Halogen-free flame-retardant nylon material and preparation method thereof

Abstract

The invention relates to the technical field of flame-retardant nylon materials, and provides a halogen-free flame-retardant nylon material and a preparation method thereof, the halogen-free flame-retardant nylon material comprises the following components by mass: 80-120 parts of nylon, 30-40 parts of modified polyacrylate, 1-10 parts of modified nylon, 20-40 parts of a halogen-free flame retardant, and 0.1-5 parts of an auxiliary agent; the modified polyacrylate is a copolymer of phosphorus pentoxide, hydroxyl acrylate, acrylic acid, acrylate, glass fiber and antimony trioxide; the modified nylon is a copolymer of nylon and acrylate. The components have good affinity, a uniform and stable mixed system can be formed, the mechanical strength and flame retardant property of the nylon composite material can be obviously improved by introducing the components, the product is endowed with more excellent comprehensive performance, harm to the environment and human bodies can be avoided, the ecological friendliness is higher, and the nylon composite material is suitable for industrial production. The problems existing in the prior art are solved, and the method has important significance on development and further popularization of nylon products.

Description

Technical Field

[0001] The invention relates to the technical field of flame-retardant nylon materials, and in particular to a halogen-free flame-retardant nylon material and a preparation method thereof. Background Art

[0002] Nylon material, also known as polyamide (PA for short), is a polymer compound with a variety of uses. It has a high melting point, excellent mechanical properties, strong heat resistance, good corrosion resistance and wear resistance. For this reason, nylon has been widely used in many fields such as chemical industry, electronic and electrical, and mechanical manufacturing. However, due to the flammable nature of nylon, there are great safety hazards in the event of a fire, which has led to the research of flame-retardant nylon materials receiving attention, and the demand for nylon materials with high flame retardancy is also growing.

[0003] In the development of flame-retardant nylon materials, the focus of early work was on using different types of flame-retardant additives to enhance the flame retardancy of materials. Specifically, bromine-based, chlorine-based, and fluorine-based flame retardants have high flame retardant efficiency and have been widely adopted. They have effectively improved the flame retardancy of materials in practical applications and ensured that the materials can meet basic fire protection standards.

[0004] However, on the one hand, traditional flame retardants contain harmful substances such as halogens, so they will release toxic gases and smoke during use, which poses a great risk of pollution to the environment and does not conform to the current concept of energy conservation, emission reduction, and green environmental protection; on the other hand, due to the poor affinity of flame retardants with organic polymers, they are easily unevenly distributed inside the material, resulting in significant differences in the flame retardant effect of different parts of the material, and cannot effectively play a flame retardant role as a whole, making it difficult to meet strict fire protection standards. In addition, the lack of compatibility between multiple components also leads to a decrease in the overall performance of the material, such as strength, stability, and service life. The flame retardant properties of polymer materials toughened with glass fiber are often worse. This is because glass fiber has a "wick effect", similar to the wick of a candle, which can guide heat and combustibles to the fire source or high-temperature area, thereby promoting combustion, further increasing safety hazards.

[0005] In summary, it is necessary to develop a new technical solution to solve the problems existing in the prior art. Summary of the invention

[0006] The present invention provides a halogen-free flame-retardant nylon material, which is compounded with modified polyacrylate, modified nylon, a flame retardant and a nylon matrix resin. The components not only have good affinity with each other and can form a uniform and stable mixed system, but also the introduced ingredients can significantly improve the mechanical strength and flame retardant properties of the nylon composite material, giving the product more excellent comprehensive performance. The halogen-free flame retardant can also avoid harm to the environment and human body, and is more eco-friendly. Therefore, the present invention solves the problems existing in the prior art and is of great significance to the development and further promotion of nylon products.

