Halogen-free flame-retardant nylon compound with multiple protection effects on metal and preparation method of halogen-free flame-retardant nylon compound

Abstract

The invention relates to the technical field of high polymer materials, in particular to a halogen-free flame-retardant nylon compound with multiple protection effects on metal and a preparation method thereof.The halogen-free flame-retardant nylon compound with the multiple protection effects on the metal is prepared from, by mass, 30-70 parts of polyamide resin, 6-50 parts of reinforcing filler, 1-3 parts of antioxidant, 1-3 parts of coupling agent, 1-3 parts of lubricant and 1-3 parts of lubricant. 5 to 20 parts of a halogen-free flame retardant, 0.1 to 2 parts of a first protective agent, 0.1 to 2 parts of a second protective agent, 0.1 to 1 part of a third protective agent, 0.1 to 0.5 part of an antioxidant and 0.1 to 0.6 part of a lubricant; wherein the first protective agent adopts a metal oxide or a metal hydroxide, the second protective agent adopts a porous adsorption material, and the third protective agent adopts at least one of a passivation type corrosion inhibitor, an adsorption type corrosion inhibitor and an isolation type corrosion inhibitor. A first protective agent, a second protective agent and a third protective agent are added into the halogen-free flame-retardant nylon compound provided by the invention, so that a multi-protection system is formed, and the corrosion of a halogen-free flame retardant as a nylon composite material of a flame-retardant system to metal can be greatly reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a halogen-free flame-retardant nylon composite having multiple protective effects on metals and a preparation method thereof. Background Art

[0002] Flame-retardant materials have very important application value in various fields, such as electronic appliances, new energy vehicles, and home appliances. The performance requirements of flame-retardant materials in different fields are different, and the properties of flame retardants used in flame-retardant materials in different fields vary greatly. Among them, red phosphorus is widely used as a high-efficiency flame retardant additive with low smoke emission and low toxicity. However, when composite materials with red phosphorus flame retardants are used in humid environments, they release highly corrosive substances such as acidic gases. When in contact with metal materials, the presence of these acidic substances causes the metal surface to lose its luster, affecting its service life. This greatly limits the further use of red phosphorus flame retardants.

[0003] To address the issue of red phosphorus flame-retardant nylon materials releasing acidic substances when exposed to humid environments, causing metal corrosion, the invention patent with publication number CN105585843A provides a low-precipitation red phosphorus flame-retardant nylon material and its preparation method. The material is composed of nylon resin, a red phosphorus flame retardant, a red phosphorus stabilizer, a toughening agent, a reinforcing filler, and other additives. By adjusting the proportions of these components, a red phosphorus flame-retardant nylon material with excellent stability is produced. In long-term high-temperature and high-humidity environments, it has low acid precipitation, thereby reducing corrosion to metals and molds. However, this red phosphorus flame-retardant nylon material still needs to further reduce phosphorus precipitation and corrosiveness. The invention patent with publication number CN107254167A provides a corrosion-resistant flame-retardant nylon material, which includes components such as nylon resin, red phosphorus flame retardant, lubricant, reinforcing agent, precipitation inhibitor and antioxidant; the material can avoid corrosion of the copper material connected to it, and has good environmental flame retardant properties, good electrical properties and excellent mechanical properties; however, the red phosphorus flame retardant nylon material still needs to further improve the thermal stability of the red phosphorus flame retardant and its compatibility with the nylon resin to further inhibit the precipitation and corrosiveness of the red phosphorus flame retardant. Summary of the Invention

[0004] Based on this, the purpose of the present invention is to provide a halogen-free flame-retardant nylon composite with multiple protective effects on metals and a preparation method thereof. Through the combination of multiple protection systems, the preparation of nylon flame-retardant materials that can effectively prevent metal corrosion is achieved.

