rotary evaporated to remove the solvent, then it is added into ice water and left to precipitate, then vacuum filtration is carried out, and the filter cake is washed with 1 mol / L hydrochloric acid and anhydrous ethanol for 2 times, then it is recrystallized with ethyl acetate, then it is placed in a vacuum drying box and dried at a temperature of 60℃ for 6 h, to obtain a polytetrazole cyclotriphosphazene compound;
[0038] Step S2: 10 mmol of the polytetrazole cyclotriphosphazene compound, 0.9 g of manganese chloride and 120 mL of deionized water are added into a hydrothermal reaction kettle, and hydrothermal reaction is carried out at a temperature of 150℃ for 20 h, after the reaction is completed, the reaction product is cooled to room temperature, then vacuum filtration is carried out, the filter cake is washed with anhydrous ethanol for 2 times, then it is placed in a vacuum drying box and dried at a temperature of 80℃ for 2 h, to obtain a manganese ion polytetrazole cyclotriphosphazene complex;
[0039] Step S3: 1g of red phosphorus powder with an average particle size of 200nm, 0.08g of polyvinylpyrrolidone K85 and 20mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer and a constant-pressure dropping funnel, and stirred at a temperature of 20℃ and a stirring rate of 200r / min for 20min, then adjusted to pH 8 with 25% ammonia water, and then 50mL of 6% magnesium chloride solution was added dropwise while stirring at a rate of 1 drop / s, and the reaction was continued for 3h after the addition was completed, and then the reaction product was vacuum filtered, the filter cake was washed with distilled water for 2 times, and then placed in a vacuum drying oven and dried at a temperature of 90℃ for 2h to obtain magnesium hydroxide-coated red phosphorus;
[0040] Step S4: 1g of magnesium hydroxide-coated red phosphorus, 0.2g of ethyl cellulose M70, 0.3g of emulsifier OP-10 and 30mL of anhydrous ethanol were added to a three-necked flask equipped with a stirrer, a thermometer and a constant-pressure dropping funnel, and stirred at a temperature of 20℃ and a stirring rate of 200r / min for 10min, then the temperature was raised to 60℃ and the reaction was continued for 30min, then the temperature was lowered to 20℃ and 50mL of deionized water was added dropwise while stirring at a rate of 1 drop / s, and the reaction was continued for 20min after the addition was completed, and then the reaction product was vacuum filtered, the filter cake was placed in a vacuum drying oven and dried at a temperature of 80℃ for 3h to obtain magnesium hydroxide-coated red phosphorus microcapsules;
[0041] Step S5: MABS resin 80 parts, manganese ion multi-nitrogen azole ring trisphosphazene complex 2 parts, magnesium hydroxide-coated red phosphorus microcapsules 1.2 parts, compatibilizer 3 parts, lubricant 0.6 parts and antioxidant 0.2 parts were weighed according to weight parts and prepared for use; the MABS resin is PA-758; the compatibilizer is ABS-g-MAH M400A; the lubricant is zinc stearate; and the antioxidant is antioxidant 1010;
[0042] Step S6: The MABS resin, manganese ion multi-nitrogen azole ring trisphosphazene complex, magnesium hydroxide-coated red phosphorus microcapsules, compatibilizer, lubricant and antioxidant were added to a high-speed mixer and stirred and mixed at a temperature of 60℃ and a stirring rate of 800r / min for 20min, then added to a twin-screw extruder and melt blended and extruded at a temperature of 180℃ and a screw speed of 100r / min, and then cooled and granulated to obtain a high-transparency flame-retardant MABS composite material.
