Synergistic flame retardant-reinforced integrated antimony trioxide substitute flame retardant and preparation method thereof

Abstract

The invention provides a synergistic flame retardant-reinforced integrated antimony trioxide substitute flame retardant and a preparation method thereof, and belongs to the technical field of flame retardants. The preparation method comprises the steps of preparing a nickel-iron compound, preparing functional composite powder and mixing. The step of preparing the nickel-iron compound comprises the following steps: heating deionized water to 60-65 DEG C, adding nickel nitrate and ferric nitrate, uniformly stirring, adding a cerium nitrate solution and citric acid, stirring for 30-35 minutes, adding ethylene glycol and a kH560 coupling agent solution, stirring for 1.5-2.0 hours, standing, aging, drying, keeping the temperature at 320-350 DEG C for 1.0-1.2 hours, and keeping the temperature at 620-630 DEG C for 3.5-4.0 hours to obtain the nickel-iron compound; the antimony trioxide substituted flame retardant disclosed by the invention can completely and equivalently replace antimony trioxide in the field, and is high in flame retardant property, mechanical property and stability.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of flame retardants, and particularly relates to a synergistic flame-retardant-reinforced integrated diantimony trioxide substitute flame retardant and a preparation method thereof. BACKGROUND

[0002] In the prior art, the preparation of flame retardants mainly includes bromine-antimony flame retardants and halogen-free (phosphorus-nitrogen) flame retardants. Compared with mature bromine-antimony flame retardants, halogen-free flame retardants have obvious advantages in environmental protection and biological safety, but indeed have some challenges or disadvantages in technical performance and application. The flame-retardant efficiency of halogen-free flame retardants is low, and a large amount of additives will seriously affect the performance of the base material. A large amount of flame retardants filled into polymers will seriously damage the structure and interaction of the high molecular chain, resulting in a significant decrease in the mechanical properties such as tensile strength, impact toughness, and elongation at break of the material, and the material will become brittle and hard, and the reliability of processing and use is reduced. In addition, halogen-free flame retardants have higher requirements for processing technology. The processing temperature of materials such as nylon is high, and most phosphorus-nitrogen flame retardants decompose at the processing temperature, which may also affect the electrical insulation, transparency, weather resistance, and compatibility of the material.

[0003] Therefore, bromine-antimony flame retardants are the most commonly used flame retardant system in the prior art.

[0004] Diantimony trioxide (Sb2O3) is a white crystalline powder, which is widely used in the flame-retardant modification of plastics, rubbers, textiles and other materials as a high-efficiency flame-retardant synergist, and is widely used in the plastic, electronic and electrical, building material, and automobile parts industries.

[0005] At present, although the bromine-antimony flame-retardant system plays an irreplaceable role in the field of flame retardants, it also has non-negligible hazards in safety and environmental protection. Some bromine-based flame retardants produce toxic smoke when burning, and antimony is also considered to have potential biological toxicity. In addition, due to the current instability of antimony price, environmental protection restrictions, import and export controls, and the like, the use cost of the bromine-antimony flame-retardant system has increased significantly. In the flame-retardant modification of materials, the addition of flame retardants will lead to a decrease in the mechanical properties of the materials.

[0006] Therefore, these disputes have prompted the flame retardant industry to continuously improve the bromine-antimony flame-retardant system, develop more environmentally friendly bromine-antimony flame retardants, reduce the amount of diantimony trioxide while reducing the impact on the environment and health, and ensure the mechanical properties of the materials.

[0007] The improvement methods of the prior art for bromine-antimony flame retardants mainly include the following: 1. Develop new bromine flame retardant; replace harmful traditional varieties (polybrominated diphenyl ether, hexabromocyclododecane, etc.) with high molecular weight / polymer type bromine flame retardant, but the synthesis process of new high molecular weight / polymer flame retardant is complex, the cost is high, and the compatibility with the matrix material will be poor, which will have a negative impact on the processing fluidity and mechanical properties of the material; 2. Find a substitute for antimony; replace antimony with phosphorus, nitrogen, metal compounds, etc., but usually the synergistic efficiency will be lower than that of antimony, and the appearance of the material will be affected; 3. Microencapsulation / coating technology; this is a physical-chemical method aimed at "wrapping" bromine-antimony flame retardant to isolate it from direct contact with the external environment; but this method will significantly increase the cost and affect the flame retardant efficiency, and the technology is complex (uniformity, integrity and coating rate of coating are technical difficulties).

