A synergistic flame-retardant-reinforced integrated antimony trioxide replacement flame retardant and a preparation method thereof

Abstract

The application 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 composite, preparing a functionalized composite powder and mixing; in the step of preparing the nickel-iron composite, deionized water is heated to 60-65 DEG C, nickel nitrate and iron nitrate are added, after being uniformly stirred, cerium nitrate solution and citric acid are added, stirring is carried out for 30-35 min, ethylene glycol and kH560 coupling agent solution are added, stirring is carried out for 1.5-2.0 h, after being aged by standing, drying is carried out, 320-350 DEG C is kept for 1.0-1.2 h, 620-630 DEG C is kept for 3.5-4.0 h, and the nickel-iron composite is obtained; the antimony trioxide substitute flame retardant of the application can completely replace antimony trioxide in an equal amount in the field, and has strong flame-retardant performance, mechanical properties and stability.

Description

Technical Field

[0001] This invention belongs to the field of flame retardant technology, specifically relating to a synergistic flame retardant-enhancing antimony trioxide substitute flame retardant and its preparation method. Background Technology

[0002] Existing technologies for preparing flame retardants mainly include bromine-antimony flame retardants and halogen-free (phosphorus-nitrogen) flame retardants. Compared with mature bromine-antimony flame retardants, halogen-free flame retardants have significant advantages in environmental protection and biosafety, but they do have some challenges or disadvantages in terms of technical performance and application. Halogen-free flame retardants have low flame retardant efficiency and require a large amount to be added, and high addition amounts can seriously affect the performance of the matrix material. A large amount of flame retardant filled into the polymer will seriously damage the structure and interaction of the polymer chain, resulting in a significant decrease in the tensile strength, impact toughness, elongation at break and other mechanical properties of the material. The material will become brittle and hard, and the reliability of processing and use will be reduced.

[0003] Furthermore, halogen-free flame retardants have higher requirements for processing technology. Materials such as nylon have high processing temperatures, and most phosphorus and nitrogen-based flame retardants decompose at these processing temperatures. They may also affect the electrical insulation, transparency, weather resistance, and compatibility of the materials.

[0004] Therefore, bromine-antimony flame retardants are the most commonly used flame retardant systems in existing technologies.

[0005] Antimony trioxide (Sb2O3) is a white crystalline powder. As a highly efficient flame retardant synergist, it is widely used in the flame retardant modification of materials such as plastics, rubber, and textiles when combined with bromine-based flame retardants to form a bromine-antimony flame retardant system. It occupies an important position in industries such as plastics, electronics, building materials, and automotive parts.

[0006] At present, although the bromine-antimony flame retardant system plays an irreplaceable role in the field of flame retardants, it also has significant safety and environmental hazards. Some bromine-based flame retardants produce toxic fumes when burning, and antimony is also considered to have potential biological toxicity. Furthermore, due to the current unstable price of antimony, environmental restrictions, and import and export controls, the cost of using the bromine-antimony flame retardant system has increased significantly. In the flame retardant modification of materials, the addition of flame retardants can lead to a decrease in the mechanical properties of the materials.

[0007] Therefore, these controversies have prompted the flame retardant industry to continuously improve bromine-antimony flame retardant systems and develop more environmentally friendly bromine-antimony flame retardants, reducing the amount of antimony trioxide used while minimizing the impact on the environment and health, and ensuring the mechanical properties of the materials.

[0008] The existing technologies for improving bromine-antimony flame retardants mainly include the following methods:

[0009] 1. Develop novel brominated flame retardants; replace harmful traditional varieties (polybrominated diphenyl ethers, hexabromocyclododecane, etc.) with high molecular weight / polymerized brominated flame retardants. However, the synthesis process of novel high molecular weight / polymerized flame retardants is complex and costly, and their compatibility with the matrix material will deteriorate, which will have a negative impact on the processing flowability and mechanical properties of the material.

[0010] 2. Find alternative synergists for antimony; use phosphorus-based, nitrogen-based, and metal compounds to replace antimony, but the synergistic effect is usually lower than that of antimony and will affect the appearance of the material;

[0011] 3. Microencapsulation / coating technology; This is a physical-chemical method designed to "encapsulate" antimony bromide flame retardants, isolating them from direct contact with the external environment; however, this method significantly increases costs and affects flame retardant efficiency, and is technically complex (the uniformity, integrity, and coating rate of the coating are all technical challenges).