[0043] Example 2:
[0044] The present embodiment is a preparation method of a high-transparency flame-retardant MABS composite material, comprising the following steps:
[0045] Step S1: 69 mmol of 5-amino tetrazole, 82 mmol of triethylamine and 75 mL of anhydrous acetonitrile were added into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a reflux condenser, and protected by nitrogen, and stirred at a temperature of 3 ℃ and a stirring speed of 250 r / min for 25 min, then 10 mmol of hexachlorocyclotriphosphazene was added and stirred for another 25 min, then the temperature was raised to 22 ℃ and the stirring was continued for 1.5 h, then the temperature was raised to reflux and the stirring was continued for 25 h, after the reaction was completed, the reaction product was cooled to room temperature, then vacuum filtration was performed, the filtrate was rotary evaporated to remove the solvent, then it was added into ice water and left to precipitate, then vacuum filtration was performed, and the filter cake was washed with 1.2 mol / L hydrochloric acid and anhydrous ethanol for two times, then recrystallized with ethyl acetate, then placed in a vacuum drying oven and dried at a temperature of 62 ℃ for 6.5 h to obtain a polyazolyl cyclotriphosphazene compound;
[0046] Step S2: 10 mmol of the polyazolyl cyclotriphosphazene compound, 1.7 g of manganese chloride and 135 mL of deionized water were added into a hydrothermal reactor, and hydrothermal reaction was carried out at a temperature of 155 ℃ for 25 h, after the reaction was completed, the reaction product was cooled to room temperature, then vacuum filtration was performed, the filter cake was washed with anhydrous ethanol for two times, then placed in a vacuum drying oven and dried at a temperature of 82 ℃ for 2.5 h to obtain a manganese ion polyazolyl cyclotriphosphazene complex;
[0047] Step S3: 1 g of red phosphorus powder with an average particle size of 200 nm, 0.1 g of polyvinylpyrrolidone K85 and 22 mL of deionized water were added into a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and stirred at a temperature of 22 ℃ and a stirring speed of 250 r / min for 25 min, then adjusted to pH 9 with 26% ammonia water, then 55 mL of 7% magnesium chloride solution was added dropwise while stirring, and the dropping rate was controlled at 2 drops / s, after the addition was completed, the stirring was continued for 4 h, after the reaction was completed, the reaction product was vacuum filtered, the filter cake was washed with distilled water for two times, then placed in a vacuum drying oven and dried at a temperature of 92 ℃ for 2.5 h to obtain magnesium hydroxide coated red phosphorus;
[0048] Step S4: 1 g of magnesium hydroxide coated red phosphorus, 0.5 g of ethyl cellulose M70, 0.4 g of emulsifier OP-10, and 35 mL of anhydrous ethanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel, and stirred at a temperature of 22°C and a stirring rate of 250 r / min for 15 min, then heated to 62°C and continued to stir for 40 min, then cooled to 22°C and added 55 mL of deionized water drop by drop while stirring, controlling the dropping rate to be 2 drops / s, and continued to stir for 25 min after the addition was completed. After the reaction was completed, the reaction product was vacuum filtered, the filter cake was placed in a vacuum drying oven, and dried at a temperature of 82°C for 3.5 h to obtain magnesium hydroxide coated red phosphorus microcapsules;
[0049] Step S5: MABS resin 85 parts, manganese ion polyazole ring triphosphazene complex 6 parts, magnesium hydroxide coated red phosphorus microcapsules 2.4 parts, compatibilizer 4 parts, lubricant 0.9 parts, and antioxidant 0.3 parts were weighed according to the weight parts, and were ready for use; the MABS resin is PA-758; the compatibilizer is ABS-g-MAH M400A; the lubricant is zinc stearate; and the antioxidant is antioxidant 1010;
[0050] Step S6: The MABS resin, manganese ion polyazole ring triphosphazene complex, magnesium hydroxide coated red phosphorus microcapsules, compatibilizer, lubricant, and antioxidant were added to a high-speed mixer and stirred and mixed at a temperature of 70°C and a stirring rate of 900 r / min for 25 min, then added to a twin-screw extruder and melt blended and extruded at a temperature of 200°C and a screw speed of 130 r / min, then cooled and granulated to obtain a high-transparency flame-retardant MABS composite material.
