Flame-retardant PA66 composite material as well as preparation method and application thereof

Abstract

The invention provides a flame-retardant PA66 composite material and a preparation method and application thereof.The flame-retardant PA66 composite material comprises PA66 resin, red phosphorus, a flexibilizer, a reinforcing material and a quaternary ammonium salt compound, and through reasonable matching of all the components, the obtained PA66 composite material further has the advantages of being low in phosphine release amount on the premise that the excellent flame-retardant performance is achieved, and the flame-retardant performance is good. The flame-retardant copper alloy has the advantages that the flame-retardant copper alloy is low in flame retardancy, low in corrosion to metal copper, excellent in mechanical property, particularly high in toughness and suitable for being applied to products with high requirements on flame retardancy, metal corrosion and toughness.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite materials, and particularly relates to a flame-retardant PA66 composite material and a preparation method and application thereof. Background Art

[0002] PA66 (poly(hexamethylene adipate)) resin has very excellent mechanical properties, wear resistance, heat resistance and solvent resistance, and is therefore widely used in machinery manufacturing, power tools, electronic appliances, transportation and other fields. However, the poor flame retardancy of PA66 resin itself limits its wide application in the field of electronic appliances, so it needs to be flame-retardant modified.

[0003] Red phosphorus is a commonly used halogen-free flame retardant. It has little impact on the mechanical properties of the substrate, and its electrical properties and smoke density are superior to halogenated flame retardant systems. It also has the advantages of low density and high cost performance. Therefore, it is often used in the flame retardant modification of PA66. However, red phosphorus is prone to produce phosphine under the influence of heat, oxygen and water. Phosphine will further convert into oxygen-containing acids. Oxygen-containing acids will corrode metals in close contact, which will seriously affect the conductivity of electronic and electrical products, causing product quality abnormalities and shortening product service life.

[0004] To address the issue of red phosphorus flame-retardant PA66 being susceptible to metal corrosion, three common approaches have been proposed: First, red phosphorus is modified to reduce the production of phosphine and oxygen-containing acids. For example, CN101503568A and CN1775664A both utilize microencapsulated red phosphorus for modification. By coating the red phosphorus, they reduce its contact with water and oxygen, thereby reducing phosphine production. However, in actual production, this method requires subjecting the red phosphorus to shearing and heating in a twin-screw extruder, followed by injection molding in a single screw, making it difficult to address the production of phosphine and oxygen-containing acids at the source. Second, phosphine production is reduced by weakening screw shear or by introducing nitrogen during production. For example, CN103304997A introduces nitrogen to prevent contact between red phosphorus and oxygen, reducing the production of phosphine and oxygen-containing acids and, in turn, metal corrosion. However, this method is complex and expensive to produce. The third approach is to use adsorbents, fillers, or metal oxides to absorb and suppress the generated phosphine. For example, EP2072566A uses activated carbon and zeolite to adsorb phosphine, reducing the formation of oxygen-containing acids and, in turn, reducing metal corrosion. Another example is CN107793749A, which adds diatomaceous earth to adsorb phosphine, CN103992634A, which reduces phosphine production by adding iron oxides, and CN105038211A, which reduces phosphine production by adding hydroxides, talc, magnesium oxide, and calcium oxide. However, these fillers, adsorbents, metal oxides, and hydroxides can significantly negatively impact the mechanical properties of the material, especially its toughness, hindering the application of the resulting PA66 composite material in high-toughness products.

[0005] Therefore, in response to the above problems, there is an urgent need to develop a flame retardant PA66 composite material with excellent flame retardant properties, low metal corrosion and high toughness. Summary of the Invention

[0006] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a flame-retardant PA66 composite material and its preparation method and application. The flame-retardant PA66 composite material has the characteristics of low phosphine release, low corrosion to metal, high toughness and excellent flame retardant performance, and can be widely used in products with high requirements for flame retardancy, metal corrosion and toughness.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a flame retardant polyamide 66 composite material, wherein the flame retardant PA66 composite material comprises the following components in parts by weight:

[0009] 20-60 parts by weight of PA66 resin;

[0010]