[0005] To achieve the above object, the present invention adopts the following technical solutions: The present invention first provides a halogen-free flame retardant nylon composite with multiple protective effects on metals, which is prepared from the following components in parts by mass: 30-70 parts of polyamide resin, 6-50 parts of reinforcing filler, 5-20 parts of halogen-free flame retardant, 0.1-2 parts of a single protective agent, 0.1-2 parts of a double protective agent, 0.1-1 parts of a triple protective agent, 0.1-0.5 parts of an antioxidant, and 0.1-0.6 parts of a lubricant; wherein the single protective agent adopts a metal oxide or a metal hydroxide, the double protective agent adopts a porous adsorption material, and the triple protective agent adopts at least one of a passivation-type corrosion inhibitor, an adsorption-type corrosion inhibitor, and an isolation-type corrosion inhibitor.

[0006] As a further improvement of the above solution of the present invention, the first protective agent is at least one of magnesium hydroxide, magnesium oxide, aluminum oxide, zinc oxide, aluminum hydroxide, and copper oxide. Preferably, the first protective agent includes magnesium oxide and zinc oxide.

[0007] As a further improvement of the above solution of the present invention, the double protective agent is at least one of molecular sieve, hydrotalcite, 3A zeolite, 4A zeolite, and 5A zeolite. Preferably, the double protective agent is hydrotalcite.

[0008] As a further improvement to the above-mentioned solution of the present invention, the triple protective agent comprises at least one of microcrystalline wax, paraffin wax, polyethylene wax, petroleum sulfonate, zinc stearate, calcium stearate, and magnesium stearate. Microcrystalline wax, paraffin wax, and polyethylene wax form an isolation film on the metal surface, providing a dense physical barrier that blocks the penetration of corrosive media; petroleum sulfonate adsorbs on the metal interface, neutralizing acidic corrosive factors; and stearate forms a passivation film on the metal surface, inhibiting electrochemical corrosion reactions. This multi-component composite can cover various corrosion scenarios (e.g., damp heat, salt spray, and acidic environments). Preferably, the triple protective agent comprises paraffin wax and zinc stearate.

[0009] As a further improvement of the above solution of the present invention, the polyamide resin is at least one of nylon 6 and nylon 66.

[0010] As a further improvement of the above solution of the present invention, the halogen-free flame retardant is a red phosphorus flame retardant. The red phosphorus flame retardant is a coated microcapsule red phosphorus masterbatch, and the coating material can be at least one of melamine coating, phenolic resin coating, and nylon 6 coating, and nylon 6 coated red phosphorus masterbatch is preferably used.

[0011] As a further improvement of the above solution of the present invention, the antioxidant is selected from at least one of antioxidant 1098, antioxidant Revonox 501, antioxidant S-9228, antioxidant Sumilizer S80, and antioxidant TFB 117.

[0012] As a further improvement of the above solution of the present invention, the reinforcing filler is glass fiber or carbon fiber. Preferably, the glass fiber is 3 mm to long glass fiber, preferably 4.5 mm alkali-free glass fiber.

[0013] The present invention also provides a method for preparing the halogen-free flame-retardant nylon composite with multiple protective effects on metals as described above, which comprises the following steps: blending a polyamide resin, a halogen-free flame retardant, a lubricant, an antioxidant, a single protective agent, a double protective agent, and a triple protective agent in proportion; then feeding the mixed materials through the main feed port of a twin-screw extruder; feeding reinforcing fillers in proportion through the side feed port of the twin-screw extruder; and melting, extruding, and granulating the mixture to obtain the halogen-free flame-retardant nylon composite with multiple protective effects on metals.

[0014] As a further improvement of the above solution of the present invention, the temperature of each zone of the twin-screw extruder is: 200~270℃ in zone 1, 235~270℃ in zone 2, 245~280℃ in zones 3 to 11, and 245~280℃ in the die head.