[0012] It is evident that the improved bromine-antimony flame retardants produced by existing technologies cannot meet the requirements of "reducing the amount of antimony trioxide, lowering costs, and being environmentally friendly while ensuring the flame retardant properties and enhancing the mechanical properties of the material". Summary of the Invention

[0013] To address the technical problems existing in the prior art, this invention provides a synergistic flame retardant-reinforcement integrated antimony trioxide substitute flame retardant and its preparation method. It can effectively reduce the amount of antimony trioxide used, lower costs, and is environmentally friendly. This flame retardant can completely replace antimony trioxide in equal amounts in the fields of polyolefin plastics and engineering plastics. It not only has excellent flame retardant rating and limiting oxygen index, but also enhances the mechanical properties of materials.

[0014] To address the aforementioned technical problems, the present invention adopts the following technical solution:

[0015] A method for preparing a synergistic flame retardant-reinforcement integrated antimony trioxide alternative flame retardant includes preparing a nickel-iron composite, preparing a functionalized composite powder, and mixing steps, as detailed below:

[0016] 1. Preparation of nickel-iron composite

[0017] Heat deionized water to 60-65℃, add nickel nitrate, and stir at 240-270 rpm for 20-30 min. Then add ferric nitrate and continue stirring for 30-35 min. Next, add cerium nitrate solution and stir until homogeneous. Then add citric acid and stir at 310-330 rpm for 30-35 min. Finally, add ethylene glycol at a rate of 0.1-0.2 g / min. After the addition is complete, add KH560 coupling agent solution at a rate of 0. Add 0.5-0.6 g / min, continue stirring for 1.5-2.0 h, allow to stand for aging at 80-82℃ for 10-12 h, dry at 100-110℃ for 20-24 h, then increase the temperature to 320-350℃ at a rate of 2.0-2.5℃ / min, hold for 1.0-1.2 h, then increase the temperature to 620-630℃ at a rate of 1.5-2.0℃ / min, hold for 3.5-4.0 h, and allow to cool naturally to room temperature to obtain the nickel-iron composite.

[0018] The cerium nitrate solution is prepared by uniformly mixing 0.40-0.45g of cerium nitrate with 5g of deionized water.

[0019] The kH560 coupling agent solution is prepared by uniformly mixing 0.5-0.6g of kH560 silane coupling agent with 5g of anhydrous ethanol.

[0020] The mass ratio of the deionized water, nickel nitrate, ferric 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.

[0021] 2. Preparation of functionalized composite powder

[0022] Add 3.5-4.0g of γ-aminopropyltriethoxysilane and 3.0-3.2g of phytic acid solution to 100g of anhydrous ethanol, stir well, and then add 5-8wt% acetic acid solution to adjust the pH to 4.5-5.0 to obtain a functionalized solution.

[0023] The mass ratio of anhydrous ethanol, γ-aminopropyltriethoxysilane, and phytic acid solution is 100:3.5-4.0:3.0-3.2.

[0024] The phytic acid solution has a mass concentration of 50-55%;

[0025] Talc, dolomite, barium sulfate, and cerium oxide are added to a high-speed mixer and mixed at 750-800 rpm for 25-35 minutes. Then, the mixture is added to a functionalized solution and the temperature is increased to 63-67℃ at a rate of 1.0-1.5℃ / min. The mixture is then kept warm and stirred for 2.0-2.5 hours. After filtration, washing, and drying, the functionalized composite powder is obtained.

[0026] The mass ratio of talc, dolomite, barium sulfate, cerium oxide, and functionalized solution is 30-35:12-18:22-26:4-6:350-400;

[0027] The talc powder has a particle size of 1.0-2.0 μm;

[0028] The dolomite has a particle size of 1.2-1.5 μm;

[0029] The barium sulfate has a particle size of 1.5-2.0 μm;

[0030] The cerium oxide has a particle size of 90-100 nm.