[0011] The flame-retardant PA66 composite material provided by the present invention includes PA66 resin, red phosphorus, a reinforcing material, a toughening agent and a quaternary ammonium salt compound; by adding the red phosphorus, the flame retardant properties of the obtained PA66 composite material are effectively improved, and by adding the toughening agent and the reinforcing material, the toughness of the obtained PA66 composite material is effectively improved. Finally, by adding the quaternary ammonium salt compound, the problem of the added red phosphorus easily generating phosphine is significantly reduced, thereby effectively reducing the corrosiveness of the obtained PA66 composite material to metals; therefore, through the reasonable combination of the above-mentioned various components, the obtained PA66 composite material has excellent flame retardant properties and also has a low phosphine release amount, thereby having very low corrosiveness to metallic copper, and also has excellent mechanical properties, especially high toughness, and is suitable for application in electronic and electrical products with high requirements for metal corrosion resistance and toughness.

[0012] Wherein, the content of the PA66 resin can be 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight or 60 parts by weight, and the mass percentage of the PA66 resin in the flame retardant PA66 composite material is not less than 25%.

[0013] The content of the red phosphorus can be 2.4 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 7 parts by weight, 9 parts by weight, 10 parts by weight or 12 parts by weight, etc.

[0014] The content of the reinforcing material can be 15 parts by weight, 17 parts by weight, 19 parts by weight, 21 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight, 29 parts by weight, 31 parts by weight, 33 parts by weight, 35 parts by weight, 40 parts by weight or 45 parts by weight, etc.

[0015] The content of the toughening agent can be 0 parts by weight, 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight or 20 parts by weight, etc.

[0016] The content of the quaternary ammonium salt compound can be 0.02 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.09 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.4 parts by weight or 0.6 parts by weight.

[0017] Preferably, the number average molecular weight of the PA66 resin is 5000-40000, for example, 5000, 7000, 9000, 11000, 13000, 15000, 20000, 25000, 30000, 35000 or 40000.

[0018] In the present invention, the number average molecular weight of the PA66 resin can be tested with reference to the ISO 16014-4:2012 standard, with the test solvent being hexafluoroisopropanol and the test column temperature being 50°C.

[0019] Preferably, the relative viscosity of the PA66 resin is 1.8 to 3.5, for example, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4 or 3.5, and more preferably 2.2 to 2.9.

[0020] In the present invention, the relative viscosity of the PA66 resin can be tested with reference to the GB / T12006.1-2009 standard. The specific test steps are: first, prepare a 0.005 g / mL PA66 resin sulfuric acid test solution; then, inject the test solution and pure solvent into an Ubbelohde viscometer, respectively, in a constant temperature water bath at 25°C, and measure the flow time of the test solution and pure solvent; finally, calculate the relative viscosity (ηr) according to the formula: ηr = t / t o , where t is the flow time of the solution to be tested, t o is the flow time of pure solvent.

[0021] Preferably, the terminal amino group concentration of the PA66 resin is ≤200 mmol / kg, for example, 200 mmol / kg, 180 mmol / kg, 160 mmol / kg, 140 mmol / kg, 120 mmol / kg, 100 mmol / kg, 80 mmol / kg, 60 mmol / kg or 40 mmol / kg.

[0022] In the present invention, the terminal amino group concentration of the PA66 resin can be tested with reference to the "HG / T4182-2012" standard.

[0023] In the present invention, the flame retardant red phosphorus is preferably added in the form of red phosphorus masterbatch, and the red phosphorus masterbatch can be obtained after microencapsulation treatment. At the same time, the present invention does not impose special restrictions on the source of the red phosphorus masterbatch. Commercially available red phosphorus masterbatch can be directly selected, or it can be homemade according to the existing microencapsulation treatment method; specifically, the microencapsulation preparation method of the red phosphorus masterbatch is: first, red phosphorus is coated with an inorganic compound, and then treated with an organic compound to increase compatibility with a polymer carrier, and finally, extrusion granulation is performed with a carrier resin to obtain the red phosphorus masterbatch; wherein, commonly used inorganic substances include zinc phosphate, calcium phosphate, calcium silicate, zinc silicate, magnesium oxide, etc.; commonly used organic substances include phenolic resin, melamine formaldehyde resin, epoxy resin, polyacrylic resin, etc.; commonly used carrier resins include PA resin, POE resin, EVA resin, EBA resin, EMA resin, etc.

[0024] Preferably, the mass percentage of red phosphorus in the red phosphorus masterbatch is 40-60%, for example, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58% or 60%.

