A red phosphorus flame-retardant long carbon chain nylon composite and a preparation method and application thereof

Abstract

The application relates to a red phosphorus flame-retardant long carbon chain nylon composite and a preparation method and application thereof, and relates to the technical field of high polymer materials; the red phosphorus flame-retardant long carbon chain nylon composite comprises the following components: long carbon chain nylon resin 40-50 parts, aromatic nylon resin 7-15 parts, non-crystalline nylon resin 8-15 parts, glass fiber 20-30 parts, red phosphorus flame-retardant agent 2.5-7.5 parts and zinc-based flame-retardant synergist 1-4 parts; the zinc-based flame-retardant synergist is selected from zinc sulfide and / or organic zinc ionomer. The long carbon chain aliphatic nylon, the aromatic nylon and the non-crystalline nylon are compounded in three different forms, the long carbon chain nylon composite prepared under the synergistic effect of the red phosphorus flame-retardant agent and the selected specific flame-retardant synergist has excellent flame-retardant performance on the basis of guaranteeing mechanical properties, the flame-retardant grade can reach UL94 V-0, the flame-retardant thickness can reach 0.8 mm, the red phosphorus corrosion is inhibited, and the requirements of miniaturization and thin-wall electronic appliances are met.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and in particular to a red phosphorus flame-retardant long carbon chain nylon composite, its preparation method and application. Background Technology

[0002] Long-chain nylons refer to nylons in which the number of methylene groups in the repeating structural units between adjacent amide bonds in the macromolecular backbone is ≥10, such as PA610, PA612, and PA1010. Compared with conventional short-chain nylons (such as PA6 and PA66), long-chain nylons have advantages such as low density, low water absorption, good dimensional stability, excellent chemical resistance, and outstanding low-temperature performance. They have been widely used in various automotive parts, such as fuel lines, copper busbar coatings, windshield wipers, and muffler gears.

[0003] Long-chain nylons, with their low moisture absorption, excellent electrical properties, and resistance to electrochemical corrosion, also hold great potential for applications in the electronics and electrical industries. However, these industries have stringent requirements for the flame-retardant properties of materials. Compared to PA6 and PA66 materials, long-chain nylons have lower carbonization efficiency, often requiring the addition of large amounts of flame-retardant components, leading to a significant decrease in the material's mechanical properties. This makes it difficult for halogen-free flame-retardant systems of long-chain nylons to simultaneously meet the requirements for both mechanical and flame-retardant properties. Patent CN114716823 A discloses a flame-retardant reinforced bio-based long-chain nylon material and its preparation method. This method involves extruding long-chain nylon with rare earth oxides and cellulose acetate to produce long-chain nylon with excellent flame-retardant properties. However, this system requires a high glass fiber content (≥40%) to ensure mechanical properties while achieving UL94 V-0 flame retardancy. Furthermore, its flame-retardant thickness is limited to 1.6mm. With the trend towards miniaturization and thinner walls in the electronics industry, 1.6mm UL94 V-0 cannot meet the industry's requirements. Using red phosphorus as a flame retardant can significantly enhance the flame-retardant properties of PA66 at lower addition levels without easily damaging the material's electrical and mechanical properties, showing great promise for thin-walled flame-retardant nylon parts. However, long-term use of red phosphorus flame-retardant nylon can lead to red phosphorus corrosion, causing corrosion of metals in electronic products and posing significant safety hazards. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects and shortcomings of the prior art and provide a red phosphorus flame-retardant long carbon chain nylon composite that has high mechanical properties, high flame retardant properties and low phosphorus corrosion, and can achieve UL94 V-0 flame retardancy in thin-walled products.

[0005] Another objective of this invention is to provide a method for preparing a red phosphorus flame-retardant long carbon chain nylon composite.

[0006] Another object of the present invention is to provide a plastic part for electronic appliances.

[0007] The above-mentioned objective of this invention is achieved through the following technical solution: This invention protects a red phosphorus flame-retardant long-chain nylon composite, comprising the following components in parts by weight: 40-50 parts of long-chain nylon resin, 7-15 parts of aromatic nylon resin, 8-15 parts of amorphous nylon resin, 20-30 parts glass fiber 2.5-7.5 parts of red phosphorus flame retardant. 1-4 parts of zinc-based flame retardant synergist; The zinc-based flame retardant synergist is selected from zinc sulfide and / or organozinc ionomers.