[0015] Compared with the prior art, the present invention has the following beneficial effects: The halogen-free flame-retardant nylon composite provided by the present invention is added with a single protective agent, a double protective agent, and a triple protective agent to form a multiple protection system, wherein the single protective agent is a reactive auxiliary agent, the double protective agent is an acidic substance absorption auxiliary agent, and the triple protective agent is a chemical interface protection auxiliary agent and a physical interface protection auxiliary agent. The composite adopts a dual combination of chemical reaction and physical protection, integrating a triple protection strategy: the first layer reacts with metal oxides and hydroxides to precipitate acidic substances when red phosphorus comes into contact with water; the second layer uses a porous adsorption material to achieve adsorption and reaction of the acidic substances; and the third layer can provide an excellent interface protection effect between the metal and nylon interface, thereby achieving efficient corrosion protection after the nylon composite material contacts the metal. The composite material can greatly reduce the corrosion of the metal material by the nylon composite material containing a halogen-free flame retardant (such as red phosphorus) as the flame retardant system, and has low metal corrosion, longer metal protection time, high flame retardant performance, and a wider range of application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The test results of the corrosion resistance of the halogen-free flame-retardant nylon composite prepared in Example 1 to metals are shown; Figure 2 The test results of the corrosion resistance of the halogen-free flame-retardant nylon composite obtained in Comparative Example 1 to metals are shown below: Figure 3 The test results of the corrosion resistance of the halogen-free flame-retardant nylon composite obtained in Comparative Example 2 to metals are shown; Figure 4 The figure shows the corrosion test results of the halogen-free flame-retardant nylon composite obtained in Comparative Example 3 on metals. DETAILED DESCRIPTION

[0017] To facilitate understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0019] The specific information of the raw materials used in the following examples and comparative examples is as follows: PA66: Jiangsu Huayang HY1500, HY1800, Huafeng Group Co., Ltd. produced EP158, EP158NH, Shenma Group EPR24, EPR27; PA6: BE3280 from Jiangsu Hongsheng New Materials Co., Ltd. 4.5mm alkali-free glass fiber: chopped strands 560A, 560K, and 568H for PA produced by China Jushi Co., Ltd.; Taishan Fiberglass T435N series chopped glass fiber; Red phosphorus masterbatch: Tongcheng Xinde FR series; Lubricant: OP wax, commercially available; Antioxidant: commercially available; Zinc oxide: Lu Chang Chemical Co., Ltd., Taiwan, China; Magnesium hydroxide, magnesium oxide, aluminum oxide, zinc oxide, aluminum hydroxide, and copper oxide were purchased from Hefei Zhongke Flame Retardant New Materials Co., Ltd. Zeolite 3A, zeolite 4A, and zeolite 5A were purchased from Hebei Huike New Materials Co., Ltd.; Hydrotalcite was purchased from Chenghe Technology Co., Ltd.; Microcrystalline wax, paraffin wax, and polyethylene wax were purchased from Sinopec Nanyang Paraffin Fine Chemical Plant.

[0020] The above raw materials are only for illustrating the sources and components of the reagents used in the experiments of the present invention so as to fully disclose the information, and do not mean that the present invention cannot be achieved by using other similar reagents or reagents provided by other suppliers.

[0021] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0022] Example 1 This embodiment proposes a halogen-free flame-retardant nylon composite with multiple protective effects on metals, which includes the following component raw materials in parts by mass: 53.4 parts of PA66 (Shenma Group EPR24), 30 parts of glass fiber (560A), 13 parts of red phosphorus masterbatch, 0.4 parts of lubricant, 0.4 parts of antioxidant, 1.8 parts of primary protective agent, 0.6 parts of secondary protective agent, and 0.4 parts of triple protective agent; wherein the primary protective agent includes magnesium oxide and zinc oxide in a mass ratio of 1:0.8, the secondary protective agent includes 3A zeolite, the triple protective agent includes paraffin and zinc stearate in a mass ratio of 1:1, and the antioxidant includes antioxidant 1098 and antioxidant S-9228 in a mass ratio of 1:1.