[0031] 3. Mixing

[0032] Functionalized composite powder was added to an ethanol solution and stirred until homogeneous. Then, nickel-iron composite was added, and the temperature was raised to 40-42℃. The mixture was stirred at 200-220 rpm for 25-35 min, and then the temperature was raised to 60-63℃ at a rate of 1.0-1.2℃ / min. The mixture was kept at this temperature and stirred for 1.5-2.0 h. After filtration, washing, and drying, an intermediate was obtained. Antimony trioxide and zinc oxide were added to an ethanol solution and stirred until homogeneous. Then, the intermediate was added and ultrasonically dispersed. The ultrasonic time was 40-45 min, the ultrasonic power was 150-160 W, and the ultrasonic frequency was 38-45 kHz. After ultrasonication, the mixture was filtered, washed, and dried to obtain an antimony trioxide flame retardant substitute.

[0033] The mass ratio of the ethanol solution, functionalized composite powder, and nickel-iron composite is 220-250:25-30:12-15;

[0034] The mass ratio of the ethanol solution, antimony trioxide, zinc oxide, and intermediate is 300-350:32-36:6-8:30-35;

[0035] The ethanol solution has a mass concentration of 55-60%;

[0036] The antimony trioxide has a particle size of 200-250 nm;

[0037] The zinc oxide has a particle size of 60-80 nm.

[0038] A synergistic flame retardant-reinforcement integrated antimony trioxide alternative flame retardant was prepared using the aforementioned preparation method.

[0039] Compared with the prior art, the present invention has achieved the following beneficial effects:

[0040] 1. This invention first prepares a nickel-iron composite material, specifically using nickel nitrate and iron nitrate as metal sources. During polymer combustion, these materials form a dense carbon layer, enhancing flame retardant properties. Then, cerium nitrate is used as a rare earth element additive, and citric acid as a complexing agent, helping to ensure more uniform composite particles. Treatment with KH560 silane coupling agent allows the epoxy groups to participate in the formation of the gel network, enhancing the stability of the nickel-iron composite material, improving its bonding with functionalized composite powders, and enhancing its interfacial compatibility with the polymer matrix. In the preparation of the functionalized composite powder, cerium oxide, a flame-retardant synergist and anti-aging functional agent, possesses excellent catalytic activity. Its combination with talc, dolomite, and barium sulfate effectively transfers stress, significantly improving the strength properties of the composite material, which exhibits good performance characteristics. The flame retardancy, smoke suppression, and enhancement properties are achieved through functionalized solution treatment. The amino groups of γ-aminopropyltriethoxysilane enhance interfacial bonding, while phytic acid enhances flame retardancy. Phytic acid also binds to the amino groups, firmly bonding the phytic acid to the powder and providing anchoring points for the nickel-iron composite. In the mixing step, the epoxy groups of the nickel-iron composite combine with the amino groups of the functionalized composite, and when combined with antimony trioxide and zinc oxide, they promote the formation of a stable char layer on the polymer matrix in the early stages of combustion, reducing the release of combustible volatiles. Simultaneously, the synergistic effect of antimony trioxide and other components improves the flame retardant performance while reducing the amount of antimony trioxide required, enhancing compatibility and bonding with the polymer matrix, and ensuring mechanical properties while enhancing flame retardancy.

[0041] 2. When the antimony trioxide substitute flame retardant prepared in this invention is applied to PP, the resulting PP flame-retardant composite material has a flame retardant rating of V-0, a limiting oxygen index of 30.28-32.56%, and a cantilever beam impact strength of 8.16-8.37 kJ / m². 2 The tensile strength is 37.95-38.79 MPa, the elongation at break is 46.34-47.02%, and the flexural strength is 48.52-50.65 MPa.

[0042] After undergoing 20 cycles of high and 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 flexural strength is 46.48-48.83 MPa.

[0043] 3. When the antimony trioxide substitute flame retardant prepared in this invention is applied to ABS, the resulting ABS flame-retardant composite material has a flame retardant rating of V-0, a limiting oxygen index of 33.48-34.04%, and a cantilever beam impact strength of 14.21-14.75 kJ / m². 2 The tensile strength is 56.13-56.71 MPa, the elongation at break is 11.48-12.05%, and the flexural strength is 82.15-83.26 MPa.

[0044] After undergoing 20 cycles of high and low temperature treatment, the cantilever beam impact strength of the ABS flame-retardant composite material 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 flexural strength is 78.54-80.51 MPa. Detailed Implementation

[0045] To provide a clearer understanding of the technical features, objectives, and effects of the present invention, specific embodiments of the present invention are now described.