[0008] The red phosphorus flame-retardant long-chain nylon composite of the present invention uses long-chain nylon resin as the matrix and is compounded with aromatic nylon resin to effectively enhance performance. At the same time, the aromatic nylon contains a benzene ring structure, which is beneficial to catalyze the carbonization of red phosphorus flame retardant at high temperature. The use of a specific amount of amorphous nylon can improve the compatibility between long-chain nylon and aromatic nylon and enhance the interfacial bonding strength between aromatic nylon and long-chain nylon. This specific nylon system also has a strong barrier effect and can inhibit the precipitation of red phosphorus. At the same time, the synergistic effect of the use of a specific zinc flame retardant synergist with the red phosphorus flame retardant can further improve the quality of the carbon layer and increase the resistance to metal corrosion. Thus, the flame retardant rating can reach UL94 V-0 with a low flame retardant content, meeting the requirements of miniaturized and thin-walled electronic appliances.

[0009] In some embodiments, the organozinc ionomer is at least one of ethylene zinc methacrylate copolymer and ethylene zinc acrylate copolymer.

[0010] In some embodiments, the amorphous nylon resin accounts for 15-27 wt% of the total mass fraction of the long-chain nylon resin and the aromatic nylon resin.

[0011] In some embodiments, the content of the long-chain nylon resin that satisfies the purpose of the present invention can be a range of one or any two of 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 ​​parts, 49 parts, and 50 parts.

[0012] In some embodiments, the content of the long-chain nylon resin that satisfies the purpose of the present invention can be a range of one or any two of 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 ​​parts, 49 parts, and 50 parts.

[0013] In some embodiments, the content of the long-chain nylon resin that satisfies the purpose of the present invention can be one or any two of the following: 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts.

[0014] In some embodiments, the content of the long-chain nylon resin that satisfies the purpose of the present invention can be one or any two of the following: 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts.

[0015] In some embodiments, the content of the red phosphorus flame retardant that satisfies the purpose of the present invention can be one or any two of the following: 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, and 7.5 parts.

[0016] In some embodiments, the mass ratio of the long-chain nylon resin to the aromatic nylon resin is (3-7):1.

[0017] In some embodiments, the long-chain nylon resin is an amide polymer having C10-C20 aliphatic segment structural units; preferably, the long-chain nylon resin is selected from at least one of PA610, PA612, PA12, PA1010 and PA1012.

[0018] In some embodiments, the aromatic nylon resin is an amide polymer having repeating structural units of aromatic ring segments and C3-C19 aliphatic segments; preferably, the aromatic nylon resin is selected from at least one of PA66 / 6T, PA MXD6 and PA MXD10.

[0019] In some embodiments, the amorphous nylon resin is selected from at least one of PA6I / 6T and TM156.

[0020] In some embodiments, the glass fiber has a diameter of 7-16 μm.

[0021] In some embodiments, the glass fiber is selected from at least one of E glass fiber, H glass fiber, S glass fiber, D glass fiber or C glass fiber.

[0022] A method for preparing a red phosphorus flame-retardant long carbon chain nylon composite includes the following steps: mixing each raw material component evenly, melt blending, extruding and granulating to obtain the red phosphorus flame-retardant long carbon chain nylon composite.

[0023] In some embodiments, the twin-screw extruder has a temperature of 190-260°C and a rotation speed of 300-500 r / min.

[0024] An electronic and electrical plastic component comprising the aforementioned red phosphorus flame-retardant long carbon chain nylon composite.

[0025] Compared with the prior art, the beneficial effects of the present invention are: This invention discloses a red phosphorus flame-retardant long-chain nylon composite. By blending three different nylons—long-chain aliphatic nylon, aromatic nylon, and amorphous nylon—it effectively enhances the strength and toughness of the material while inhibiting the precipitation of red phosphorus. The red phosphorus flame retardant and a specific zinc-based flame retardant synergist system work synergistically to inhibit metal corrosion of the red phosphorus flame retardant system. With a low flame retardant content, it achieves a flame retardant rating of UL94 V-0, meeting the requirements for miniaturized and thin-walled electronic appliances. Detailed Implementation

[0026] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise stated, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0027] 1. Long-chain carbon nylon resin: PA610: PA610F120, relative viscosity 2.3, test standard ISO 307-2007 (25℃, solvent 98wt% concentrated sulfuric acid, the same below), Shandong Guangyin New Material Co., Ltd.