[0051] Example 3:
[0052] The present embodiment is a preparation method of a high-transparency flame-retardant MABS composite material, comprising the following steps:
[0053] Step S1: 72 mmol of 5-amino tetrazole, 85 mmol of triethylamine and 80 mL of anhydrous acetonitrile were added into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a reflux condenser, protected by nitrogen, stirred at a temperature of 5 ℃ and a stirring rate of 300 r / min for 30 min, then 10 mmol of hexachlorocyclotriphosphazene was added and stirred for another 30 min, then the temperature was raised to 25 ℃ and the reaction was continued for 2 h, then the temperature was raised to reflux and the reaction was continued for 30 h. After the reaction was completed, the reaction product was cooled to room temperature, then vacuum filtered, the filtrate was rotary evaporated to remove the solvent, then added to ice water and left to precipitate, then vacuum filtered, and the filter cake was washed with 1.5 mol / L hydrochloric acid, anhydrous ethanol three times, then recrystallized with ethyl acetate, then placed in a vacuum drying oven and dried at a temperature of 65 ℃ for 7 h to obtain a polyazolyl cyclotriphosphazene compound;
[0054] Step S2: 10 mmol of polyazolyl cyclotriphosphazene compound, 2.5 g of manganese chloride and 150 mL of deionized water were added into a hydrothermal reactor, and hydrothermal reaction was carried out at a temperature of 160 ℃ for 30 h. After the reaction was completed, the reaction product was cooled to room temperature, then vacuum filtered, the filter cake was washed with anhydrous ethanol three times, then placed in a vacuum drying oven and dried at a temperature of 85 ℃ for 3 h to obtain a manganese ion polyazolyl cyclotriphosphazene complex;
[0055] Step S3: 1 g of red phosphorus powder with an average particle size of 200 nm, 0.12 g of polyvinylpyrrolidone K85 and 25 mL of deionized water were added into a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and stirred at a temperature of 25 ℃ and a stirring rate of 300 r / min for 30 min. Then the pH was adjusted to 10 with 27% ammonia water, then 60 mL of 8% magnesium chloride solution was added dropwise while stirring, and the dropping rate was controlled at 3 drops / s. After the addition was completed, the reaction was continued for 5 h. After the reaction was completed, the reaction product was vacuum filtered, the filter cake was washed with distilled water three times, then placed in a vacuum drying oven and dried at a temperature of 95 ℃ for 3 h to obtain magnesium hydroxide coated red phosphorus;
[0056] Step S4: 1 g of magnesium hydroxide coated red phosphorus, 0.8 g of ethyl cellulose M70, 0.5 g of emulsifier OP-10, and 40 mL of anhydrous ethanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel, and stirred at a temperature of 25°C and a stirring rate of 300 r / min for 20 min, then the temperature was raised to 65°C and the stirring was continued for 50 min, then the temperature was lowered to 25°C and 60 mL of deionized water was added dropwise while stirring, the dropping rate was controlled at 3 drops / s, after the addition was completed, the reaction was continued for 30 min, and then the reaction product was vacuum filtered, the filter cake was placed in a vacuum drying oven and dried at a temperature of 85°C for 4 h to obtain magnesium hydroxide coated red phosphorus microcapsules;
[0057] Step S5: MABS resin 90 parts, manganese ion multi-nitrogen heterocyclic ring trisphosphazene complex 10 parts, magnesium hydroxide coated red phosphorus microcapsules 3.6 parts, compatibilizer 5 parts, lubricant 1.2 parts, and antioxidant 0.4 parts were weighed according to the weight parts, and were ready for use; the MABS resin was PA-758; the compatibilizer was ABS-g-MAH M400A; the lubricant was zinc stearate; and the antioxidant was antioxidant 1010;
[0058] Step S6: The MABS resin, manganese ion multi-nitrogen heterocyclic ring trisphosphazene complex, magnesium hydroxide coated red phosphorus microcapsules, compatibilizer, lubricant, and antioxidant were added to a high-speed mixer and stirred and mixed at a temperature of 80°C and a stirring rate of 1000 r / min for 30 min, then were added to a twin-screw extruder and melt blended and extruded at a temperature of 220°C and a screw speed of 150 r / min, then were cooled and granulated to obtain a high-transparency flame-retardant MABS composite material.
[0059] Comparative Example 1
[0060] This comparative example is a method for preparing a high-transparency flame-retardant MABS composite material, comprising the following steps:
[0061] Step S1: MABS resin 90 parts, compatibilizer 5 parts, lubricant 1.2 parts, and antioxidant 0.4 parts were weighed according to the weight parts, and were ready for use; the MABS resin was PA-758; the compatibilizer was ABS-g-MAH M400A; the lubricant was zinc stearate; and the antioxidant was antioxidant 1010;
[0062] Step S2: the MABS resin, the compatibilizer, the lubricant and the antioxidant were added into a high-speed mixer, stirred and mixed at a temperature of 80°C and a stirring speed of 1000 r / min for 30 min, and then added into a twin-screw extruder for melt blending and extrusion at a temperature of 220°C and a screw speed of 150 r / min, and then cooled and granulated to obtain the high-transparent flame-retardant MABS composite material.