[0046] Example 1

[0047] 1. Preparation of nickel-iron composite

[0048] 50g of deionized water was heated to 65℃, 2.95g of nickel nitrate was added, and the mixture was stirred at 270rpm for 30min. Then, 7.30g of ferric nitrate was added, and the mixture was stirred for another 35min. Next, 5.45g of cerium nitrate solution was added, and the mixture was stirred until homogeneous. Then, 7.3g of citric acid was added, and the mixture was stirred at 330rpm for 35min. Then, 2.2g of ethylene glycol was added at a rate of 0.2g / min. After the addition was complete, 5.5g of KH560 coupling agent solution was added at a rate of 0.6g / min. The mixture was stirred for another 2.0h. After aging at 82℃ for 10h, the mixture was dried at 100℃ for 24h. Then, the temperature was increased to 350℃ at a rate of 2.5℃ / min and held for 1.2h. Then, the temperature was increased to 630℃ at a rate of 2.0℃ / min and held for 4.0h. The mixture was then allowed to cool naturally to room temperature to obtain the nickel-iron composite.

[0049] The cerium nitrate solution was prepared by uniformly mixing 0.45g of cerium nitrate with 5g of deionized water.

[0050] The kH560 coupling agent solution was prepared by uniformly mixing 0.6g of kH560 silane coupling agent with 5g of anhydrous ethanol.

[0051] 2. Preparation of functionalized composite powder

[0052] Add 4.0g of γ-aminopropyltriethoxysilane and 3.2g of phytic acid solution to 100g of anhydrous ethanol, stir well, and then add 8wt% acetic acid solution to adjust the pH to 5.0 to obtain a functionalized solution.

[0053] Add 35g of talc powder, 18g of dolomite, 26g of barium sulfate and 6g of cerium oxide to a high-speed mixer, control the speed at 800rpm, mix at high speed for 25min, then add to 400g of functionalized solution, raise the temperature to 67℃ at a rate of 1.5℃ / min, keep warm and stir for 2.5h, filter, wash and dry to obtain functionalized composite powder.

[0054] The phytic acid solution has a mass concentration of 55%.

[0055] The talc powder has a particle size of 2.0 μm;

[0056] The dolomite has a particle size of 1.5 μm;

[0057] The barium sulfate has a particle size of 2.0 μm;

[0058] The cerium oxide has a particle size of 100 nm.

[0059] 3. Mixing

[0060] Add 30g of functionalized composite powder to 250g of 60wt% ethanol solution, stir evenly, then add 15g of nickel-iron composite, raise the temperature to 42℃, stir at 220rpm for 35min, then raise the temperature to 63℃ at a rate of 1.2℃ / min, keep stirring at this temperature for 2.0h, filter, wash and dry to obtain an intermediate; add 36g of antimony trioxide and 8g of zinc oxide to 350g of 60wt% ethanol solution, stir evenly, then add 35g of the intermediate, and perform ultrasonic dispersion for 45min at a power of 160W and a frequency of 45kHz. After ultrasonication, filter, wash and dry to obtain an antimony trioxide flame retardant substitute.

[0061] The antimony trioxide has a particle size of 250 nm;

[0062] The zinc oxide has a particle size of 80 nm.

[0063] Example 2

[0064] 1. Preparation of nickel-iron composite

[0065] 50g of deionized water was heated to 62℃, 2.93g of nickel nitrate was added, and the mixture was stirred at 250rpm for 25min. Then, 7.25g of ferric nitrate was added, and the mixture was stirred for another 32min. Next, 5.42g of cerium nitrate solution was added, and the mixture was stirred until homogeneous. Then, 7.0g of citric acid was added, and the mixture was stirred at 320rpm for 32min. Then, 2.1g of ethylene glycol was added at a rate of 0.1g / min. After the addition was complete, 5.5g of KH560 coupling agent solution was added at a rate of 0.5g / min, and the mixture was stirred for another 1.8h. The mixture was then allowed to stand at 82℃ for 12h, dried at 110℃ for 20h, and then the temperature was increased to 330℃ at a rate of 2.2℃ / min and held for 1.2h. Finally, the temperature was increased to 625℃ at a rate of 1.8℃ / min and held for 3.8h. The mixture was then allowed to cool naturally to room temperature to obtain the nickel-iron composite.

