Flame retardant, preparation method thereof and resin containing flame retardant
By using a compound flame retardant method of POSS-DOPO, MPP and HAp, the problems of low flame retardant efficiency, toxic gas release and insufficient thermal stability in resins have been solved, achieving high-efficiency flame retardancy, low smoke density and excellent thermal stability, while maintaining good mechanical properties.
Patent Information
- Application Number
- CN202511337734.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-18
- Publication Date
- 2025-11-11
AI Technical Summary
Existing flame retardants in resins have problems such as low flame retardant efficiency, release of toxic gases, and insufficient thermal stability, or poor compatibility and uneven dispersion of compound flame retardants, which lead to a decline in mechanical properties.
Flame retardants are compounded using POSS-DOPO, MPP, and HAp and prepared through free radical reaction and spray drying processes. Combined with epoxy resin, they form a chemically bonded copolymer, which improves dispersibility and thermal stability.
It achieves high flame retardant efficiency (LOI of 38.4%, UL-94 V0), low maximum smoke density (150.6), excellent thermal stability (TGA 5% weight loss temperature ≥300℃), and high mechanical property retention (tensile strength ≥80 MPa, retention rate ≥85%).
Abstract
Description
Technical Field
[0001] This invention relates to the field of resin technology, and more specifically to a flame retardant, its preparation method, and a resin containing the flame retardant. Background Technology
[0002] In existing technologies, flame retardants are added to resins to improve the flame retardant properties of products. Traditional flame retardants include halogenated flame retardants, phosphorus-based flame retardants, silicone-based flame retardants, and compound flame retardants, etc. Each flame retardant has its own limitations. For example, halogenated flame retardants have high flame retardant efficiency, but release toxic gases when burning. Phosphorus-based flame retardants are environmentally friendly, but their thermal stability is insufficient when used alone. Silicone-based flame retardants can improve thermal stability, but their flame retardant efficiency is low when used alone. Compound flame retardants have problems such as poor compatibility and uneven dispersion, which leads to a decrease in mechanical properties.
[0003] Therefore, we propose a flame retardant, its preparation method, and a resin containing the flame retardant. Summary of the Invention
[0004] This invention provides a flame retardant, its preparation method, and a resin containing the flame retardant, which solves the technical problems of existing single flame retardants being unable to simultaneously achieve flame retardant efficiency, release of toxic gases, environmental protection, and thermal stability, as well as the technical problems of poor compatibility and uneven dispersion of compound flame retardants.
[0005] To achieve the above objectives, the present invention provides the following technical solution: A flame retardant, characterized in that it comprises the following components in parts by weight: POSS-DOPO 16-20 servings; Melamine polyphosphate (MPP) 5-8 parts; Nano-hydroxyapatite (HAp) 3-5 parts.
[0006] Furthermore, the flame retardant also includes the following components by weight: 0.5-1 parts of silane coupling agent.
[0007] Furthermore, the flame retardant comprises the following components in parts by weight: 18 copies of POSS-DOPO; 7 parts of melamine polyphosphate (MPP); 3 parts of nano-hydroxyapatite (HAp); 0.5 parts of silane coupling agent.
[0008] Furthermore, POSS-DOPO was prepared by the following method, S1. Mixing raw materials: Dissolve octavinyl-octasilsesquioxane (octavinyl-POSS) and DOPO in toluene at a molar ratio of 1:8, and stir for 30 minutes under nitrogen protection to obtain a mixed raw material; S2, Free radical addition reaction: Add 0.5 wt% of the mixed raw materials according to step S1 to dicumyl peroxide (DCP), react at 110℃ for 6 hours to obtain a viscous solution; S3. Purification: Add methanol to the viscous solution from step S2 to precipitate, filter, and vacuum dry to obtain a white powder.
[0009] This invention provides a method for preparing the above-mentioned flame retardant, characterized by comprising the following steps: S11, ultrasonic dispersion (40 kHz, 300 W, 30 min) followed by spray drying (inlet 180℃, outlet 80℃).
[0010] S12. After sieving, a composite flame retardant with a particle size ≤50μm is obtained.
[0011] Furthermore, in step S11, before ultrasonic treatment, POSS-DOPO and MPP are dissolved in anhydrous ethanol, wherein the total mass of POSS-DOPO and MPP is 20% of the mass of ethanol.
[0012] Furthermore, in step S11, the spray drying conditions are: inlet temperature 180°C, outlet temperature 80°C, feed rate 5 ml / min, and atomization pressure 0.3 MPa.