[0025] The specific content of red phosphorus in the flame retardant PA66 composite material can be obtained by multiplying the added amount of the red phosphorus masterbatch by the mass percentage of red phosphorus in the red phosphorus masterbatch.

[0026] Preferably, the reinforcing material includes at least one of glass fiber, carbon fiber, aramid fiber or ceramic fiber.

[0027] Preferably, the content of the toughening agent in the flame retardant PA66 composite material is 6 to 20 parts by weight.

[0028] Preferably, the toughening agent includes at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted thermoplastic elastomer, maleic anhydride grafted EPDM rubber, acrylic acid grafted polyethylene, acrylic acid grafted thermoplastic elastomer, glycidyl acrylate grafted polyethylene, glycidyl acrylate grafted thermoplastic elastomer, glycidyl acrylate grafted EPDM rubber or ethylene-methyl acrylate copolymer, and is more preferably maleic anhydride grafted thermoplastic elastomer.

[0029] Preferably, the chemical formula of the quaternary ammonium salt compound is [R1R2R3R4N] + X -, wherein R1 to R3 are each independently selected from at least one of C1 to C6 (e.g., C1, C2, C3, C4, C5, or C6) alkyl, C6 to C20 (e.g., C6, C8, C10, C12, C14, C16, C18, or C20, etc.) aryl, R4 is selected from C10 to C30 (e.g., C10, C14, C18, C22, C24, C26, C28, or C30, etc.) alkyl, and X is halogen (e.g., F, Cl, Br, I, At, etc.).

[0030] Preferably, the quaternary ammonium salt compound includes any one or a combination of at least two of dimethyloctadecylbenzylammonium chloride, trimethylhexadecylammonium bromide, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, eicosyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyltriethylammonium chloride, hexacosyltrimethylammonium chloride, octadecyltrimethylammonium chloride, triacontyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, eicosyltrimethylammonium bromide, behenyltrimethylammonium bromide, behenyltriethylammonium bromide, hexacosyltrimethylammonium bromide, octadecyltrimethylammonium bromide or triacontyltrimethylammonium bromide, and further preferably dimethyloctadecylbenzylammonium chloride.

[0031] Preferably, at least one of R1 to R3 is selected from C6 to C20 aryl groups, X is selected from Cl or Br, and the quaternary ammonium salt compound is further preferably dimethyloctadecylbenzylammonium chloride.

[0032] Preferably, the mass percentage of the quaternary ammonium salt compound in the flame retardant PA66 composite material is 0.05-0.8%, for example, 0.05%, 0.07%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8%, and more preferably 0.1-0.3%. It is further preferred to limit the mass percentage of the quaternary ammonium salt compound to the above preferred range, which can ensure that the flame retardant PA66 composite material has lower metal corrosion and higher toughness. On the one hand, if the mass percentage of the quaternary ammonium salt compound is less than 0.1%, the phosphine release of the obtained PA66 composite material will increase, the metal corrosion level will be high, and the phosphorus content in the solution after immersion will be very high. On the other hand, if the mass percentage of the quaternary ammonium salt compound exceeds 0.3%, although the phosphine release and metal corrosion level of the obtained PA66 composite material can be ensured to be very low, the Izod notched impact strength of the PA66 composite material will be reduced and the toughness will be deteriorated.

[0033] Preferably, the flame retardant PA66 composite material further comprises an antioxidant and / or a lubricant.

[0034] Preferably, the content of the antioxidant in the flame retardant PA66 composite material is 0.1 to 1 part by weight, for example, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight or 1 part by weight.

[0035] Preferably, the antioxidant includes at least one of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine (antioxidant 1098), triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate (antioxidant 245), tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester (antioxidant 1010), tris[2,4-di-tert-butylphenyl]phosphite (antioxidant 168), tetrakis(2,4-di-tert-butylphenol)4,4'-biphenyl diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate or a copper salt antioxidant.

[0036] Preferably, the copper salt antioxidant comprises a mixture containing +1-valent copper salts, such as a mixture of potassium iodide, cuprous iodide and zinc stearate.

[0037] Preferably, the content of lubricant in the flame retardant PA66 composite material is 0.1 to 1 part by weight, for example, 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight or 1 part by weight.