[0008] It can be seen that the improved bromine-antimony flame retardant prepared by the prior art cannot meet the requirements of "reducing the amount of antimony trioxide, reducing the cost and being environmentally friendly while ensuring the flame retardant performance of the material and enhancing the mechanical properties". SUMMARY

[0009] In order to solve the technical problems existing in the prior art, the present application provides a synergistic flame-retardant-reinforced integrated antimony trioxide replacement flame retardant and a preparation method thereof, which can effectively reduce the amount of antimony trioxide, reduce the cost, and have environmental friendliness. The flame retardant can completely replace antimony trioxide in equal amount in the field of polyolefin plastics and engineering plastics, not only has excellent flame retardant grade and limiting oxygen index, but also can enhance the mechanical properties of the material.

[0010] In view of the above technical problems, the present application adopts the following technical solutions: A preparation method of a synergistic flame-retardant-reinforced integrated antimony trioxide replacement flame retardant, comprising the steps of preparing a nickel-iron composite, preparing a functionalized composite powder and mixing, the specific operation being as follows: 1. Preparation of nickel-iron composite The deionized water is raised to 60-65℃, and then nickel nitrate is added, stirred at 240-270 rpm for 20-30 min, then iron nitrate is added, and stirred for another 30-35 min, then cerium nitrate solution is added, stirred uniformly, then citric acid is added, stirred at 310-330 rpm for 30-35 min, then ethylene glycol is added at a rate of 0.1-0.2 g / min, after the addition is completed, kH560 coupling agent solution is added at a rate of 0.5-0.6 g / min, and then stirred for another 1.5-2.0 h, and then aged at 80-82℃ for 10-12 h, and then dried at 100-110℃ for 20-24 h, then the temperature is raised to 320-350℃ at a rate of 2.0-2.5℃ / min, and then held for 1.0-1.2 h, then the temperature is raised to 620-630℃ at a rate of 1.5-2.0℃ / min, and then held for 3.5-4.0 h, and then naturally cooled to room temperature, to obtain a nickel-iron composite; The cerium nitrate solution is prepared by uniformly mixing 0.40-0.45 g of cerium nitrate with 5 g of deionized water; The kH560 coupling agent solution is prepared by uniformly mixing 0.5-0.6 g of kH560 silane coupling agent with 5 g of anhydrous ethanol; The mass ratio of the deionized water, nickel nitrate, iron nitrate, cerium nitrate solution, citric acid, ethylene glycol, and kH560 coupling agent solution is 50:2.90-2.95:7.20-7.30:5.40-5.45:6.8-7.3:2.0-2.2:5.5-5.6.

[0011] 2. Preparation of functionalized composite powder To 100 g of anhydrous ethanol, 3.5-4.0 g of γ-aminopropyl triethoxysilane and 3.0-3.2 g of phytic acid solution are added, and then stirred uniformly, and then 5-8 wt% acetic acid solution is added to adjust the pH to 4.5-5.0, to obtain a functionalized solution; The mass ratio of the anhydrous ethanol, γ-aminopropyl triethoxysilane and phytic acid solution is 100:3.5-4.0:3.0-3.2; The mass concentration of the phytic acid solution is 50-55%; The talc, dolomite, barium sulfate and cerium oxide are added to a high-speed mixer, and the rotation speed is controlled at 750-800 rpm, and then high-speed mixed for 25-35 min, and then added to the functionalized solution, and then the temperature is raised to 63-67℃ at a rate of 1.0-1.5℃ / min, and then held for 2.0-2.5 h, and then filtered, washed and dried, to obtain a functionalized composite powder; The mass ratio of the talc, dolomite, barium sulfate, cerium oxide and functionalized solution is 30-35:12-18:22-26:4-6:350-400; The particle size of the talc powder is 1.0-2.0 microns; The particle size of the dolomite is 1.2-1.5 microns; The particle size of the barium sulfate is 1.5-2.0 microns; The particle size of the cerium oxide is 90-100 nanometers.