[0013] This invention provides a resin comprising the flame retardant, characterized in that it comprises the following raw materials in parts by weight: 18-25 parts flame retardant; 100 parts of epoxy resin.
[0014] Furthermore, the resin containing the flame retardant is prepared by adding the flame retardant to epoxy resin preheated to 60°C, stirring (500 rpm, 30 minutes), and then curing under vacuum (120°C / 2h + 180°C / 2h).
[0015] This invention provides a flame retardant, its preparation method, and a resin containing the flame retardant, which has the following beneficial effects: 1. Chemically bonded POSS-DOPO copolymer: DOPO is grafted onto the POSS cage structure through a free radical reaction, combining high phosphorus content (≥12%) and the heat resistance of silicon.
[0016] 2. Compound optimization: MPP (nitrogen source) and n-HAP (charring agent) are introduced, and the dispersibility is improved by spray drying process.
[0017] 3. High flame retardancy efficiency: LOI is 38.4%, UL-94 is V0, and maximum smoke density (Ds) is 150.6.
[0018] 4. Excellent thermal stability: TGA 5% weight loss temperature ≥300℃.
[0019] 5. High retention of mechanical properties: tensile strength ≥80 MPa (retention rate ≥85%). Detailed Implementation
[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0021] Material description: Serial Number Components Manufacturers model 1 Octavinyl-POSS Sigma 475424 2 DOPO TCI D1874 3 MPP McLean M850103 4 HAp McLean H861730 5 Coupling agent Japan Shin-Etsu KBM-403 6 Epoxy resin Mitsubishi Chemical JER828 7 DCP Sigma 329541 Example 1
[0022] A flame retardant comprising the following components in parts by weight, 18 copies of POSS-DOPO; 7 parts of melamine polyphosphate (MPP); 3 parts of nano-hydroxyapatite (HAp); 0.5 parts of silane coupling agent.
[0023] POSS-DOPO is prepared by the following method. S1. Mix the raw materials by dissolving octavinyl-POSS and DOPO in 10 times their volume (w / v) of toluene at a molar ratio of 1:8 and stirring for 30 minutes under nitrogen protection to obtain the mixed raw materials. S2, Free radical addition reaction: Add 0.5 wt% of the mixed raw materials according to step S1 to dicumyl peroxide (DCP), react at 110℃ for 6 hours to obtain a viscous solution; S3. Purification: Add methanol to the viscous solution from step S2 to precipitate, filter, and vacuum dry to obtain a white powder, namely POSS-DOPO.
[0024] The method for pretreating HAp with a silane coupling agent is as follows: S21. Preparation of silane coupling agent hydrolysis solution: Slowly add silane coupling agent to ethanol-water mixture, water:ethanol (v / v) = 1:2, stir magnetically, 300 rpm, 25℃, for 30 minutes, until the solution is clear and transparent; S22. HAp surface modification: In a 60℃ water bath, the hydrolysis solution of silane coupling agent was added dropwise to an ethanol suspension of HAp, the HAp content of which was 10wt%. The mixture was stirred at 500 rpm while being sonicated at 200 W and 40 kHz. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 minutes and the supernatant was discarded to obtain HAp pretreated with silane coupling agent.
[0025] The preparation method of the above flame retardant includes the following steps: S11. Dissolve POSS-DOPO and MPP in anhydrous ethanol, with the total mass of POSS-DOPO and MPP in the solution being 20% of the mass of ethanol. Disperse by sonication at 40 kHz, 300 W, for 30 minutes. Then, add HAp pretreated with silane coupling agent and continue sonication for 15 minutes. Finally, spray dry the solution under the following conditions: inlet temperature 180℃, outlet temperature 80℃, feed rate 5 ml / min, and atomization pressure 0.3 MPa.
[0026] S12, passing through a 200-mesh sieve, yields a composite flame retardant with a particle size ≤50μm.
[0027] A resin comprising the above-mentioned flame retardant, comprising the following raw materials in parts by weight: 18 parts flame retardant; 100 parts of epoxy resin.
[0028] The resin containing the flame retardant was prepared by adding the flame retardant to epoxy resin preheated to 60°C, stirring, 500 rpm for 30 minutes, and then curing under vacuum degassing conditions of 120°C / 2h + 180°C / 2h.
[0029] To reduce the risk of flame retardant migration, resin can also be prepared by in-situ polymerization. For example, first, 20 parts by weight of flame retardant are added to 80 parts by weight of epoxy monomer, and the mixture is heated at 60°C for 1 hour; then, 80% by weight of MHHPA epoxy monomer is added, and the mixture is heated at 100°C for 1 hour; finally, the mixture is cured in stages at 80°C for 1 hour and at 150°C for 3 hours.