[0028] PA612: PA612A120, relative viscosity 2.4, test standard ISO 307-2007, Shandong Guangyin New Materials Co., Ltd.

[0029] PA1010: PA1010G150, relative viscosity 2.6, test standard ISO 307-2007, Shandong Guangyin New Materials Co., Ltd.

[0030] PA1012: Hiprolon 400NNLM, relative viscosity 2.6, test standard ISO 307-2007, Arkema Ltd., France.

[0031] 2. Aromatic nylon resin: PA66 / 6T: Relative viscosity is 2.3, test standard is ISO 307-2007, NPD-652, Invista Ltd.

[0032] PAMXD6: Relative viscosity is 2.5, test standard is ISO 307-2007, MXD6AP250, Shanghai Yinggu Co., Ltd.

[0033] 3. Amorphous nylon resin: Amorphous Nylon-1: Relative viscosity is 2.0, test standard is ISO 307-2007, PA6I / 6T; TI1207, Shandong Guangyin New Materials Co., Ltd.

[0034] Amorphous Nylon-2: Melt index of 7.8 g / 10 min at 260℃ / 1.2 kg, test standard is ISO 1133-1:2022, TM156, Shandong Guangyin New Materials Co., Ltd.

[0035] 4. Fiberglass: Glass fiber-1: 10um in diameter, ECS10-3.0-568H, China Jushi Co., Ltd.

[0036] Glass fiber-2: 13um in diameter, ECS13-4.5-568H, China Jushi Co., Ltd.

[0037] 5. Red phosphorus flame retardant: Red phosphorus masterbatch: Red phosphorus content is 50wt%, matrix resin is PA6; FR9950KF, Tongcheng Xinde New Materials Co., Ltd.

[0038] 6. Zinc-based flame retardant synergists Zinc borate, commercially available.

[0039] Zinc stannate, commercially available.

[0040] Zinc sulfide, commercially available.

[0041] Organic zinc ionomer-1: ethylene zinc methacrylate copolymer, melt index 0.8 g / 10 min at 190℃ / 2.16 kg, melt index test standard is ISO 1133-1:2022, Surlyn 9320, Dow Chemical, USA.

[0042] Organic zinc ionomer-2: ethylene zinc acrylate copolymer, melt index 5.2 g / 10 min at 190℃ / 2.16 kg, melt index test standard is ISO 1133-1:2022; IONIA 2610, SK Geo Centric, South Korea.

[0043] Magnesium stannate: Henan Jiashun Chemical Products Co., Ltd.

[0044] The following examples and comparative methods describe the preparation of red phosphorus flame-retardant long-chain nylon composites: Each component was weighed according to its weight, and the components were added to a premixer and mixed until homogeneous to obtain a premix. The premix was then fed into a twin-screw extruder for melt mixing and extrusion granulation. The temperature of the twin-screw extruder was 190-260℃, and the speed was 400 r / min.

[0045] The test methods for the red phosphorus flame-retardant long-chain nylon composites in the following examples and comparative examples are as follows: Flame retardancy: The flame retardancy of the sample was tested according to the relevant standard UL 94-2015, and the sample thickness was 0.8 mm. Tensile strength: Tested according to the standard ISO 527-2012.

[0046] Notched impact strength of cantilever beam: tested according to standard ISO 180-2000.

[0047] Phosphorus corrosion: Take 50g of red phosphorus flame-retardant nylon composite sample and place it in a 500ml wide-mouth bottle. Then take a copper sheet with a specification of 80mm×10mm×1.0mm and insert it into the particle, with the exposed part being 40mm in length. Put 8mL of deionized water into a test tube, place the test tube into the wide-mouth bottle, seal it, and then place the wide-mouth bottle at 85℃ for 3 days. Take out the copper sheet and then soak the corroded copper sheet in 30mL of 5 parts HCl solution for 1h. Use ICP to test the phosphorus content in the solution after rinsing. The higher the phosphorus content, the more severe the corrosion of the copper sheet.