[0066] The cerium nitrate solution was prepared by uniformly mixing 0.42g of cerium nitrate with 5g of deionized water.

[0067] The kH560 coupling agent solution was prepared by uniformly mixing 0.53g of kH560 silane coupling agent with 5g of anhydrous ethanol.

[0068] 2. Preparation of functionalized composite powder

[0069] Add 3.8g of γ-aminopropyltriethoxysilane and 3.2g of phytic acid solution to 100g of anhydrous ethanol, stir well, and then add 6wt% acetic acid solution to adjust the pH to 4.8 to obtain a functionalized solution.

[0070] Add 32g of talc, 16g of dolomite, 23g of barium sulfate and 5g of cerium oxide to a high-speed mixer, control the speed at 780rpm, mix at high speed for 30min, then add to 380g of functionalized solution, raise the temperature to 65℃ at a rate of 1.25℃ / min, keep warm and stir for 2.3h, filter, wash and dry to obtain functionalized composite powder;

[0071] The phytic acid solution has a mass concentration of 52%.

[0072] The talc powder has a particle size of 1.5 μm;

[0073] The dolomite has a particle size of 1.3 μm;

[0074] The barium sulfate has a particle size of 1.7 μm;

[0075] 3. Mixing

[0076] Add 28g of functionalized composite powder to 230g of 57wt% ethanol solution, stir evenly, then add 13g of nickel-iron composite, raise the temperature to 42℃, stir at 210rpm for 30min, then raise the temperature to 62℃ at a rate of 1.2℃ / min, keep stirring at this temperature for 1.8h, filter, wash and dry to obtain an intermediate; add 34g of antimony trioxide and 7g of zinc oxide to 320g of 57wt% ethanol solution, stir evenly, then add 32g of the intermediate, and perform ultrasonic dispersion for 43min, ultrasonic power of 155W and ultrasonic frequency of 40kHz. After ultrasonication, filter, wash and dry to obtain antimony trioxide alternative flame retardant;

[0077] The antimony trioxide has a particle size of 230 nm;

[0078] The zinc oxide has a particle size of 70 nm.

[0079] Example 3

[0080] 1. Preparation of nickel-iron composite

[0081] 50g of deionized water was heated to 60℃, 2.90g of nickel nitrate was added, and the mixture was stirred at 240rpm for 20min. Then, 7.20g of ferric nitrate was added, and the mixture was stirred for another 30min. Next, 5.40g of cerium nitrate solution was added, and the mixture was stirred until homogeneous. Then, 6.8g of citric acid was added, and the mixture was stirred at 310rpm for 30min. Then, 2.0g of ethylene glycol was added at a rate of 0.2g / min. After the addition was complete, 5.6g of KH560 coupling agent solution was added at a rate of 0.6g / min. The mixture was stirred for another 1.5h. The mixture was then allowed to stand at 80℃ for 10h and dried at 110℃ for 20h. The temperature was then increased to 320℃ at a rate of 2.0℃ / min and held for 1.0h. The temperature was then increased to 620℃ at a rate of 1.5℃ / min and held for 3.5h. The mixture was then allowed to cool naturally to room temperature to obtain the nickel-iron composite.

[0082] The cerium nitrate solution was prepared by uniformly mixing 0.40g of cerium nitrate with 5g of deionized water.

[0083] The kH560 coupling agent solution was prepared by uniformly mixing 0.5g of kH560 silane coupling agent with 5g of anhydrous ethanol.

[0084] 2. Preparation of functionalized composite powder

[0085] Add 3.5g of γ-aminopropyltriethoxysilane and 3.0g of phytic acid solution to 100g of anhydrous ethanol, stir well, and then add 5wt% acetic acid solution to adjust the pH to 4.5 to obtain a functionalized solution.

[0086] Add 30g of talc, 12g of dolomite, 22g of barium sulfate, and 4g of cerium oxide to a high-speed mixer, control the speed at 750rpm, and mix at high speed for 35min. Then add it to 350-400g of functionalized solution, raise the temperature to 63℃ at a rate of 1.0℃ / min, keep it warm and stir for 2.0h, filter, wash and dry to obtain functionalized composite powder.