[0038] Preferably, the lubricant includes at least one of oxidized polyethylene wax, calcium stearate, modified ethylene bis fatty acid amide, aliphatic fatty acid ester or ethylene-acrylic acid copolymer.

[0039] In addition, for the flame-retardant PA66 composite material provided by the present invention, colorants, other fillers other than reinforcing materials, weathering agents, antistatic agents, etc. can be added according to actual needs without affecting the technical effects.

[0040] For example, the colorant can be selected from quinacridone red, azo substances, azo orange, phthalocyanine blue, phthalocyanine green, naphthoxydibenzoylmethane red, anthrone red, anthrone blue, anthraquinone violet, azo orange, methylene orange, zinc sulfide, cerium sulfide, carbon black, ultramarine blue, ultramarine violet, etc.

[0041] For example, the fillers other than the reinforcing material may be glass microbeads, talc, wollastonite or magnesium hydroxide.

[0042] For example, the weathering agent may be selected from salicylate, benzotriazole, hydroxybenzophenone, and the like.

[0043] Exemplarily, the antistatic agent can be selected from ionic antistatic agents (such as sulfonates, carboxylates), nonionic antistatic agents (such as glycerides, polyoxyethylene ethers, etc.), conductive filled antistatic agents (such as carbon black, carbon nanotubes, graphene, metals and their oxides), etc.

[0044] In a second aspect, the present invention provides a method for preparing the flame-retardant PA66 composite material as described in the first aspect, the preparation method comprising: mixing the various components, extruding and granulating through an extruder, to obtain the flame-retardant PA66 composite material.

[0045] Preferably, the mixing time is 3 to 5 min, for example, 3.2 min, 3.4 min, 3.6 min, 3.8 min, 4 min, 4.2 min, 4.4 min, 4.6 min, 4.8 min or 5 min.

[0046] Preferably, the extruder is a twin-screw extruder.

[0047] Preferably, the temperature of the extrusion granulation is 250-290°C, for example, 250°C, 260°C, 270°C, 280°C or 290°C.

[0048] In a third aspect, the present invention provides a product, characterized in that the product comprises the flame-retardant PA66 composite material as described in the first aspect.

[0049] Preferably, the manufactured part comprises at least one of a household appliance component, an electronic component, a household appliance component, a gardening appliance component, a medical technology device component or a motor vehicle component.

[0050] In particular, the flame-retardant PA66 composite material can be used to prepare parts with good toughness, flame retardancy and metal corrosion resistance, and more particularly, can be used to prepare photovoltaic connector bodies.

[0051] The numerical range described in the present invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] The flame-retardant PA66 composite material provided by the present invention includes PA66 resin, red phosphorus masterbatch, toughening agent, reinforcing material and quaternary ammonium salt compound. Through the rational combination of the above components, the obtained PA composite material has excellent flame retardant properties and low phosphine release, and thus has very low corrosion to metallic copper. At the same time, it also has excellent mechanical properties, especially high toughness, and is suitable for use in electronic parts with high requirements for flame retardant properties, metal corrosion resistance and toughness. DETAILED DESCRIPTION

[0054] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0055] The detailed information of some raw materials involved in the following examples and comparative examples are as follows:

[0056] (1) PA66 resin

[0057] PA66-1: relative viscosity 2.6 purchased from Huafeng Chemical Co., Ltd., brand EP-158;

[0058] PA66-2: relative viscosity 2.4, purchased from Shenma Industrial Co., Ltd., brand EPR24;

[0059] PA66-3: relative viscosity 2.8, purchased from Shenma Industrial Co., Ltd., brand EPR27;

[0060] PA66-4: relative viscosity 2.1, purchased from Ascend Performance Materials, brand PA6621SPC;

[0061] PA66-5: relative viscosity is 3.2, purchased from Shenma Industrial Co., Ltd., brand EPR32.

[0062] (2) Red phosphorus masterbatch

[0063] Red phosphorus masterbatch: red phosphorus with an effective content of 45 wt % was purchased from Tongcheng Xinde New Materials Co., Ltd. with the brand name FR9950T.

[0064] (3) Reinforcement materials

[0065] Glass fiber: purchased from Jushi Group, brand ECS10-03-568H.

[0066] (4) Toughening agent

[0067] POE-g-MAH: maleic anhydride grafted thermoplastic elastomer, purchased from DowDuPont, brand FUSABONDN493;

[0068] Ethylene-methyl acrylate copolymer: purchased from Arkema SA, brand 35BA40.