[0007] An object of the present invention is to provide a halogen-free flame-retardant nylon material, comprising the following components in parts by weight: Nylon 80-120 parts Modified polyacrylate 30-40 parts Modified nylon 1-10 parts Halogen-free flame retardant 20-40 parts Additives 0.1-5 parts; in, The modified polyacrylate is a copolymer of phosphorus pentoxide, hydroxy acrylate, acrylic acid, acrylate, glass fiber and antimony trioxide; The modified nylon is a copolymer of nylon and acrylate.

[0008] Furthermore, the nylon is selected from one or more of nylon 6, nylon 66, nylon 1010 and nylon 610.

[0009] Furthermore, the halogen-free flame retardant is selected from phosphate flame retardants or silicone flame retardants.

[0010] Furthermore, the halogen-free flame retardant is preferably a phosphate flame retardant.

[0011] Furthermore, the auxiliary agent is selected from one or more of an antioxidant, a lubricant, a light stabilizer, an odor inhibitor, a toughening agent, a crosslinking agent, and an initiator.

[0012] Another object of the present invention is to provide a method for preparing the above-mentioned halogen-free flame-retardant nylon material, the method for preparing the halogen-free flame-retardant nylon material comprising the following steps: S1, hydroxylating antimony trioxide and glass fiber, then adding them into acrylic acid, heating at 70-90°C for reaction, to obtain intermediate product 1; S2, mixing phosphorus pentoxide and hydroxy acrylate, heating at 60-90° C. to react, to obtain an intermediate product 2; S3, mixing the intermediate product 1, the intermediate product 2, the acrylic ester and the catalyst, heating and stirring at 60-90° C. under an inert gas atmosphere to react, to obtain a modified polyacrylate; S4, mixing nylon, acrylate and initiator, heating and stirring at 60-90°C for reaction, and obtaining modified nylon; S5. Mix the modified polyacrylate, modified nylon, nylon, halogen-free flame retardant and additives, add them into an extruder, melt-extrude and granulate to obtain a halogen-free flame retardant nylon material.

[0013] Furthermore, in step S1, the mass ratio of antimony trioxide to glass fiber is 1:(1-3).

[0014] Furthermore, in step S2, the molar ratio of phosphorus pentoxide to hydroxy acrylate is 1:(1.5-3).

[0015] Furthermore, in step S3, the mass ratio of the intermediate product 1, the intermediate product 2 and the acrylic ester is (4-8):(1-5):(1-3).

[0016] Furthermore, in step S4, the mass ratio of nylon to acrylate is 1:(4-8).

[0017] The present invention has the following beneficial effects: The present invention provides a halogen-free flame-retardant nylon material, which is compounded with nylon, modified polyacrylate, modified nylon and halogen-free flame retardant and other components. Among them, the modified polyacrylate first grafts hydroxylated antimony trioxide and glass fiber mixture with acrylic acid to obtain intermediate product 1, and reacts phosphorus pentoxide with hydroxyl acrylic acid ester to obtain intermediate product 2 with phosphate structure, and then the intermediate product 1, intermediate product 2 and acrylate monomer with double bonds are subjected to free radical polymerization to obtain modified polyacrylate, which not only has flame-retardant antimony trioxide and phosphate groups, but also introduces glass fiber, which can improve the strength of the composite material. At the same time, since the flame retardant material and the glass fiber are connected by chemical bonds, the situation of combustibles being conducted through the glass fiber is avoided, and the possibility of combustion is effectively reduced. In addition, the modified polyacrylate has excellent affinity with the phosphate flame retardant, which helps to promote the uniform dispersion and combination of the halogen-free flame retardant in the mixed system, thereby maximizing the function of the flame retardant and meeting various strict and extreme fire protection requirements.

[0018] The modified nylon of the present invention is obtained by copolymerizing acrylate and nylon, and the polyacrylate macromolecule is grafted into the nylon material, thereby playing the role of a compatibilizer. After being melt-mixed with nylon, modified polyacrylate, additives and other components, the compatibility between different substances can be enhanced, and the bonding strength of nylon, modified polyacrylate and flame retardant is further enhanced, thereby ensuring the reliability of the product's mechanical properties, flame retardant properties, stability, durability and other aspects. DETAILED DESCRIPTION

[0019] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0020] The words "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0021] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers indicating, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that vary depending on the desired properties to be obtained by the present invention.