[0087] The phytic acid solution has a mass concentration of 50%.

[0088] The talc powder has a particle size of 1.0 μm;

[0089] The dolomite has a particle size of 1.2 μm;

[0090] The barium sulfate has a particle size of 1.5 μm;

[0091] The cerium oxide has a particle size of 90 nm.

[0092] 3. Mixing

[0093] Add 25g of functionalized composite powder to 220g of 55wt% ethanol solution, stir evenly, then add 12g of nickel-iron composite, raise the temperature to 40℃, stir at 200rpm for 25min, then raise the temperature to 60℃ at a rate of 1.0℃ / min, keep stirring for 1.5h, filter, wash and dry to obtain intermediate; add 32g of antimony trioxide and 6g of zinc oxide to 300g of 55wt% ethanol solution, stir evenly, then add 30g of intermediate, and perform ultrasonic dispersion for 40min at a power of 150W and a frequency of 38kHz. After ultrasonication, filter, wash and dry to obtain antimony trioxide flame retardant substitute.

[0094] The antimony trioxide has a particle size of 200 nm;

[0095] The zinc oxide has a particle size of 60 nm.

[0096] Comparative Example 2-1

[0097] 1. Omit the step of preparing the nickel-iron composite.

[0098] 2. Preparation of functionalized composite powder

[0099] Add 32g of talc, 16g of dolomite, 23g of barium sulfate and 5g of cerium oxide to a high-speed mixer, control the speed at 780rpm, and mix at high speed for 30min to obtain functionalized composite powder.

[0100] The talc powder has a particle size of 1.5 μm;

[0101] The dolomite has a particle size of 1.3 μm;

[0102] The barium sulfate has a particle size of 1.7 μm;

[0103] The cerium oxide has a particle size of 95 nm;

[0104] 3. Mixing

[0105] The nickel-iron composite was replaced with an equal amount of a mixture of nickel oxide and iron oxide in a mass ratio of 1:1, and the rest of the operation was exactly the same.

[0106] The nickel oxide has a particle size of 100 nm; the iron oxide has a particle size of 100 nm.

[0107] Comparative Example 2-2

[0108] 1. Preparation of nickel-iron composite

[0109] 50g of deionized water was heated to 62℃, 2.93g of nickel nitrate was added, and the mixture was stirred at 250rpm for 25min. Then, 7.25g of ferric nitrate was added, and the mixture was stirred for another 32min. Next, 7.0g of citric acid was added, and the mixture was stirred at 320rpm for 32min. Then, 2.1g of ethylene glycol was added, and the mixture was stirred until homogeneous. The mixture was then aged at 82℃ for 12h, dried at 110℃ for 20h, and then the temperature was increased to 330℃ at a rate of 2.2℃ / min and held for 1.2h. Finally, the temperature was increased to 625℃ at a rate of 1.8℃ / min and held for 3.8h. The mixture was then allowed to cool naturally to room temperature to obtain the nickel-iron composite.

[0110] 2. Preparation of functionalized composite powder

[0111] The operation steps are exactly the same as in Example 2;

[0112] 3. Mixing

[0113] The operation steps are exactly the same as in Example 2.

[0114] Application performance

[0115] 1. Application of antimony trioxide as a substitute for flame retardants in PP

[0116] (1) Basic performance

[0117] 1. Mix 26g of copolymer PP (Ningbo Shengke Plastics Co., Ltd. K8003) and 26g of homopolymer PP (Ningbo Shengke Plastics Co., Ltd. 1100N), add 21g of decabromodiphenyl ethane and 7g of antimony trioxide substitute flame retardant prepared in Examples 1-3 and Comparative Examples 1-2, respectively. After stirring evenly, add 20g of talc powder, mix evenly, and then add to a twin-screw extruder. Control the extrusion temperature at 150℃, 165℃, 175℃, 175℃, and 165℃, and the screw speed at 320rpm. After extrusion, granulate to obtain PP flame-retardant composite material. The flame-retardant properties and mechanical properties of the PP flame-retardant composite material are tested, and the test results are as follows:

[0118]