[0030] The oxygen index (LOI) obtained in this embodiment is 38.4%, UL-94 is V0, and the maximum smoke density is 150.6.
[0031] Example 2
[0032] A flame retardant comprising the following components in parts by weight, 16 copies of POSS-DOPO; 8 parts of melamine polyphosphate (MPP); 5 parts of nano-hydroxyapatite (HAp); One part of silane coupling agent.
[0033] POSS-DOPO is prepared by the following method. S1. Mix the raw materials by dissolving octavinyl-POSS and DOPO in 10 times their volume (w / v) of toluene at a molar ratio of 1:8 and stirring for 30 minutes under nitrogen protection to obtain the mixed raw materials. S2, Free radical addition reaction: Add 0.5 wt% of the mixed raw materials according to step S1 to dicumyl peroxide (DCP), react at 110℃ for 6 hours to obtain a viscous solution; S3. Purification: Add methanol to the viscous solution from step S2 to precipitate, filter, and vacuum dry to obtain a white powder, namely POSS-DOPO.
[0034] The method for pretreating HAp with a silane coupling agent is as follows: S21. Preparation of silane coupling agent hydrolysis solution: Slowly add silane coupling agent to ethanol-water mixture, water:ethanol (v / v) = 1:2, stir magnetically, 300 rpm, 25℃, for 30 minutes, until the solution is clear and transparent; S22. HAp surface modification: In a 60℃ water bath, the hydrolysis solution of silane coupling agent was added dropwise to an ethanol suspension of HAp, the HAp content of which was 10wt%. The mixture was stirred at 500 rpm while being sonicated at 200 W and 40 kHz. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 minutes and the supernatant was discarded to obtain HAp pretreated with silane coupling agent.
[0035] The preparation method of the above flame retardant includes the following steps: S11. Dissolve POSS-DOPO and MPP in anhydrous ethanol, with the total mass of POSS-DOPO and MPP in the solution being 20% of the mass of ethanol. Disperse by sonication at 40 kHz, 300 W, for 30 minutes. Then, add HAp pretreated with silane coupling agent and continue sonication for 15 minutes. Finally, spray dry the solution under the following conditions: inlet temperature 180℃, outlet temperature 80℃, feed rate 5 ml / min, and atomization pressure 0.3 MPa.
[0036] S12, passing through a 200-mesh sieve, yields a composite flame retardant with a particle size ≤50μm.
[0037] A resin comprising the above-mentioned flame retardant, comprising the following raw materials in parts by weight: 25 parts flame retardant; 100 parts of epoxy resin.
[0038] The resin containing the flame retardant was prepared by adding the flame retardant to epoxy resin preheated to 60°C, stirring, 500 rpm for 30 minutes, and then curing under vacuum degassing conditions of 120°C / 2h + 180°C / 2h.
[0039] To reduce the risk of flame retardant migration, resin can also be prepared by in-situ polymerization. For example, first, 20 parts by weight of flame retardant are added to 80 parts by weight of epoxy monomer, and the mixture is heated at 60°C for 1 hour; then, 80% by weight of MHHPA epoxy monomer is added, and the mixture is heated at 100°C for 1 hour; finally, the mixture is cured in stages at 80°C for 1 hour and at 150°C for 3 hours.
[0040] The oxygen index (LOI) obtained in this embodiment is 36.7%, UL-94 is V0, and the maximum smoke density is 162.4. Example
[0041] A flame retardant comprising the following components in parts by weight, 20 copies of POSS-DOPO; 5 parts of melamine polyphosphate (MPP); 5 parts of nano-hydroxyapatite (HAp); 0.8 parts of silane coupling agent.
[0042] POSS-DOPO is prepared by the following method. S1. Mix the raw materials by dissolving octavinyl-POSS and DOPO in 10 times their volume (w / v) of toluene at a molar ratio of 1:8 and stirring for 30 minutes under nitrogen protection to obtain the mixed raw materials. S2, Free radical addition reaction: Add 0.5 wt% of the mixed raw materials according to step S1 to dicumyl peroxide (DCP), react at 110℃ for 6 hours to obtain a viscous solution; S3. Purification: Add methanol to the viscous solution from step S2 to precipitate, filter, and vacuum dry to obtain a white powder, namely POSS-DOPO.
