Glass fiber reinforced red phosphorus flame-retardant high-scorching-heat PA material and preparation method thereof

Abstract

The invention belongs to the technical field of engineering plastics, and particularly discloses a glass fiber reinforced red phosphorus flame-retardant high-scorching-heat PA material which comprises the following components in parts by weight: 41.2-67.4 parts of PA6 resin, 20-30 parts of glass fiber, 8-15 parts of microencapsulated red phosphorus, 2-5 parts of nano layered double hydroxide, 1-3 parts of zinc borate, 0.3-0.8 part of an antioxidant, 0.3-1 part of a lubricant and 1-4 parts of a flexibilizer. By adding the microencapsulated red phosphorus, the nano layered double hydroxide and the zinc borate, the mechanical property and the flame-retardant grade of the material can be improved, a 750 DEG C glowing filament can be prevented from ignition and precipitation resistance in the whole process, and the market demand of the PA material is met.

Description

Technical Field

[0001] The present invention relates to the technical field of engineering plastics, and in particular to a glass fiber reinforced red phosphorus flame retardant high-heat PA material and a preparation method thereof. Background Art

[0002] Nylon 6 (PA6), also known as polycaprolactam, also known as polyamide (Polyamide-6), is a semi-crystalline granular engineering plastic with a melting point of 215-225°C and a relative density of 1.14g / cm 3 .

[0003] The rapid development of the electronics, electrical, and new energy industries has placed higher demands on the flame retardancy and precipitation resistance of PA materials. Glass fiber reinforced red phosphorus flame retardant high-scorching PA materials have emerged to meet these demands.

[0004] Patent CN103382302A discloses a red phosphorus flame-retardant nylon composition and its preparation method. The composition comprises the following components, by weight: 55-75% nylon resin; 15-35% glass fiber; 6-8% red phosphorus flame retardant; 2-5% toughening agent; 0.2-1% lubricant; and 0.2-1% antioxidant. While red phosphorus is used in the composition, which improves the material's flame retardancy, it is susceptible to precipitation on the surface of the finished product, and no additives are added to raise the glow-wire temperature.

[0005] Existing technologies for increasing the glow-wire temperature of glass-fiber-reinforced PA modified materials primarily involve adding magnesium hydroxide or aluminum hydroxide. However, these additions significantly degrade the material's mechanical properties. Another approach involves adding melamine cyanurate (MCA). However, small amounts of MCA lead to unstable glow-wire temperatures, while large amounts can cause the material to foam during the manufacturing process, hindering production. Summary of the Invention

[0006] In order to overcome the defects of the prior art, the present invention provides a glass fiber reinforced red phosphorus flame retardant high-heat PA material and a preparation method thereof.

[0007] The technical solution adopted by the present invention to solve the technical problem is: a glass fiber reinforced red phosphorus flame retardant high-heat PA material, comprising the following components by weight: 41.2-67.4 parts of PA6 resin, 20-30 parts of glass fiber, 8-15 parts of microencapsulated red phosphorus, 2-5 parts of nano-layered double hydroxide, 1-3 parts of zinc borate, 0.3-0.8 parts of antioxidant, 0.3-1 parts of lubricant, and 1-4 parts of toughening agent.

[0008] As a further solution, the microencapsulated red phosphorus is red phosphorus coated with melamine formaldehyde resin microcapsules, and the mass ratio of melamine formaldehyde resin to red phosphorus is 30-40:60-70.

[0009] As a further solution, the nano-layered double hydroxide is one or more of magnesium-aluminum-based layered double hydroxide, zinc-aluminum-based layered double hydroxide, and montmorillonite layered double hydroxide.

[0010] As a further solution, the antioxidant is one or more of 1010, 168, and 1098.

[0011] As a further solution, the lubricant is one or more of pentaerythritol stearate, zinc stearate, calcium stearate, and silicone powder.

[0012] As a further solution, the toughening agent is one or two of POE grafted maleic anhydride and ethylene propylene rubber.

[0013] As a further solution, the intrinsic viscosity of the PA6 resin is 2.4-2.5 dl / g, and the melt flow rate is 50-80 g / (10 min) under the test conditions of 250° C. / 2.16 kg.

[0014] As a further solution, the diameter of the glass fiber is 8-16 μm.

[0015] The present invention also provides a preparation method of a glass fiber reinforced red phosphorus flame retardant high ignition PA material, the preparation method is used to prepare the above-mentioned glass fiber reinforced red phosphorus flame retardant high ignition PA material, the preparation method comprises the following steps: 1) Melamine formaldehyde resin and red phosphorus were mixed in a mass ratio of 30-40:60-70, stirred at 30-50 rpm for 3 minutes, and after mixing evenly, melt blended and extruded to obtain microencapsulated red phosphorus; 2) adding the PA6 resin, the microencapsulated red phosphorus prepared in step 1), the nano-layered double hydroxide, zinc borate, an antioxidant, a lubricant, and a toughening agent into a blender, and mixing and stirring uniformly to obtain a mixture; 3) The mixture and glass fiber are fed into a twin-screw extruder, heated until melted and extruded, thereby producing the glass fiber reinforced red phosphorus flame retardant high-scorching PA material.