[0119] (2) Aging resistance

[0120] The above-mentioned PP flame-retardant composite material was cooled to -40℃ at a rate of 5.0℃ / min and held at that temperature for 6.0h. Then, the temperature was increased to 86℃ at a rate of 5.0℃ / min and held at that temperature for 6.0h. This process was repeated as one treatment cycle. After 20 consecutive treatment cycles, the mechanical properties of the PP flame-retardant composite material were tested again. The test results are as follows:

[0121]

[0122] 2. Application of antimony trioxide as a substitute for flame retardants in ABS

[0123] (1) Basic performance

[0124] 81g of ABS (grade 0215H), 14.25g of brominated triazine, and 4.75g of antimony trioxide as a flame retardant were mixed and thoroughly mixed before being fed into a twin-screw extruder. The extrusion temperatures were controlled at 165℃, 180℃, 190℃, 185℃, and 180℃, and the screw speed was 300rpm. After extrusion, the mixture was granulated to obtain the ABS flame-retardant composite material. The flame-retardant properties and mechanical properties of the ABS flame-retardant composite material were tested, and the test results are as follows:

[0125]

[0126] (2) Aging resistance

[0127] The above-mentioned ABS flame-retardant composite material was cooled to -40℃ at a rate of 5.0℃ / min and held at that temperature for 6.0h. Then, the temperature was increased to 86℃ at a rate of 5.0℃ / min and held at that temperature for 6.0h. This process was repeated as one treatment cycle. After 20 consecutive treatment cycles, the mechanical properties of the ABS flame-retardant composite material were tested again. The test results are as follows:

[0128]

[0129] Comparative Example 2-1 omits the preparation step of the nickel-iron composite, directly using nickel oxide and iron oxide to prepare the flame retardant. This lacks a synergistic effect between the two, and the omission of cerium reduces flame retardant performance and smoke suppression. In the preparation step of the functionalized composite powder, the functionalized solution components are omitted, and talc, dolomite, barium sulfate, and cerium oxide are directly mixed. This results in the inability to form a continuous and stable protective layer during combustion, poor bonding with the nickel-iron composite, and poor compatibility with the polymer substrate. The mixing step also exhibits severe agglomeration, leading to poor homogeneity of the obtained flame retardant. This not only reduces flame retardancy but also significantly weakens mechanical properties. In complex environments with high and low temperatures, stability is greatly reduced, severely shortening the service life.

[0130] In Comparative Example 2-2, the cerium nitrate component was omitted during the preparation of the nickel-iron composite, which reduced its smoke suppression and catalytic char formation ability. Furthermore, the treatment with kH560 silane coupling agent was omitted, resulting in a certain degree of agglomeration of the nickel-iron composite, a reduction in the active surface area, and a decrease in its binding with the functionalized composite powder. It could not be firmly anchored with the functionalized composite powder during the mixing step, and its binding with the polymer substrate was poor. Ultimately, this resulted in a decrease in its flame retardant properties, a reduction in its mechanical properties, and a deterioration in its overall performance.

[0131] Unless otherwise specified, all proportions mentioned in this invention are mass proportions, and all percentages are mass percentages.

[0132] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention 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 substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

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 steps for preparing the functionalized composite powder are as follows: 3.5-4.0g of γ-aminopropyltriethoxysilane and 3.0-3.2g of phytic acid solution are added to 100g of anhydrous ethanol and stirred until homogeneous. Then, 5-8wt% acetic acid solution is added to adjust the pH to 4.5-5.0 to obtain a functionalized solution. Talc, dolomite, barium sulfate, and cerium oxide are added to a high-speed mixer, and the mixing speed is controlled at 750-800 rpm for 25-35 min. Then, these are added to the functionalized solution, and the temperature is increased to 63-67℃ at a rate of 1.0-1.5℃ / min. The mixture is kept at this temperature and stirred for 2.0-2.5 h. After filtration, washing, and drying, the functionalized composite powder is obtained. 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, In the step of preparing the functionalized composite powder, 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.

4. The preparation method of a synergistic flame retardant-reinforcement integrated antimony trioxide substitute flame retardant according to claim 3, characterized in that, In the functionalized solution, the phytic acid solution has a mass concentration of 50-55%.

5. 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.

6. The preparation method of a synergistic flame retardant-reinforcement integrated antimony trioxide substitute flame retardant according to claim 5, 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.

7. The antimony trioxide alternative flame retardant prepared by the preparation method according to any one of claims 1-6.

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