[0012] 3. Mixing The functional composite powder is added to the ethanol solution, after stirring uniformly, the nickel-iron compound is added, the temperature is raised to 40-42 DEG C, stirring at 200-220 rpm for 25-35 min, then the temperature is raised to 60-63 DEG C at a rate of 1.0-1.2 DEG C / min, and the temperature is kept for 1.5-2.0 h, after filtration, washing and drying, the intermediate is obtained; the antimony trioxide and zinc oxide are added to the ethanol solution, after stirring uniformly, the intermediate is added, ultrasonic dispersion is carried out, the ultrasonic time is 40-45 min, the ultrasonic power is 150-160 W, the ultrasonic frequency is 38-45 kHz, after ultrasonic, filtration, washing and drying, the antimony trioxide substitution flame retardant is obtained; The mass ratio of the ethanol solution, the functional composite powder and the nickel-iron compound is 220-250:25-30:12-15; The mass ratio of the ethanol solution, the antimony trioxide, the zinc oxide and the intermediate is 300-350:32-36:6-8:30-35; The mass concentration of the ethanol solution is 55-60%; The particle size of the antimony trioxide is 200-250 nanometers; The particle size of the zinc oxide is 60-80 nanometers.

[0013] A synergistic flame-retardant-reinforced integrated antimony trioxide substitution flame retardant is prepared by the preparation method.

[0014] Compared with the prior art, the present application has the following beneficial effects: 1. The present application first prepares a nickel-iron composite, specifically using nickel nitrate and iron nitrate as metal sources, which can form a dense carbon layer during polymer combustion, enhancing the flame retardant performance, then using cerium nitrate as a rare earth element additive, citric acid as a complexing agent, which helps to ensure that the composite particles are more uniform, treated with kH560 silane coupling agent, the epoxy groups in it participate in the formation of the gel network, which can enhance the stability of the nickel-iron composite, at the same time can improve the combination with functional composite powder, also can enhance the interfacial compatibility with the polymer matrix; in the preparation of functional composite powder step, cerium oxide is a flame retardant synergist and anti-aging functional body, which has excellent catalytic activity, which is compounded with talc, dolomite, barium sulfate, effectively transmits stress, greatly improves the strength performance of the composite material, which has good flame retardant and smoke suppression and enhancement, after functional solution treatment, the amino group of gamma-aminopropyl triethoxysilane can enhance the interfacial bonding force, phytic acid can enhance the flame retardant performance, and phytic acid can be combined with the amino group, so that the phytic acid and the powder are firmly combined, also provides an anchoring site for the combination of the nickel-iron composite; in the mixing step, the epoxy groups of the nickel-iron composite are combined with the amino groups of the functional composite, compounded with antimony trioxide, combined with zinc oxide components, which can promote the formation of a stable carbon layer in the early stage of polymer matrix combustion, reduce the release of flammable volatile matter, at the same time synergize with components such as antimony trioxide, thereby reducing the amount of antimony trioxide while improving the flame retardant performance of the flame retardant, enhancing the compatibility and combination with the polymer matrix, enhancing the flame retardant performance while ensuring the mechanical properties; 2. The prepared antimony trioxide substitute flame retardant is applied in PP, and the obtained PP flame-retardant composite material has a flame-retardant grade of V-0, an ultimate oxygen index of 30.28-32.56%, a cantilever beam impact strength of 8.16-8.37 kJ / m 2 , a tensile strength of 37.95-38.79 MPa, an elongation at break of 46.34-47.02%, and a bending strength of 48.52-50.65 MPa; After 20 cycles of high-low temperature treatment, the cantilever beam impact strength of the PP flame-retardant composite material is 7.78-8.09 kJ / m 2 , the tensile strength is 36.05-37.32 MPa, the elongation at break is 44.07-45.05%, and the bending strength is 46.48-48.83 MPa; 3. The prepared antimony trioxide substitute flame retardant is applied in ABS, and the obtained ABS flame-retardant composite material has a flame-retardant grade of V-0, an ultimate oxygen index of 33.48-34.04%, a cantilever beam impact strength of 14.21-14.75 kJ / m 2 , a tensile strength of 56.13-56.71 MPa, an elongation at break of 11.48-12.05%, and a bending strength of 82.15-83.26 MPa; The cantilever beam impact strength of the ABS flame-retardant composite after 20 cycles of high and low temperature treatment is 13.64-14.32 kJ / m 2 , the tensile strength is 53.38-54.73 MPa, the elongation at break is 10.87-11.60%, and the bending strength is 78.54-80.51 MPa. DETAILED DESCRIPTION