[0023] The method for preparing a halogen-free flame-retardant nylon composite with multiple metal protection effects in this embodiment comprises the following steps: first, PA66, red phosphorus masterbatch, lubricant, antioxidant, magnesium oxide, 3A zeolite, paraffin wax, and zinc oxide are preliminarily blended in a blender in proportion; then, the mixed materials are fed through the main feed port of a twin-screw extruder; glass fiber is fed in proportion through the five zones of the twin-screw extruder; and after melting, extrusion, and granulation, a halogen-free flame-retardant nylon composite with multiple metal protection effects is obtained. The experimental temperatures of the different zones of the twin-screw extruder are: 265°C for zone 1, 265°C for zone 2, 275°C for zone 3, 275°C for zone 4, 275°C for zone 5, 275°C for zone 6, 275°C for zone 7, 275°C for zone 8, 275°C for zone 9, 275°C for zone 10, and 275°C for zone 11, with the die head temperature being 275°C.

[0024] Example 2 The difference between this embodiment and Example 1 is that the halogen-free flame-retardant nylon composite with multiple protective effects on metals in this embodiment includes the following component raw materials in parts by mass: 77.5 parts of PA66 (HY1800), 6 parts of glass fiber (568H), 13 parts of red phosphorus masterbatch, 0.4 parts of lubricant, 0.4 parts of antioxidant, 0.1 parts of primary protective agent, 2 parts of secondary protective agent, and 0.6 parts of triple protective agent; wherein the primary protective agent includes magnesium hydroxide and zinc oxide in a mass ratio of 1:0.8, the secondary protective agent includes hydrotalcite, the triple protective agent includes paraffin and zinc magnesium stearate in a mass ratio of 4:2, and the antioxidant includes antioxidant 1098 and antioxidant TFB 117 in a mass ratio of 1:1.

[0025] Example 3 The difference between this embodiment and Example 1 is that the halogen-free flame-retardant nylon composite with multiple protective effects on metals in this embodiment includes the following component raw materials in parts by mass: 45.8 parts of PA66 (HY1500), 30 parts of glass fiber (560K), 20 parts of red phosphorus masterbatch, 0.4 parts of lubricant, 0.4 parts of antioxidant, 1.8 parts of primary protective agent, 1 part of secondary protective agent, and 0.6 parts of triple protective agent; wherein the primary protective agent includes magnesium oxide and aluminum oxide in a mass ratio of 1:0.8, the secondary protective agent includes hydrotalcite, the triple protective agent includes polyethylene wax and zinc stearate in a mass ratio of 2:4, and the antioxidant includes antioxidant 1098 and antioxidant Revonox 501 in a mass ratio of 1:1.

[0026] Example 4 The difference between this embodiment and Example 1 is that the halogen-free flame-retardant nylon composite with multiple protective effects on metals in this embodiment includes the following component raw materials in parts by mass: 40.9 parts of PP66 (EP158), 50 parts of glass fiber (568H), 5 parts of red phosphorus masterbatch, 0.4 parts of lubricant, 0.4 parts of antioxidant, 2 parts of primary protective agent, 0.6 parts of secondary protective agent, and 0.7 parts of triple protective agent; wherein the primary protective agent includes magnesium oxide and copper oxide in a mass ratio of 1:1, the secondary protective agent includes 3A zeolite, the triple protective agent includes microcrystalline wax and petroleum sulfonate in a mass ratio of 3:4, and the antioxidant includes antioxidant 1098 and antioxidant Sumilizer S80 in a mass ratio of 1:1.

[0027] Example 5 The difference between this embodiment and Example 1 is that the halogen-free flame-retardant nylon composite with multiple protective effects on metals in this embodiment includes the following component raw materials in parts by mass: 53.6 parts of PA6 (BE3280), 30 parts of glass fiber (568H), 13 parts of red phosphorus masterbatch, 0.4 parts of lubricant, 0.4 parts of antioxidant, 1.5 parts of single protective agent, 0.1 parts of double protective agent, and 1 part of triple protective agent; wherein the single protective agent includes aluminum hydroxide and zinc oxide in a mass ratio of 1:0.5, the double protective agent includes 4A zeolite, the triple protective agent includes paraffin and calcium stearate in a mass ratio of 3:4, and the antioxidant includes antioxidant 1098 and antioxidant TFB117 in a mass ratio of 1:1.