[0063] Comparative Example 2
[0064] The present comparative example is a preparation method of a high-transparent flame-retardant MABS composite material, comprising the following steps:
[0065] Step S1: 72 mmol of 5-amino tetrazole, 85 mmol of triethylamine and 80 mL of anhydrous acetonitrile were added into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube and a reflux condenser, protected by nitrogen, stirred at a temperature of 5°C and a stirring speed of 300 r / min for 30 min, and then 10 mmol of hexachlorocyclotriphosphazene was added for continuous stirring for 30 min, and then the temperature was increased to 25°C for continuous stirring for 2 h, and then the temperature was increased to reflux for continuous stirring for 30 h, and then the reaction product was cooled to room temperature, and then vacuum filtration was performed, the filtrate was rotary evaporated to remove the solvent, and then added into ice water for standing and precipitating, and then vacuum filtration was performed, and the filter cake was washed with 1.5 mol / L hydrochloric acid, anhydrous ethanol and ethyl acetate for 3 times, and then recrystallized from ethyl acetate, and then placed in a vacuum drying oven for drying at a temperature of 65°C for 7 h to obtain a polyazolyl cyclotriphosphazene compound;
[0066] Step S2: 10 mmol of the polyazolyl cyclotriphosphazene compound, 2.5 g of manganese chloride and 150 mL of deionized water were added into a hydrothermal reaction kettle for hydrothermal reaction at a temperature of 160°C for 30 h, and then the reaction product was cooled to room temperature, and then vacuum filtration was performed, the filter cake was washed with anhydrous ethanol for 3 times, and then placed in a vacuum drying oven for drying at a temperature of 85°C for 3 h to obtain a manganese ion polyazolyl cyclotriphosphazene complex;
[0067] Step S3: MABS resin 90 parts, manganese ion polyazolyl cyclotriphosphazene complex 10 parts, compatibilizer 5 parts, lubricant 1.2 parts and antioxidant 0.4 parts were weighed according to weight parts for standby; the MABS resin was PA-758; the compatibilizer was ABS-g-MAH M400A; the lubricant was zinc stearate; and the antioxidant was antioxidant 1010;
[0068] Step S4: the MABS resin, manganese ion polyazole ring trisphosphazene complex, compatibilizer, lubricant and antioxidant were added into a high-speed mixer, stirred and mixed at a temperature of 80°C and a stirring speed of 1000 r / min for 30 min, and then added into a twin-screw extruder for melt blending and extrusion at a temperature of 220°C and a screw speed of 150 r / min, and then cooled and granulated to obtain a high-transparency flame-retardant MABS composite material.
[0069] Comparative Example 3
[0070] The present comparative example is a preparation method of a high-transparency flame-retardant MABS composite material, comprising the following steps:
[0071] Step S1: 1 g of red phosphorus powder with an average particle size of 200 nm, 0.12 g of polyvinylpyrrolidone K85 and 25 mL of deionized water were added into a three-necked flask equipped with a stirrer, a thermometer and a constant-pressure dropping funnel, and stirred at a temperature of 25°C and a stirring speed of 300 r / min for 30 min, and then adjusted to pH 10 with 27% ammonia water, and then 60 mL of 8% magnesium chloride solution was added dropwise while stirring, the dropping speed was controlled at 3 drops / s, and after the addition was completed, the reaction was continued for 5 h, and after the reaction was completed, the reaction product was vacuum filtered, the filter cake was washed with distilled water for 3 times, and then placed in a vacuum drying oven and dried at a temperature of 95°C for 3 h to obtain magnesium hydroxide-coated red phosphorus;
[0072] Step S2: 1 g of magnesium hydroxide-coated red phosphorus, 0.8 g of ethyl cellulose M70, 0.5 g of emulsifier OP-10 and 40 mL of anhydrous ethanol were added into a three-necked flask equipped with a stirrer, a thermometer and a constant-pressure dropping funnel, and stirred at a temperature of 25°C and a stirring speed of 300 r / min for 20 min, and then the temperature was increased to 65°C and the stirring was continued for 50 min, and then the temperature was decreased to 25°C and 60 mL of deionized water was added dropwise while stirring, the dropping speed was controlled at 3 drops / s, and after the addition was completed, the reaction was continued for 30 min, and after the reaction was completed, the reaction product was vacuum filtered, the filter cake was placed in a vacuum drying oven and dried at a temperature of 85°C for 4 h to obtain magnesium hydroxide-coated red phosphorus microcapsules;
[0073] Step S3: MABS resin 90 parts, magnesium hydroxide-coated red phosphorus microcapsules 3.6 parts, compatibilizer 5 parts, lubricant 1.2 parts and antioxidant 0.4 parts were weighed according to the weight parts, and prepared for use; the MABS resin was PA-758; the compatibilizer was ABS-g-MAHM400A; the lubricant was zinc stearate; and the antioxidant was antioxidant 1010;
[0074] Step S4: the MABS resin, magnesium hydroxide coated red phosphorus microcapsules, compatibilizer, lubricant and antioxidant were added into a high-speed mixer and stirred and mixed at a temperature of 80°C and a stirring rate of 1000 r / min for 30 min, and then added into a twin-screw extruder for melt blending and extrusion at a temperature of 220°C and a screw rotation speed of 150 r / min, and then cooled and granulated to obtain a high-transparency flame-retardant MABS composite material.