[0015] In order to more clearly understand the technical features, objectives and effects of the present application, the specific embodiments of the present application will now be described.

[0016] Example 1 1. Preparation of nickel-iron composite 50 g of deionized water was heated to 65℃, 2.95 g of nickel nitrate was added, stirred at 270 rpm for 30 min, then 7.30 g of iron nitrate was added, and the stirring was continued for 35 min, then 5.45 g of cerium nitrate solution was added, stirred uniformly, then 7.3 g of citric acid was added, stirred at 330 rpm for 35 min, 2.2 g of ethylene glycol was added at a rate of 0.2 g / min, after the addition was completed, 5.5 g of kH560 coupling agent solution was added at a rate of 0.6 g / min, and the stirring was continued for 2.0 h, then it was aged at 82℃ for 10 h, dried at 100℃ for 24 h, then heated to 350℃ at a rate of 2.5℃ / min, kept for 1.2 h, then heated to 630℃ at a rate of 2.0℃ / min, kept for 4.0 h, and naturally cooled to room temperature, to obtain a nickel-iron composite; The cerium nitrate solution was prepared by uniformly mixing 0.45 g of cerium nitrate with 5 g of deionized water; The kH560 coupling agent solution was prepared by uniformly mixing 0.6 g of kH560 silane coupling agent with 5 g of anhydrous ethanol.

[0017] 2. Preparation of functionalized composite powder 4.0 g of γ-aminopropyl triethoxysilane and 3.2 g of phytic acid solution were added to 100 g of anhydrous ethanol, stirred uniformly, then 8 wt% acetic acid solution was added to adjust the pH to 5.0, to obtain a functionalized solution; 35 g of talc powder, 18 g of dolomite, 26 g of barium sulfate, and 6 g of cerium oxide were added to a high-speed mixer, the rotation speed was controlled at 800 rpm, and high-speed mixing was performed for 25 min, then it was added to 400 g of the functionalized solution, heated to 67℃ at a rate of 1.5℃ / min, and kept stirring for 2.5 h, then filtered, washed, and dried, to obtain a functionalized composite powder; The mass concentration of the phytic acid solution is 55%; The particle size of the talc powder is 2.0 μm; The particle size of the dolomite is 1.5 μm; The particle size of the barium sulfate is 2.0 μm; The particle size of the cerium oxide is 100 nm.

[0018] 3. Mixing Into 250 g of 60 wt% ethanol solution, 30 g of functionalized composite powder is added, after stirring uniformly, 15 g of nickel-iron composite is added, the temperature is raised to 42℃, stirring at 220 rpm for 35 min, then the temperature is raised to 63℃ at a rate of 1.2℃ / min, and stirring is maintained for 2.0 h, after filtration, washing and drying, an intermediate is obtained; into 350 g of 60 wt% ethanol solution, 36 g of antimony trioxide and 8 g of zinc oxide are added, after stirring uniformly, 35 g of the intermediate is added, ultrasonic dispersion is carried out, the ultrasonic time is 45 min, the ultrasonic power is 160 W, and the ultrasonic frequency is 45 kHz, after ultrasonic, filtration, washing and drying, an antimony trioxide substitution flame retardant is obtained; The particle size of the antimony trioxide is 250 nm; The particle size of the zinc oxide is 80 nm.