[0043] The method for pretreating HAp with a silane coupling agent is as follows: S21. Preparation of silane coupling agent hydrolysis solution: Slowly add silane coupling agent to ethanol-water mixture, water:ethanol (v / v) = 1:2, stir magnetically, 300 rpm, 25℃, for 30 minutes, until the solution is clear and transparent; S22. HAp surface modification: In a 60℃ water bath, the hydrolysis solution of silane coupling agent was added dropwise to an ethanol suspension of HAp, the HAp content of which was 10wt%. The mixture was stirred at 500 rpm while being sonicated at 200 W and 40 kHz. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 minutes and the supernatant was discarded to obtain HAp pretreated with silane coupling agent.
[0044] The preparation method of the above flame retardant includes the following steps: S11. Dissolve POSS-DOPO and MPP in anhydrous ethanol, with the total mass of POSS-DOPO and MPP in the solution being 20% of the mass of ethanol. Disperse by sonication at 40 kHz, 300 W, for 30 minutes. Then, add HAp pretreated with silane coupling agent and continue sonication for 15 minutes. Finally, spray dry the solution under the following conditions: inlet temperature 180℃, outlet temperature 80℃, feed rate 5 ml / min, and atomization pressure 0.3 MPa.
[0045] S12, passing through a 200-mesh sieve, yields a composite flame retardant with a particle size ≤50μm.
[0046] A resin comprising the above-mentioned flame retardant, comprising the following raw materials in parts by weight: 20 parts flame retardant; 100 parts of epoxy resin.
[0047] The resin containing the flame retardant was prepared by adding the flame retardant to epoxy resin preheated to 60°C, stirring, 500 rpm for 30 minutes, and then curing under vacuum degassing conditions of 120°C / 2h + 180°C / 2h.
[0048] To reduce the risk of flame retardant migration, resin can also be prepared by in-situ polymerization. For example, first, 20 parts by weight of flame retardant are added to 80 parts by weight of epoxy monomer, and the mixture is heated at 60°C for 1 hour; then, 80% by weight of MHHPA epoxy monomer is added, and the mixture is heated at 100°C for 1 hour; finally, the mixture is cured in stages at 80°C for 1 hour and at 150°C for 3 hours.
[0049] The oxygen index (LOI) obtained in this embodiment is 35.9%, UL-94 is V0, and the maximum smoke density is 168.5.
[0050] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.
[0051] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A flame retardant, characterized in that: Includes the following components by weight: POSS-DOPO16-20 copies; 5-8 parts of melamine polyphosphate; 3-5 parts of nano-hydroxyapatite.
2. The flame retardant as described in claim 1, characterized in that: The flame retardant also includes the following components by weight: 0.5-1 part silane coupling agent.
3. The flame retardant as described in claim 2, characterized in that: The flame retardant comprises the following components in parts by weight: 18 copies of POSS-DOPO; 7 parts of melamine polyphosphate; Three parts of nano-hydroxyapatite; 0.5 parts of silane coupling agent.
4. The flame retardant as described in claim 1, characterized in that: POSS-DOPO was prepared by the following method. S1. Mixing raw materials: Dissolve octavinyloctasilylsesquioxane and DOPO in toluene at a molar ratio of 1:8, and stir for 30 minutes under nitrogen protection to obtain a mixed raw material. S2, Free radical addition reaction: Add 0.5 wt% of the mixed raw materials according to step S1 to dicumyl peroxide, react at 110℃ for 6 hours to obtain a viscous solution; S3. Purification: Add methanol to the viscous solution from step S2 to precipitate, filter, and vacuum dry to obtain a white powder.
5. The method for preparing the flame retardant according to any one of claims 1-4, characterized in that: Includes the following steps, S11. Ultrasonic dispersion followed by spray drying; S12. After sieving, a composite flame retardant with a particle size ≤50μm is obtained.
6. The method for preparing the flame retardant as described in claim 5, characterized in that: In step S11, before ultrasonic treatment, POSS-DOPO and MPP are dissolved in anhydrous ethanol, wherein the total mass of POSS-DOPO and MPP is 20% of the mass of ethanol.
7. The method for preparing the flame retardant as described in claim 5, characterized in that: In step S11, the spray drying conditions are: inlet temperature 180℃, outlet temperature 80℃, feed rate 5ml / min, and atomization pressure 0.3Mpa.
8. A resin comprising the flame retardant as described in any one of claims 1-4, characterized in that, Including the following raw materials by weight, 18-25 parts flame retardant; 100 parts of epoxy resin.
9. The method for preparing the resin according to claim 8, characterized in that, The method includes the following steps: adding flame retardant to epoxy resin preheated to 60°C, stirring, and then curing under vacuum degassing.