[0028] Example 6 The difference between this embodiment and Example 1 is that the halogen-free flame-retardant nylon composite with multiple protective effects on metals in this embodiment includes the following component raw materials in parts by mass: 53.8 parts of PP66 (EP158NH), 30 parts of glass fiber (568H), 13 parts of red phosphorus masterbatch, 0.4 parts of lubricant, 0.4 parts of antioxidant, 1.8 parts of primary protective agent, 0.5 parts of secondary protective agent, and 0.8 parts of triple protective agent; wherein the primary protective agent includes zinc hydroxide and zinc oxide in a mass ratio of 1:0.8, the secondary protective agent includes 5A zeolite, the triple protective agent includes paraffin and zinc stearate in a mass ratio of 1:1, and the antioxidant includes Sumilizer S80 and antioxidant S-9228 in a mass ratio of 1:1.

[0029] Comparative Example 1 The difference between this comparative example and Example 1 is that the halogen-free flame-retardant nylon composite of this comparative example includes the following component raw materials in parts by mass: 56.2 parts of PA66 (EPR24), 30 parts of glass fiber (568H), 13 parts of red phosphorus masterbatch, 0.4 parts of lubricant, and 0.4 parts of antioxidant; wherein the antioxidant includes antioxidant 1098 and antioxidant S-9228 in a mass ratio of 1:1.

[0030] Comparative Example 2 The difference between this comparative example and Example 1 is that the halogen-free flame retardant nylon composite of this comparative example includes the following component raw materials in parts by mass: 55.2 parts of PA66 (EPR24), 30 parts of glass fiber (T435N), 13 parts of red phosphorus masterbatch, 0.4 parts of lubricant, 0.4 parts of antioxidant, and 1 part of a first-layer protective agent; wherein the first-layer protective agent includes magnesium oxide, and the antioxidant includes antioxidant 1098 and antioxidant S-9228 in a mass ratio of 1:1.

[0031] Comparative Example 3 The difference between this comparative example and Example 1 is that the halogen-free flame retardant nylon composite of this comparative example includes the following component raw materials in parts by mass: 54.6 parts of PA66 (EPR27), 30 parts of glass fiber (568H), 13 parts of red phosphorus masterbatch, 0.4 parts of lubricant, 0.4 parts of antioxidant, 1 part of primary protective agent, and 0.6 parts of secondary protective agent; wherein the primary protective agent includes magnesium oxide, the secondary protective agent includes 3A zeolite, and the antioxidant includes antioxidant 1098 and antioxidant S-9228 in a mass ratio of 1:1.

[0032] The amounts of the components used in Examples 1-6 and Comparative Examples 1-3 are shown in Table 1.

[0033] Table 1 Amount of each component used in Examples 1-6 and Comparative Examples 1-3 (parts by mass)

[0034] Test Case (1) The halogen-free flame-retardant nylon composites prepared in Examples 1-6 and Comparative Examples 1-3 were dried in a 120°C oven for 4 h and then injection molded into 1.6 mm strips. The strips were then flame-retardant tested in accordance with the vertical combustion method in accordance with GB / T 2408-2008. The test results are shown in Table 2.

[0035] Table 2 Flame retardant test results

[0036] The results in Table 2 show that the halogen-free flame-retardant nylon composites prepared in Examples 1-6 of the present application have excellent flame retardant properties.

[0037] (2) Corrosion test: The halogen-free flame-retardant nylon composites prepared in Example 1 and Comparative Examples 1-3 were placed in an oven at 120°C for 4 hours and then injection-molded into 1.6 mm strips. The strips were then subjected to corrosion tests: The strips were placed on rectangular copper specimens and placed in an environment with a temperature of 85°C and a humidity of 85%. The rectangular copper specimens were subjected to a corrosion test for 50 days × 24 hours. The test results are shown in the figure. Figure 1-4 shown.