[0019] Example 2 1. Preparation of nickel-iron composite Into 50 g of deionized water, the temperature is raised to 62℃, 2.93 g of nickel nitrate is added, stirring at 250 rpm for 25 min, then 7.25 g of iron nitrate is added, stirring is continued for 32 min, then 5.42 g of cerium nitrate solution is added, after stirring uniformly, 7.0 g of citric acid is added, stirring at 320 rpm for 32 min, 2.1 g of ethylene glycol is added at a rate of 0.1 g / min, after completion of addition, 5.5 g of kH560 coupling agent solution is added at a rate of 0.5 g / min, stirring is continued for 1.8 h, after standing at 82℃ for 12 h, drying is carried out at 110℃ for 20 h, then the temperature is raised to 330℃ at a rate of 2.2℃ / min, and maintained for 1.2 h, then the temperature is raised to 625℃ at a rate of 1.8℃ / min, and maintained for 3.8 h, after natural cooling to room temperature, a nickel-iron composite is obtained; The cerium nitrate solution is prepared by uniformly mixing 0.42 g of cerium nitrate with 5 g of deionized water; The kH560 coupling agent solution is prepared by uniformly mixing 0.53 g of kH560 silane coupling agent with 5 g of anhydrous ethanol.

[0020] 2. Preparation of functionalized composite powder Into 100 g of anhydrous ethanol, 3.8 g of γ-aminopropyl triethoxysilane and 3.2 g of phytic acid solution are added, after stirring uniformly, 6 wt% acetic acid solution is added to adjust the pH to 4.8, and a functionalized solution is obtained; Put 32 g talc powder, 16 g dolomite, 23 g barium sulfate, 5 g cerium oxide into a high-speed mixer, control the rotating speed at 780 rpm, high-speed mix for 30 min, then add into 380 g functionalized solution, increase the temperature to 65 ℃ at a rate of 1.25 ℃ / min, keep stirring for 2.3 h, filter, wash and dry to obtain the functionalized composite powder; The mass concentration of the phytic acid solution is 52%; The particle size of the talc powder is 1.5 μm; The particle size of the dolomite is 1.3 μm; The particle size of the barium sulfate is 1.7 μm; 3. Mixing Put 28 g functionalized composite powder into 230 g 57 wt% ethanol solution, stir uniformly, then add 13 g nickel-iron composite, increase the temperature to 42 ℃, stir at 210 rpm for 30 min, then increase the temperature to 62 ℃ at a rate of 1.2 ℃ / min, keep stirring for 1.8 h, filter, wash and dry to obtain the intermediate; Put 34 g antimony trioxide, 7 g zinc oxide into 320 g 57 wt% ethanol solution, stir uniformly, then add 32 g intermediate, ultrasonic dispersion, ultrasonic time is 43 min, ultrasonic power is 155 W, ultrasonic frequency is 40 kHz, after ultrasonic, filter, wash and dry to obtain the antimony trioxide substitution flame retardant; The particle size of the antimony trioxide is 230 nm; The particle size of the zinc oxide is 70 nm.

[0021] Example 3 1. Preparation of nickel-iron composite Put 50 g deionized water to increase the temperature to 60 ℃, add 2.90 g nickel nitrate, stir at 240 rpm for 20 min, then add 7.20 g iron nitrate, continue to stir for 30 min, then add 5.40 g cerium nitrate solution, stir uniformly, then add 6.8 g citric acid, stir at 310 rpm for 30 min, add 2.0 g ethylene glycol, control the adding rate at 0.2 g / min, after the addition is completed, add 5.6 g kH560 coupling agent solution, control the adding rate at 0.6 g / min, continue to stir for 1.5 h, stand for aging at 80 ℃ for 10 h, then dry at 110 ℃ for 20 h, then increase the temperature to 320 ℃ at a rate of 2.0 ℃ / min, keep for 1.0 h, then increase the temperature to 620 ℃ at a rate of 1.5 ℃ / min, keep for 3.5 h, naturally cool to room temperature to obtain the nickel-iron composite; The cerium nitrate solution is prepared by uniformly mixing 0.40 g cerium nitrate with 5 g deionized water; The kH560 coupling agent solution is prepared by uniformly mixing 0.5 g kH560 silane coupling agent with 5 g anhydrous ethanol.