[0016] As a further solution, in step 3), the temperature of the melt extrusion is 220-250° C., and the screw speed of the twin-screw extruder is 300-550 r / min.

[0017] The present invention has at least one of the following beneficial effects: 1. By microencapsulating red phosphorus, the stability of the production process is improved, the PA material can achieve the effect of precipitation resistance, and the material appearance is brighter.

[0018] 2. The PA material is added with nano-layered double hydroxide, which not only retains the mechanical properties of the material under normal conditions, but also ensures that the material will not burn at a 750°C hot wire.

[0019] 3. By adding microencapsulated red phosphorus, nano-layered double hydroxide and zinc borate, the mechanical properties and flame retardant grade of the material can be improved. It can also meet the requirements of non-ignition and precipitation resistance of the glow wire at 750°C, meeting the market demand for PA materials. DETAILED DESCRIPTION

[0020] The following is a further description of specific embodiments of the present invention. It should be noted that the description of these embodiments is intended to facilitate understanding of the present invention and does not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

[0021] It should be noted that in the following examples and comparative examples, in the glass fiber reinforced red phosphorus flame retardant high-scorching PA material, the intrinsic viscosity of the PA6 resin can be selected between 2.45 dl / g, the melt flow rate is 65 g / (10 min) under the test conditions of 250°C / 2.16 kg, and the diameter of the glass fiber is selected in the range of 8-16 μm.

[0022] Example 1 This embodiment provides a glass fiber reinforced red phosphorus flame retardant high-scorching PA material, including the following components in parts by weight: 41.2 parts of PA6 resin, 20 parts of glass fiber, 8 parts of microencapsulated red phosphorus, 5 parts of nano-layered double hydroxide, 1 part of zinc borate, 0.3 parts of antioxidant, 0.3 parts of lubricant, and 2 parts of toughening agent.

[0023] Among them, microencapsulated red phosphorus is red phosphorus coated with melamine formaldehyde resin microcapsules, with the mass ratio of melamine formaldehyde resin to red phosphorus being 40:60; the nano-layered double hydroxide is magnesium-aluminum-based layered double hydroxide; the antioxidant is antioxidant 1010; the lubricant is pentaerythritol stearate; and the toughening agent is POE grafted maleic anhydride.

[0024] The present invention also provides a method for preparing a glass fiber reinforced red phosphorus flame retardant high-heat PA material, comprising the following steps: 1) Melamine formaldehyde resin and red phosphorus were mixed in a mass ratio of 40:60, stirred at 30-50 rpm for 3 minutes, and after mixing evenly, melt blended and extruded to obtain microencapsulated red phosphorus; 2) adding the PA6 resin, the microencapsulated red phosphorus prepared in step 1), the nano-layered double hydroxide, zinc borate, an antioxidant, a lubricant, and a toughening agent into a blender, and mixing and stirring uniformly to obtain a mixture; 3) The mixture and glass fiber are fed into a twin-screw extruder, heated to melt and extruded, the temperature of the melt extrusion is controlled between 220-250° C., and the screw speed of the twin-screw extruder is controlled between 300-550 r / min, thereby producing a glass fiber reinforced red phosphorus flame retardant high-scorching PA material.

[0025] Example 2 This embodiment provides a glass fiber reinforced red phosphorus flame retardant high-scorching PA material, including the following components in parts by weight: 50.8 parts of PA6 resin, 20 parts of glass fiber, 10 parts of microencapsulated red phosphorus, 4 parts of nano-layered double hydroxide, 2 parts of zinc borate, 0.4 parts of antioxidant, 0.5 parts of lubricant, and 2 parts of toughening agent.

[0026] Among them, microencapsulated red phosphorus is red phosphorus coated with melamine formaldehyde resin microcapsules, with the mass ratio of melamine formaldehyde resin to red phosphorus being 40:60; the nano-layered double hydroxide is zinc-aluminum-based layered double hydroxide; the antioxidant is antioxidant 168; the lubricant is zinc stearate; and the toughening agent is POE grafted maleic anhydride.