[0075] Comparative Example 4:
[0076] The present comparative example is a preparation method of a high-transparency flame-retardant MABS composite material, comprising the following steps:
[0077] Step S1: MABS resin 90 parts, hexachlorocyclotriphosphazene 10 parts, magnesium hydroxide with an average particle size of 30 nm 3.6 parts, compatibilizer 5 parts, lubricant 1.2 parts and antioxidant 0.4 parts were weighed according to the weight parts, and prepared for use; the MABS resin is PA-758; the compatibilizer is ABS-g-MAH M400A; the lubricant is zinc stearate; and the antioxidant is antioxidant 1010;
[0078] Step S2: the MABS resin, hexachlorocyclotriphosphazene, magnesium hydroxide with an average particle size of 30 nm, compatibilizer, lubricant and antioxidant were added into a high-speed mixer and stirred and mixed at a temperature of 80°C and a stirring rate of 1000 r / min for 30 min, and then added into a twin-screw extruder for melt blending and extrusion at a temperature of 220°C and a screw rotation speed of 150 r / min, and then cooled and granulated to obtain a high-transparency flame-retardant MABS composite material.
[0079] Performance test
[0080] The high-transparency flame-retardant MABS composite materials of Examples 1-3 and Comparative Examples 1-4 were tested for limiting oxygen index according to GB / T2406.2-2009 and for glow wire ignition temperature according to IEC 60695-2-12, and the test results are shown in Table 1. Figure 1
[0081] Referring to Figure 1 As shown in Table 1, according to the comparison between Examples 1-3 and Comparative Examples 1-4, it can be seen that the addition of manganese ion polyazole ring cyclotriphosphazene complex and magnesium hydroxide coated red phosphorus microcapsules can significantly increase the limiting oxygen index and the glow wire ignition temperature, indicating that the flame-retardant properties of the composite material can be significantly improved, and the composite material of the present application has excellent flame-retardant properties.
[0082] The high transparent flame-retardant MABS composite materials of Examples 1-3 and Comparative Examples 1-4 were tested for UL-94 combustion grade according to GB / T2408-2021, and the test results are shown in the following table.
[0083] Sample UL-94 burn rating Presence or absence of dripping Example 1 V-0 No Example 2 V-0 No Example 3 V-0 No Comparative Example 1 NR Yes Comparative Example 2 V-1 No Comparative Example 3 V-1 No Comparative Example 4 V-0 No
[0084] Referring to the data shown in the above table, according to the comparison between Examples 1-3 and Comparative Examples 1-4, it can be seen that the addition of manganese ion polyazole ring triphosphazene complex and magnesium hydroxide coated red phosphorus microcapsules makes the UL-94 combustion grade of the composite material of the present application excellent, and there is no dripping phenomenon, further indicating that the composite material has excellent flame-retardant performance.
[0085] In the description of the present specification, the description referring to the terms "one embodiment", "an example", "a specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
[0086] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the invention or exceed the scope defined in the present application, which shall belong to the protection scope of the present application.