[0022] 2. Preparation of functionalized composite powder Into 100 g of anhydrous ethanol, 3.5 g of γ-aminopropyl triethoxysilane and 3.0 g of phytic acid solution were added, and after stirring, 5 wt% acetic acid solution was added to adjust the pH to 4.5 to obtain a functionalized solution; Into a high-speed mixer, 30 g of talc powder, 12 g of dolomite, 22 g of barium sulfate, and 4 g of cerium oxide were added, and the rotation speed was controlled at 750 rpm, and high-speed mixing was performed for 35 min, and then it was added to 350-400 g of the functionalized solution, and the temperature was increased to 63°C at a rate of 1.0°C / min, and stirring was performed for 2.0 h, and after filtration, washing and drying, a functionalized composite powder was obtained; The mass concentration of the phytic acid solution was 50%; The particle size of the talc powder was 1.0 μm; The particle size of the dolomite was 1.2 μm; The particle size of the barium sulfate was 1.5 μm; The particle size of the cerium oxide was 90 nm.

[0023] 3. Mixing Into 220 g of a 55 wt% ethanol solution, 25 g of the functionalized composite powder was added, and after stirring, 12 g of a nickel-iron composite was added, and the temperature was increased to 40°C, and stirring was performed at 200 rpm for 25 min, and then the temperature was increased to 60°C at a rate of 1.0°C / min, and stirring was performed for 1.5 h, and after filtration, washing and drying, an intermediate was obtained; into 300 g of a 55 wt% ethanol solution, 32 g of antimony trioxide and 6 g of zinc oxide were added, and after stirring, 30 g of the intermediate was added, and ultrasonic dispersion was performed, and the ultrasonic time was 40 min, the ultrasonic power was 150 W, and the ultrasonic frequency was 38 kHz, and after ultrasonic dispersion, filtration, washing and drying, an antimony trioxide substitution flame retardant was obtained; The particle size of the antimony trioxide was 200 nm; The particle size of the zinc oxide was 60 nm.

[0024] Comparative Example 2-1 1. The step of preparing a nickel-iron composite was omitted 2. Preparation of functionalized composite powder Into a high-speed mixer, 32 g of talc powder, 16 g of dolomite, 23 g of barium sulfate, and 5 g of cerium oxide were added, and the rotation speed was controlled at 780 rpm, and high-speed mixing was performed for 30 min to obtain a functionalized composite powder; The particle size of the talc powder was 1.5 μm; The particle size of the dolomite was 1.3 μm; The particle size of the barium sulfate was 1.7 μm; The particle size of the cerium oxide was 95 nm; 3. Mixing The nickel-iron composite is replaced by an equal amount of a mixture of nickel oxide and iron oxide in a mass ratio of 1:1, and the rest of the operations are exactly the same; The particle size of the nickel oxide is 100 nm; the particle size of the iron oxide is 100 nm.

[0025] Comparative Example 2-2 1. Preparation of a nickel-iron composite 50 g of deionized water was heated to 62℃, 2.93 g of nickel nitrate was added, stirred at 250 rpm for 25 min, then 7.25 g of ferric nitrate was added, and stirring was continued for 32 min, then 7.0 g of citric acid was added, stirring at 320 rpm for 32 min, then 2.1 g of ethylene glycol was added, and after stirring evenly, it was aged at 82℃ for 12 h, then dried at 110℃ for 20 h, then heated to 330℃ at a rate of 2.2℃ / min, held for 1.2 h, then heated to 625℃ at a rate of 1.8℃ / min, held for 3.8 h, and then naturally cooled to room temperature to obtain a nickel-iron composite; 2. Preparation of a functional composite powder The same as the operation steps of Example 2; 3. Mixing The same as the operation steps of Example 2.