[0048] Examples 1-13 This embodiment provides a series of red phosphorus flame-retardant long carbon chain nylon composites. The raw material composition and performance test results by weight are shown in Table 1.

[0049] Table 1

[0050] Comparative Examples 1-8 This comparative example provides a series of red phosphorus flame-retardant long carbon chain nylon composites. The raw material composition and performance test results by weight are shown in Table 2.

[0051] Table 2

[0052] As shown in Tables 1-2, the red phosphorus flame-retardant long-chain nylon composite obtained in this invention possesses excellent flame-retardant properties, mechanical properties, and phosphorus corrosion resistance. Its vertical burning performance reaches V-0 rating, tensile strength ≥127 MPa, and cantilever beam notched impact strength ≥12.5 kJ / m². 2 Phosphorus content ≤ 9.2 ppm.

[0053] Compared to Example 1, when Comparative Example 1 does not contain amorphous nylon, the material has poorer mechanical properties, flame retardant properties, and phosphorus corrosion resistance.

[0054] When Comparative Example 2 does not contain aromatic nylon, its mechanical properties, flame retardant properties, and phosphorus corrosion resistance decrease significantly.

[0055] In Comparative Examples 3-5, the use of zinc borate, zinc stannate, and magnesium stannate as flame retardant synergists affected the flame retardant performance and failed to effectively inhibit phosphorus corrosion. In Comparative Examples 6-7, both insufficient and excessive amorphous nylon content resulted in poor mechanical properties, flame retardant properties, and reduced corrosion resistance. Similarly, in Comparative Example 8, excessive aromatic nylon content led to a decrease in mechanical properties and phosphorus corrosion resistance.

[0056] The above embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the implementation of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all possible implementations here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A red phosphorus flame-retardant long carbon chain nylon composite, characterized in that, Includes the following components by weight: 40-50 parts of long-chain nylon resin, 7-15 parts of aromatic nylon resin, 8-15 parts of amorphous nylon resin, 20-30 parts glass fiber 2.5-7.5 parts of red phosphorus flame retardant. 1-4 parts of zinc-based flame retardant synergist; The zinc-based flame retardant synergist is selected from zinc sulfide and / or organozinc ionomers.

2. The red phosphorus flame-retardant long carbon chain nylon composite according to claim 1, characterized in that, The organozinc ionomer is at least one of ethylene zinc methacrylate copolymer and ethylene zinc acrylate copolymer.

3. The red phosphorus flame-retardant long carbon chain nylon composite according to claim 1, characterized in that, The amorphous nylon resin accounts for 15-27 wt% of the total mass fraction of the long-chain nylon resin and aromatic nylon resin.

4. The red phosphorus flame-retardant long carbon chain nylon composite according to claim 1, characterized in that, The mass ratio of the long-chain nylon resin to the aromatic nylon resin is (3-7):

1.

5. The red phosphorus flame-retardant long carbon chain nylon composite according to claim 1, characterized in that, The long-chain nylon resin is an amide polymer having C10-C20 aliphatic segment structural units; preferably, the long-chain nylon resin is selected from at least one of PA610, PA612, PA12, PA1010 and PA1012.

6. The red phosphorus flame-retardant long carbon chain nylon composite according to claim 1, characterized in that, The aromatic nylon resin is an amide polymer having repeating structural units of aromatic ring segments and C3-C19 aliphatic segments; preferably, the aromatic nylon resin is selected from at least one of PA66 / 6T, PA MXD6 and PA MXD10.

7. The red phosphorus flame-retardant long carbon chain nylon composite according to claim 1, characterized in that, The amorphous nylon resin is selected from at least one of PA6I / 6T and TM156.

8. The red phosphorus flame-retardant long carbon chain nylon composite according to claim 1, characterized in that, The glass fiber has a diameter of 7-16 μm.

9. A method for preparing the red phosphorus flame-retardant long carbon chain nylon composite according to any one of claims 1-8, characterized in that, Includes the following steps: All raw material components are mixed evenly, melt-blended, extruded and granulated to obtain the red phosphorus flame-retardant long carbon chain nylon composite.

10. A plastic part for electronic appliances, characterized in that, It comprises the red phosphorus flame-retardant long carbon chain nylon composite according to any one of claims 1-8.

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