Claims
1. A highly transparent flame-retardant MABS composite material, characterized in that: It comprises the following components in parts by weight: 80-90 parts of MABS resin, 2-10 parts of manganese ion polyazole cyclotriphosphazene complex, 1.2-3.6 parts of magnesium hydroxide coated red phosphorus microcapsules, 3-5 parts of compatibilizer, 0.6-1.2 parts of lubricant and 0.2-0.4 parts of antioxidant; Wherein, the manganese ion polyazole cyclotriphosphazene complex is prepared by the following steps: Step s11: stirring 5-aminotetrazole, triethylamine, and anhydrous acetonitrile to react, then adding hexachlorocyclotriphosphazene and continuing stirring to react. After the reaction is completed, the reaction product is cooled, then vacuum filtered, the filtrate is rotary evaporated, then added to ice water and allowed to stand to precipitate, then vacuum filtered, the filter cake is washed, recrystallized, and dried to obtain a polyazole cyclotriphosphazene compound; Step s12: hydrothermally reacting a polyazole cyclotriphosphazene compound, manganese chloride and deionized water. After the reaction is completed, the reaction product is cooled and then vacuum filtered. The filter cake is washed and dried to obtain a manganese ion polyazole cyclotriphosphazene complex.
2. The highly transparent flame-retardant MABS composite material according to claim 1, characterized in that: The usage ratio of the 5-aminotetrazole, triethylamine, anhydrous acetonitrile and hexachlorocyclotriphosphazene in step s11 is 66-72 mmol:80-85 mmol:70-80 mL:10 mmol.
3. The highly transparent flame-retardant MABS composite material according to claim 1, characterized in that: The usage ratio of the polyazole cyclotriphosphazene compound, manganese chloride and deionized water in step s12 is 10 mmol: 0.9-2.5 g: 120-150 mL.
4. The highly transparent flame-retardant MABS composite material according to claim 1, characterized in that: The magnesium hydroxide-coated red phosphorus microcapsules are prepared by the following steps: Step s21: stirring red phosphorus powder, polyvinyl pyrrolidone K85 and deionized water to react, then adjusting the pH with ammonia water, then dropwise adding magnesium chloride solution and continuing stirring to react. After the reaction is completed, vacuum filtering the reaction product, washing the filter cake, and drying to obtain magnesium hydroxide-coated red phosphorus; Step s22: magnesium hydroxide-coated red phosphorus, ethyl cellulose, an emulsifier and anhydrous ethanol are stirred and reacted, and then deionized water is added dropwise and the stirring reaction is continued. After the reaction is completed, the reaction product is vacuum filtered and the filter cake is dried to obtain magnesium hydroxide-coated red phosphorus microcapsules.
5. The highly transparent flame-retardant MABS composite material according to claim 4, characterized in that: The red phosphorus powder, polyvinyl pyrrolidone K85, deionized water and magnesium chloride solution in step s21 are 1g:0.08-0.12g:20-25mL:50-60mL; the average particle size of the red phosphorus powder is 200nm; the mass fraction of the ammonia water is 25-27%; and the mass fraction of the magnesium chloride solution is 6-8%.
6. The highly transparent flame-retardant MABS composite material according to claim 4, characterized in that: In step s22, the dosage ratio of the magnesium hydroxide-coated red phosphorus, ethyl cellulose, emulsifier, anhydrous ethanol and deionized water is 1g:0.2-0.8g:0.3-0.5g:30-40mL:50-60mL; the ethyl cellulose is ethyl cellulose M70; and the emulsifier is emulsifier OP-10.
7. A method for preparing a highly transparent flame-retardant MABS composite material, characterized in that: The following steps are involved: Step 1: Weigh 80-90 parts of MABS resin, 2-10 parts of manganese ion polyazole cyclotriphosphazene complex, 1.2-3.6 parts of magnesium hydroxide-coated red phosphorus microcapsules, 3-5 parts of compatibilizer, 0.6-1.2 parts of lubricant and 0.2-0.4 parts of antioxidant according to weight parts, and set aside; Step 2: Add MABS resin, manganese ion polyazole cyclotriphosphazene complex, magnesium hydroxide-coated red phosphorus microcapsules, compatibilizer, lubricant and antioxidant into a high-speed mixer, stir and mix for 20-30 minutes at a temperature of 60-80° C. and a stirring rate of 800-1000 r / min, then add into a twin-screw extruder, melt-blend and extrude at a temperature of 180-220° C. and a screw speed of 100-150 r / min, and then cool and granulate to obtain a highly transparent flame-retardant MABS composite material.
8. The method for preparing a highly transparent flame-retardant MABS composite material according to claim 7, characterized in that: The MABS resin is PA-758.
9. The method for preparing a highly transparent flame-retardant MABS composite material according to claim 7, characterized in that: The compatibilizer is ABS-g-MAH M400A; The lubricant is zinc stearate; The antioxidant is antioxidant 1010.