[0026] Application performance 1. Application of antimony trioxide substitute flame retardant in PP (1) Basic performance 1. Mix 26 g of copolymerized PP (K8003, Ningbo Shengke Plastic Co., Ltd.) and 26 g of homopolymerized PP (1100N, Ningbo Shengke Plastic Co., Ltd.), add 21 g of decabromodiphenyl ethane and 7 g of antimony trioxide substitute flame retardant prepared in Example 1-3 and Comparative Example 1-2 respectively, stir evenly, then add 20 g of talc powder, mix evenly, then add to a twin-screw extruder, control the extrusion temperature to be 150℃, 165℃, 175℃, 175℃, 165℃ respectively, the screw rotation speed is 320 rpm, after extrusion, granulate to obtain a PP flame-retardant composite material, test the flame-retardant performance and mechanical properties of the PP flame-retardant composite material respectively, and the test results are as follows:

[0027] (2) Aging resistance The above PP flame-retardant composite material is reduced in temperature to -40℃ at a rate of 5.0℃ / min, and is kept for 6.0h, and then is increased in temperature to 86℃ at a rate of 5.0℃ / min, and is kept for 6.0h, which is one treatment cycle, and after 20 treatment cycles are continuously carried out, the mechanical properties of the PP flame-retardant composite material are tested again, and the test results are as follows:

[0028] 2. Application of antimony trioxide substitute flame retardant in ABS (1) Basic properties 81g ABS (brand 0215H), 14.25g brominated triazine and 4.75g antimony trioxide substitute flame retardant are mixed, after uniform mixing, they are put into a double screw extruder, the extrusion temperature is controlled to be 165℃, 180℃, 190℃, 185℃, 180℃ respectively, the screw rotation speed is 300rpm, after extrusion, granulation is carried out, and ABS flame-retardant composite material is obtained, the flame-retardant properties and mechanical properties of the ABS flame-retardant composite material are tested respectively, and the test results are as follows:

[0029] (2) Aging resistance The above ABS flame-retardant composite material is reduced in temperature to -40℃ at a rate of 5.0℃ / min, and is kept for 6.0h, and then is increased in temperature to 86℃ at a rate of 5.0℃ / min, and is kept for 6.0h, which is one treatment cycle, and after 20 treatment cycles are continuously carried out, the mechanical properties of the ABS flame-retardant composite material are tested again, and the test results are as follows:

[0030] Comparative example 2-1 omits the preparation step of nickel-iron composite, directly uses nickel oxide and iron oxide to prepare flame retardant, and lacks synergistic effect between the two, and omits cerium element, which reduces the flame retardant properties and smoke suppression property; in the preparation of functionalized composite powder step, the functionalized solution components are omitted, and talc, dolomite, barium sulfate and cerium oxide are directly mixed, which cannot form a continuous and stable protective layer during combustion, and also makes the combination with nickel-iron composite poor, and the compatibility with the polymer matrix is poor, and in the mixing step, the agglomeration phenomenon is serious, the prepared flame retardant has poor homogeneity, not only reduces the flame retardant property, but also greatly weakens the mechanical properties, and in the complex environment of high and low temperature, the stability is greatly reduced, and the service life is seriously shortened; Comparative Example 2-2: In the preparation of the nickel-iron composite, the cerium nitrate component is omitted, which reduces its smoke suppression property and catalytic charring ability, and the kH560 silane coupling agent treatment is also omitted. The obtained nickel-iron composite has a certain degree of agglomeration, the active surface is reduced, the combination with the functionalized composite powder is reduced, it cannot be firmly anchored with the functionalized composite powder in the mixing step, and the combination with the polymer matrix is poor. Finally, the flame retardant performance, mechanical properties and comprehensive performance of the obtained product are reduced.

[0031] Unless otherwise specified, the proportions described in the present application are mass proportions, and the percentages described are mass percentages.