[0069] (5) Quaternary ammonium salt compounds

[0070] Trimethylhexadecyl ammonium bromide: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand CTAB;

[0071] Dimethyloctadecylbenzyl ammonium chloride: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand 1827;

[0072] Dodecyltrimethylammonium chloride: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand DTAC;

[0073] Dodecyltrimethylammonium bromide: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., brand DTAB.

[0074] (6) Antioxidants

[0075] Antioxidant 1098: N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, commonly available on the market.

[0076] (7) Lubricant

[0077] Oxidized polyethylene wax: purchased from Honeywell, brand A-C540A.

[0078] Examples 1 to 15 and Comparative Examples 1 to 3

[0079] Examples 1 to 15 and Comparative Examples 1 to 3 respectively provide a flame retardant PA66 composite material, the components of which are shown in Table 1 and Table 2. In Table 1 and Table 2, the units of the amounts of the components are all “parts by weight”.

[0080] Table 1

[0081]

[0082]

[0083] Table 2

[0084]

[0085] The preparation method of the flame-retardant PA66 composite material provided in Examples 1 to 15 and Comparative Examples 1 to 3 includes: mixing the components for 4 minutes, placing them in a twin-screw extruder and extruding and granulating them at 280° C. to obtain the flame-retardant PA66 composite material.

[0086] Performance testing:

[0087] (1) Izod notched impact strength: tested in accordance with ISO 180-2020.

[0088] (2) Flame retardant performance: The test was conducted in accordance with the UL 94-2023 standard, and the sample specifications were 125×13×1.6mm.

[0089] (3) Phosphine release: ① Equipment: drying dish (caliber 300 mm), Dräger phosphine tester and stopwatch; ② Test steps: continuous injection molding at 285°C, 280°C, 275°C, and 270°C, take 20 molds, take 21 molds of specimens and place them in a drying dish, seal it, press the stopwatch, and take the reading at 5 minutes; ③ Results: Phosphine release = detector reading / specimen mass (kg).

[0090] (4) Metal corrosivity and phosphorus content in the solution after immersion: ① Equipment: thermal aging oven, wide-mouth bottle, test tube with a diameter of 12 mm and a length of 100 mm, analytical balance, inductively coupled atomic emission spectrometer (ICP), and tweezers; ② Test steps: 50 g of sample particles were placed in a 500 mL wide-mouth bottle, and then a copper sheet with a specification of 80 mm × 10 mm × 1.0 mm was inserted into the sample particles, with the exposed portion being 40 mm long. 8 mL of deionized water was filled into the test tube, and the test tube was placed in the wide-mouth bottle and sealed. The wide-mouth bottle was then placed at 85°C for 3 days, the copper sheet was removed, the corrosion effect was visually inspected, and the corrosion level was recorded. The corroded copper sheet was then immersed in 30 mL of 5 wt% HCl solution for 1 h, and the phosphorus content in the solution was tested using ICP.

[0091] Copper sheet corrosion level 1: There is basically no corrosion or rust on the copper sheet;

[0092] Copper corrosion level 2: 1 / 3 of the copper sheet is corroded and rusted;

[0093] Copper corrosion level 3: 2 / 3 of the copper sheet is corroded and rusted;

[0094] Copper corrosion level 4: More than 2 / 3 of the copper sheet is corroded and rusted.

[0095] The flame retardant PA66 composite materials provided in Examples 1 to 15 and Comparative Examples 1 to 3 were tested according to the above test method. The test results are shown in Table 3:

[0096] Table 3

[0097]

[0098]

[0099] According to the data in Table 3, we can see that:

[0100] The flame retardant PA66 composite materials provided in Examples 1 to 15 all have an Izod notched impact strength of 15 kJ / m 2 The flame retardant properties can reach V-1 to V-0 levels, the phosphine release is less than 30ppm / kg, the metal corrosion level is 1 to 2, and the phosphorus content in the solution after immersion is less than 60ppm, with high toughness, low metal corrosion and excellent flame retardant properties.

[0101] Comparison of the data of Example 1 and Comparative Example 1 shows that not adding the quaternary ammonium salt compound results in a high phosphine release amount of the obtained PA66 composite material, a high metal corrosion level, and a high phosphorus content in the solution after immersion.