[0022] The present invention uses the following raw materials: Nylon:Nylon 66.

[0023] Glass fiber: Chopped glass fiber, purchased from Taian Senyang Composite Materials Co., Ltd.

[0024] Halogen-free flame retardant: triphenyl phosphate.

[0025] Additives: light stabilizer UV-3529, antioxidant 1010, lubricant calcium stearate and initiator DTBP in a mass ratio of 1:1:1:1.

[0026] Example 1 A halogen-free flame-retardant nylon material is prepared from the following raw materials in parts by weight: Nylon 80 parts 30 parts of modified polyacrylate Modified nylon 3 parts Halogen-free flame retardant 25 parts 2 parts of auxiliary agent; The preparation method of the above-mentioned halogen-free flame-retardant nylon material comprises the following steps: S1, Sb2O3 powder (average particle size 30 μm) and glass fiber in a mass ratio of 1:3 were immersed in a 5 mol / L sodium hydroxide solution, ultrasonically treated for 3 h, then washed to neutrality, dried and mixed with glucose (Sb2O3: glucose = 1:10, m / m) for ball milling (ball-to-material ratio 5:1), washed and dried, the product was immersed in acrylic acid, ultrasonically reacted at 80 ° C for 10 h, filtered, washed and dried to obtain the intermediate product 1; S2, phosphorus pentoxide and hydroxypropyl methacrylate in a molar ratio of 1:2 were mixed, reacted at 75°C for 3 h, then 4 wt% of water was added to the system for hydrolysis, and kept at 90°C for 2 h to obtain intermediate product 2; S3, using water as solvent, mixing the intermediate product 1, intermediate product 2 and methyl methacrylate in a mass ratio of 6:3:1, under nitrogen atmosphere and BPO catalyst (1% by mass of reactants), stirring at 80° C. for 12 h, filtering, washing and drying to obtain modified polyacrylate; S4, using water and isopropanol in a volume ratio of 4:1 as solvent, mixing nylon and methyl methacrylate in a mass ratio of 1:5, using copper nitrate (1% by mass of the reactants) and DMA (5% by mass of the reactants) as initiator system, stirring and reacting at 70°C for 4 h, filtering, washing, and drying to obtain modified nylon; S5. According to the above mass fractions, the modified polyacrylate, modified nylon, nylon, halogen-free flame retardant and additives are uniformly mixed and added into a twin-screw extruder at 230° C. for melt extrusion and granulation to obtain a halogen-free flame retardant nylon material.

[0027] Example 2 A halogen-free flame-retardant nylon material is prepared from the following raw materials in parts by weight: Nylon 100 parts 35 parts of modified polyacrylate Modified nylon 4 parts Halogen-free flame retardant 30 parts 2.5 parts of additives; The preparation method of the above-mentioned halogen-free flame-retardant nylon material comprises the following steps: S1, Sb2O3 powder (average particle size 30 μm) and glass fiber in a mass ratio of 1:3 were immersed in a 5 mol / L sodium hydroxide solution, ultrasonically treated for 3 h, then washed to neutrality, dried and mixed with glucose (Sb2O3: glucose = 1:10, m / m) for ball milling (ball-to-material ratio 5:1), washed and dried, the product was immersed in acrylic acid, ultrasonically reacted at 80 ° C for 10 h, filtered, washed and dried to obtain the intermediate product 1; S2, phosphorus pentoxide and hydroxypropyl methacrylate in a molar ratio of 1:2 were mixed, reacted at 75°C for 3 h, then 4 wt% of water was added to the system for hydrolysis, and kept at 90°C for 2 h to obtain intermediate product 2; S3, using water as solvent, mixing the intermediate product 1, intermediate product 2 and methyl methacrylate in a mass ratio of 6:3:1, under nitrogen atmosphere and BPO catalyst (1% by mass of reactants), stirring at 80° C. for 12 h, filtering, washing and drying to obtain modified polyacrylate; S4, using water and isopropanol in a volume ratio of 4:1 as solvent, mixing nylon and methyl methacrylate in a mass ratio of 1:5, using copper nitrate (1% by mass of the reactants) and DMA (5% by mass of the reactants) as initiator system, stirring and reacting at 70°C for 4 h, filtering, washing, and drying to obtain modified nylon; S5. According to the above mass fractions, the modified polyacrylate, modified nylon, nylon, halogen-free flame retardant and additives are uniformly mixed and added into a twin-screw extruder at 230° C. for melt extrusion and granulation to obtain a halogen-free flame retardant nylon material.