[0032] Finally, it should be noted that the above description is only a preferred embodiment of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a synergistic flame retardant-reinforcement integrated antimony trioxide substitute flame retardant, characterized in that, The preparation method includes preparing nickel-iron composites, preparing functionalized composite powders, and mixing steps. The steps for preparing the nickel-iron composite are as follows: Deionized water is heated to 60-65℃, nickel nitrate and iron nitrate are added, and the mixture is stirred until homogeneous. Cerium nitrate solution and citric acid are then added, and the mixture is stirred for 30-35 minutes. Ethylene glycol is added, and after the addition is complete, KH560 coupling agent solution is added at a rate of 0.5-0.6 g / min. The mixture is stirred for 1.5-2.0 hours, allowed to stand for aging, and then dried. The mixture is then kept at 320-350℃ for 1.0-1.2 hours and at 620-630℃ for 3.5-4.0 hours to obtain the nickel-iron composite. The mixing step is as follows: add functionalized composite powder to ethanol solution, stir evenly, add nickel-iron composite, stir at 40-42℃, stir at 60-63℃ for 1.5-2.0h to obtain intermediate; Antimony trioxide, zinc oxide, and an intermediate were added to an ethanol solution and then ultrasonically dispersed to obtain an antimony trioxide alternative flame retardant.

2. The preparation method of the antimony trioxide substitute flame retardant with synergistic flame retardancy and reinforcement as described in claim 1, characterized in that, In the step of preparing the nickel-iron composite, the mass ratio of deionized water, nickel nitrate, iron nitrate, cerium nitrate solution, citric acid, ethylene glycol, and KH560 coupling agent solution is 50:2.90-2.95:7.20-7.30:5.40-5.45:6.8-7.3:2.0-2.2:5.5-5.

6. The cerium nitrate solution is prepared by uniformly mixing 0.40-0.45g of cerium nitrate with 5g of deionized water. The kH560 coupling agent solution is prepared by uniformly mixing 0.5-0.6g of kH560 silane coupling agent with 5g of anhydrous ethanol.

3. The preparation method of the antimony trioxide substitute flame retardant with synergistic flame retardancy and reinforcement as described in claim 1, characterized in that, The steps for preparing the functionalized composite powder are as follows: Add 3.5-4.0g of γ-aminopropyltriethoxysilane and 3.0-3.2g of phytic acid solution to 100g of anhydrous ethanol, stir until homogeneous, then add 5-8wt% acetic acid solution to adjust the pH to 4.5-5.0 to obtain a functionalized solution; add talc, dolomite, barium sulfate, and cerium oxide to a high-speed mixer, control the speed at 750-800rpm, mix at high speed for 25-35min, then add to the functionalized solution, raise the temperature to 63-67℃ at a rate of 1.0-1.5℃ / min, keep warm and stir for 2.0-2.5h, filter, wash and dry to obtain the functionalized composite powder.

4. The preparation method of a synergistic flame retardant-reinforcement integrated antimony trioxide substitute flame retardant according to claim 3, characterized in that, The mass ratio of talc, dolomite, barium sulfate, cerium oxide, and functionalized solution is 30-35:12-18:22-26:4-6:350-400; The talc powder has a particle size of 1.0-2.0 μm; The dolomite has a particle size of 1.2-1.5 μm; The barium sulfate has a particle size of 1.5-2.0 μm; The cerium oxide has a particle size of 90-100 nm.

5. The preparation method of a synergistic flame retardant-reinforcement integrated antimony trioxide substitute flame retardant according to claim 4, characterized in that, In the functionalized solution, the mass ratio of anhydrous ethanol, γ-aminopropyltriethoxysilane, and phytic acid solution is 100:3.5-4.0:3.0-3.

2. The phytic acid solution has a mass concentration of 50-55%.

6. The preparation method of a synergistic flame retardant-reinforcement integrated antimony trioxide substitute flame retardant according to claim 1, characterized in that, In the mixing step, the mass ratio of the ethanol solution, antimony trioxide, zinc oxide, and intermediate is 300-350:32-36:6-8:30-35; The ethanol solution has a mass concentration of 55-60%; The antimony trioxide has a particle size of 200-250 nm; The zinc oxide has a particle size of 60-80 nm.

7. The preparation method of a synergistic flame retardant-reinforcement integrated antimony trioxide substitute flame retardant according to claim 6, characterized in that, In the intermediate, the mass ratio of the ethanol solution, the functionalized composite powder, and the nickel-iron composite is 220-250:25-30:12-15.

8. The antimony trioxide alternative flame retardant prepared by the preparation method according to any one of claims 1-7.

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