[0102] Further comparison of the data of Example 1 and Comparative Examples 3 to 4 shows that the absence of the addition of red phosphorus masterbatch (Comparative Example 3) or the addition of reinforcing material (Comparative Example 4) will directly result in the obtained PA66 composite material having no flame retardant grade, that is, no flame retardant performance, and the absence of the addition of reinforcing material (Comparative Example 4) will also result in a decrease in the notched cantilever impact strength of the obtained PA66 composite material and deterioration in toughness.

[0103] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A flame retardant PA66 composite material, characterized in that: The flame retardant PA66 composite material comprises the following components in parts by weight:

2. The flame retardant PA66 composite material according to claim 1, characterized in that: The relative viscosity of the PA66 resin is 1.8 to 3.5, preferably 2.2 to 2.9; Preferably, the reinforcing material comprises at least one of glass fiber, carbon fiber, aramid fiber or ceramic fiber; Preferably, the content of the toughening agent in the flame retardant PA66 composite material is 6 to 20 parts by weight; Preferably, the toughening agent includes at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted thermoplastic elastomer, maleic anhydride grafted EPDM rubber, acrylic acid grafted polyethylene, acrylic acid grafted thermoplastic elastomer, glycidyl acrylate grafted polyethylene, glycidyl acrylate grafted thermoplastic elastomer, glycidyl acrylate grafted EPDM rubber or ethylene-methyl acrylate copolymer, and is more preferably maleic anhydride grafted thermoplastic elastomer.

3. The flame retardant PA66 composite material according to claim 1 or 2, characterized in that: The chemical formula of the quaternary ammonium salt compound is [R1R2R3R4N] + X - , wherein R1 to R3 are each independently selected from at least one of C1 to C6 alkyl and C6 to C20 aryl, R4 is selected from C10 to C30 alkyl, and X is halogen.

4. The flame retardant PA66 composite material according to claim 3, characterized in that: The quaternary ammonium salt compound includes at least one of dimethyloctadecylbenzylammonium chloride, trimethylhexadecylammonium bromide, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, eicosyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyltriethylammonium chloride, hexacosyltrimethylammonium chloride, octadecyltrimethylammonium chloride, triacontyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, eicosyltrimethylammonium bromide, behenyltrimethylammonium bromide, behenyltriethylammonium bromide, hexacosyltrimethylammonium bromide, octadecyltrimethylammonium bromide or triacontyltrimethylammonium bromide, preferably dimethyloctadecylbenzylammonium chloride.

5. The flame retardant PA66 composite material according to claim 3, characterized in that: At least one of R1 to R3 is selected from C6 to C20 aryl groups, X is selected from Cl or Br, and the quaternary ammonium salt compound is preferably dimethyloctadecylbenzylammonium chloride.

6. The flame retardant PA66 composite material according to any one of claims 1 to 5, characterized in that: The flame retardant PA66 composite material further includes an antioxidant and / or a lubricant; Preferably, the content of the antioxidant in the flame retardant PA66 composite material is 0.1 to 1 parts by weight; Preferably, the antioxidant includes at least one of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, tris[2,4-di-tert-butylphenyl]phosphite, tetrakis(2,4-di-tert-butylphenol)4,4'-biphenyl diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate or a copper salt antioxidant; Preferably, the content of the lubricant in the flame retardant PA66 composite material is 0.1 to 1 parts by weight; Preferably, the lubricant includes at least one of oxidized polyethylene wax, calcium stearate, modified ethylene bis fatty acid amide, aliphatic fatty acid ester or ethylene-acrylic acid copolymer.

7. A method for preparing the flame-retardant PA66 composite material according to any one of claims 1 to 6, characterized in that: The preparation method comprises: mixing the various components, and extruding and granulating the mixture through an extruder to obtain the flame-retardant PA66 composite material.

8. The preparation method according to claim 7, characterized in that The mixing time is 3 to 5 minutes; Preferably, the extruder is a twin-screw extruder; Preferably, the temperature of the extrusion granulation is 250-290°C.

9. A manufactured article, characterized in that: The component comprises the flame-retardant PA66 composite material according to any one of claims 1 to 6.

10. The article according to claim 9, characterized in that The manufactured part comprises at least one of a household item, an electronic component, a household appliance part, a gardening equipment part, a medical technology equipment part, or a motor vehicle part.

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