[0028] Example 3 A halogen-free flame-retardant nylon material is prepared from the following raw materials in parts by weight: Nylon 120 parts 40 parts of modified polyacrylate Modified nylon 5 parts 35 parts of halogen-free flame retardant 3 parts of additives; The preparation method of the above-mentioned halogen-free flame-retardant nylon material comprises the following steps: S1, Sb2O3 powder (average particle size 30 μm) and glass fiber in a mass ratio of 1:3 were immersed in a 5 mol / L sodium hydroxide solution, ultrasonically treated for 3 h, then washed to neutrality, dried and mixed with glucose (Sb2O3: glucose = 1:10, m / m) for ball milling (ball-to-material ratio 5:1), washed and dried, the product was immersed in acrylic acid, ultrasonically reacted at 80 ° C for 10 h, filtered, washed and dried to obtain the intermediate product 1; S2, phosphorus pentoxide and hydroxypropyl methacrylate in a molar ratio of 1:2 were mixed, reacted at 75°C for 3 h, then 4 wt% of water was added to the system for hydrolysis, and kept at 90°C for 2 h to obtain intermediate product 2; S3, using water as solvent, mixing the intermediate product 1, intermediate product 2 and methyl methacrylate in a mass ratio of 6:3:1, under nitrogen atmosphere and BPO catalyst (1% by mass of reactants), stirring at 80° C. for 12 h, filtering, washing and drying to obtain modified polyacrylate; S4, using water and isopropanol in a volume ratio of 4:1 as solvent, mixing nylon and methyl methacrylate in a mass ratio of 1:5, using copper nitrate (1% by mass of the reactants) and DMA (5% by mass of the reactants) as initiator system, stirring and reacting at 70°C for 4 h, filtering, washing, and drying to obtain modified nylon; S5. According to the above mass fractions, the modified polyacrylate, modified nylon, nylon, halogen-free flame retardant and additives are uniformly mixed and added into a twin-screw extruder at 230° C. for melt extrusion and granulation to obtain a halogen-free flame retardant nylon material.

[0029] Comparative Example 1 A halogen-free flame-retardant nylon material. The difference between this comparative example and Example 1 is that step S1 is deleted, and the intermediate product 1 is replaced by a mixture of Sb2O3 and glass fiber in a mass ratio of 1:2. The remaining ingredients and preparation method are the same as those in Example 1.

[0030] Comparative Example 2 A halogen-free flame-retardant nylon material. The difference between this comparative example and Example 1 is that step S2 is deleted, and in step S3, intermediate product 2 is not added. The remaining ingredients and preparation method are the same as those in Example 1.

[0031] Comparative Example 3 A halogen-free flame-retardant nylon material. The difference between this comparative example and Example 1 is that step S4 is deleted and modified nylon is not added. The remaining ingredients and preparation method are the same as those of Example 1.

[0032] Test Case The performance of the halogen-free flame-retardant nylon materials prepared in Examples 1-3 and Comparative Examples 1-3 was tested.