[0038] from Figure 1-4 The results clearly show that as the protection system increases from one layer to three layers, the metal surface shows obvious differences: the copper sample of comparative example 1 (without adding protection system) has serious acidic substances precipitated on the surface, such as Figure 2 As shown; Comparative Example 2 (adding a layer of protection system) significantly reduced the corrosion of the copper sample, as shown Figure 3 As shown; when the protection system is increased to 3 levels, as shown Figure 1 As shown, the copper sample of Example 1 is essentially corrosion-free under the conditions of 50 days × 24 hours. This is because using only one protective agent is difficult to achieve the desired effect of preventing metal corrosion. This is because a single protective system or two protective systems cannot achieve an effective anti-corrosion effect with a small amount, while increasing the amount easily causes precipitation and metal corrosion. This shows that the triple protective system of the present invention has a high synergistic protective effect.

[0039] In summary, with the same flame retardancy level, after long-term aging, the triple-system halogen-free flame retardant nylon composite of the present invention has a better metal protection effect.

[0040] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0041] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A halogen-free flame-retardant nylon composite having multiple protective effects on metals, characterized in that: It is prepared from the following components in parts by mass: 30-70 parts of polyamide resin, 6-50 parts of reinforcing filler, 5-20 parts of halogen-free flame retardant, 0.1-2 parts of single protective agent, 0.1-2 parts of double protective agent, 0.1-1 parts of triple protective agent, 0.1-0.5 parts of antioxidant, and 0.1-0.6 parts of lubricant; wherein, the single protective agent adopts metal oxide or metal hydroxide, the double protective agent adopts porous adsorption material, and the triple protective agent adopts at least one of passivation corrosion inhibitor, adsorption corrosion inhibitor and isolation corrosion inhibitor.

2. The halogen-free flame-retardant nylon composite with multiple protective effects on metals according to claim 1, characterized in that: The first protective agent is at least one of magnesium hydroxide, magnesium oxide, aluminum oxide, zinc oxide, aluminum hydroxide, and copper oxide.

3. The halogen-free flame-retardant nylon composite with multiple protective effects on metals according to claim 1, characterized in that: The double protective agent is at least one of molecular sieve, hydrotalcite, 3A zeolite, 4A zeolite and 5A zeolite.

4. The halogen-free flame-retardant nylon composite with multiple protective effects on metals according to claim 1, characterized in that: The triple protective agent is at least one of microcrystalline wax, paraffin wax, polyethylene wax, petroleum sulfonate, zinc stearate, calcium stearate, and magnesium stearate.

5. The halogen-free flame-retardant nylon composite with multiple protective effects on metals according to claim 1, characterized in that: The polyamide resin is at least one of nylon 6 and nylon 66.

6. The halogen-free flame-retardant nylon composite with multiple protective effects on metals according to claim 1, characterized in that: The halogen-free flame retardant is a red phosphorus flame retardant.

7. The halogen-free flame-retardant nylon composite with multiple protective effects on metals according to claim 1, characterized in that: The antioxidant is selected from at least one of antioxidant 1098, antioxidant Revonox 501, antioxidant S-9228, antioxidant Sumilizer S80, and antioxidant TFB 117.

8. The halogen-free flame-retardant nylon composite with multiple protective effects on metals according to claim 1, characterized in that: The reinforcing filler is glass fiber or carbon fiber.

9. A method for preparing the halogen-free flame-retardant nylon composite having multiple protective effects on metals according to any one of claims 1 to 8, characterized in that: It includes the following steps: Polyamide resin, halogen-free flame retardant, lubricant, antioxidant, single protective agent, double protective agent and triple protective agent are blended in proportion, and then the mixed materials are fed through the main feeding port of a twin-screw extruder. Reinforcing fillers are fed through the side feeding port of the twin-screw extruder in proportion. After melting, extrusion and granulation, a halogen-free flame retardant nylon compound with multiple protective effects on metals is obtained.

10. The method for preparing a halogen-free flame-retardant nylon composite having multiple protective effects on metals according to claim 9, characterized in that: The temperature of each zone of the twin-screw extruder is: 200-270°C in zone 1, 235-270°C in zone 2, 245-280°C in zones 3 to 11, and 245-280°C in the die head.

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