[0033] Test method: The tensile strength, flexural strength and flame retardancy are measured according to ISO 527, ISO 178, UL-94 and other standards.

[0034] The test results are shown in Table 1.

[0035] Table 1 Performance test results According to Table 1, it can be seen that the compatibility of various components in the halogen-free flame-retardant nylon materials prepared in Examples 1-3 is good, and the glass fiber, Sb2O3 and phosphate in the modified polyacrylate can maximize their own functions. Under the volume-increasing effect of the modified nylon, the combination effect with nylon and the halogen-free flame retardant is further improved, and synergistic synergy is achieved, with excellent comprehensive performance. However, Comparative Examples 1-3 replace the modified polyacrylate or modified nylon components, reduce the affinity between different substances, and the stability, uniformity and degree of combination of the mixed system are reduced, resulting in the mechanical strength and flame retardancy of the samples being less than ideal. In summary, the halogen-free flame-retardant nylon material of the present invention has excellent performance, overcomes the defects existing in the prior art, and has good application prospects.

[0036] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0037] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A halogen-free flame-retardant nylon material, characterized in that: The halogen-free flame-retardant nylon material comprises the following components in parts by mass: Nylon 80-120 parts Modified polyacrylate 30-40 parts Modified nylon 1-10 parts Halogen-free flame retardant 20-40 parts Additives 0.1-5 parts; in, The modified polyacrylate is a copolymer of phosphorus pentoxide, hydroxy acrylate, acrylic acid, acrylate, glass fiber and antimony trioxide; The modified nylon is a copolymer of nylon and acrylate.

2. The halogen-free flame-retardant nylon material according to claim 1, characterized in that: The nylon is selected from one or more of nylon 6, nylon 66, nylon 1010 and nylon 610.

3. The halogen-free flame-retardant nylon material according to claim 1, characterized in that: The halogen-free flame retardant is selected from phosphate flame retardants or organosilicon flame retardants.

4. The halogen-free flame-retardant nylon material according to claim 1, characterized in that: The auxiliary agent is selected from one or more of an antioxidant, a lubricant, a light stabilizer, an odor inhibitor, a toughening agent, a crosslinking agent, and an initiator.

5. A method for preparing a halogen-free flame-retardant nylon material, for preparing the halogen-free flame-retardant nylon material according to any one of claims 1 to 4, characterized in that: The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: S1, hydroxylating antimony trioxide and glass fiber, then adding them into acrylic acid, heating at 70-90°C for reaction, to obtain intermediate product 1; S2, mixing phosphorus pentoxide and hydroxy acrylate, heating at 60-90° C. to react, to obtain an intermediate product 2; S3, mixing the intermediate product 1, the intermediate product 2, the acrylic ester and the catalyst, heating and stirring at 60-90° C. under an inert gas atmosphere to react, to obtain a modified polyacrylate; S4, mixing nylon, acrylate and initiator, heating and stirring at 60-90°C for reaction, and obtaining modified nylon; S5. Mix the modified polyacrylate, modified nylon, nylon, halogen-free flame retardant and additives, add them into an extruder, melt-extrude and granulate to obtain a halogen-free flame retardant nylon material.

6. The method for preparing the halogen-free flame-retardant nylon material according to claim 5, characterized in that: In step S1, the mass ratio of antimony trioxide to glass fiber is 1:(1-3).

7. The method for preparing the halogen-free flame-retardant nylon material according to claim 5, characterized in that: In step S2, the molar ratio of phosphorus pentoxide to hydroxy acrylate is 1:(1.5-3).

8. The method for preparing the halogen-free flame-retardant nylon material according to claim 5, characterized in that: In step S3, the mass ratio of the intermediate product 1, the intermediate product 2 and the acrylic ester is (4-8):(1-5):(1-3).

9. The method for preparing the halogen-free flame-retardant nylon material according to claim 5, characterized in that: In step S4, the mass ratio of nylon to acrylate is 1:(4-8).

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