[0027] The present invention also provides a method for preparing a glass fiber reinforced red phosphorus flame retardant high-heat PA material, comprising the following steps: 1) Melamine formaldehyde resin and red phosphorus were mixed in a mass ratio of 40:60, stirred at 30-50 rpm for 3 minutes, and after mixing evenly, melt blended and extruded to obtain microencapsulated red phosphorus; 2) adding the PA6 resin, the microencapsulated red phosphorus prepared in step 1), the nano-layered double hydroxide, zinc borate, an antioxidant, a lubricant, and a toughening agent into a blender, and mixing and stirring uniformly to obtain a mixture; 3) The mixture and glass fiber are fed into a twin-screw extruder, heated to melt and extruded, the temperature of the melt extrusion is controlled between 220-250° C., and the screw speed of the twin-screw extruder is controlled between 300-550 r / min, thereby producing a glass fiber reinforced red phosphorus flame retardant high-scorching PA material.

[0028] Example 3 This embodiment provides a glass fiber reinforced red phosphorus flame retardant high-scorching PA material, including the following components in parts by weight: 60.3 parts of PA6 resin, 25 parts of glass fiber, 13 parts of microencapsulated red phosphorus, 3 parts of nano-layered double hydroxide, 3 parts of zinc borate, 0.6 parts of antioxidant, 0.7 parts of lubricant, and 1 part of toughening agent.

[0029] Among them, microencapsulated red phosphorus is red phosphorus coated with melamine formaldehyde resin microcapsules, with the mass ratio of melamine formaldehyde resin to red phosphorus being 30:70; the nano-layered double hydroxide is montmorillonite layered double hydroxide; the antioxidant is antioxidant 1098; the lubricant is calcium stearate; and the toughening agent is ethylene propylene rubber.

[0030] The present invention also provides a method for preparing a glass fiber reinforced red phosphorus flame retardant high-heat PA material, comprising the following steps: 1) Melamine formaldehyde resin and red phosphorus were mixed in a mass ratio of 30:70, stirred at 30-50 rpm for 3 minutes, and after mixing evenly, melt blended and extruded to obtain microencapsulated red phosphorus; 2) adding the PA6 resin, the microencapsulated red phosphorus prepared in step 1), the nano-layered double hydroxide, zinc borate, an antioxidant, a lubricant, and a toughening agent into a blender, and mixing and stirring uniformly to obtain a mixture; 3) The mixture and glass fiber are fed into a twin-screw extruder, heated to melt and extruded, the temperature of the melt extrusion is controlled between 220-250° C., and the screw speed of the twin-screw extruder is controlled between 300-550 r / min, thereby producing a glass fiber reinforced red phosphorus flame retardant high-scorching PA material.

[0031] Example 4 This embodiment provides a glass fiber reinforced red phosphorus flame retardant high-scorching PA material, including the following components by weight: 67.4 parts of PA6 resin, 30 parts of glass fiber, 15 parts of microencapsulated red phosphorus, 2 parts of nano-layered double hydroxide, 3 parts of zinc borate, 0.8 parts of antioxidant, 1 part of lubricant, and 4 parts of toughening agent.

[0032] Among them, microencapsulated red phosphorus is red phosphorus coated with melamine formaldehyde resin microcapsules, with the mass ratio of melamine formaldehyde resin to red phosphorus being 30:70; the nano-layered double hydroxide is magnesium-aluminum-based layered double hydroxide; the antioxidant is antioxidant 1010; the lubricant is silicone powder; and the toughening agent is ethylene propylene rubber.

[0033] The present invention also provides a method for preparing a glass fiber reinforced red phosphorus flame retardant high-heat PA material, comprising the following steps: 1) Melamine formaldehyde resin and red phosphorus were mixed in a mass ratio of 30:70, stirred at 30-50 rpm for 3 minutes, and after mixing evenly, melt blended and extruded to obtain microencapsulated red phosphorus; 2) adding the PA6 resin, the microencapsulated red phosphorus prepared in step 1), the nano-layered double hydroxide, zinc borate, an antioxidant, a lubricant, and a toughening agent into a blender, and mixing and stirring uniformly to obtain a mixture; 3) The mixture and glass fiber are fed into a twin-screw extruder, heated to melt and extruded, the temperature of the melt extrusion is controlled between 220-250° C., and the screw speed of the twin-screw extruder is controlled between 300-550 r / min, thereby producing a glass fiber reinforced red phosphorus flame retardant high-scorching PA material.

[0034] Comparative Example 1 The difference from Example 2 is that the PA material lacks microencapsulated red phosphorus, and the other components and preparation method are consistent with those of Example 2.

[0035] Comparative Example 2 The difference from Example 2 is that the microencapsulated red phosphorus in the PA material component is replaced with red phosphorus, that is, red phosphorus coated with melamine formaldehyde resin microcapsules is not used. Other components and preparation methods are consistent with those of Example 2.

[0036] Comparative Example 3 The difference from Example 2 is that the PA material lacks nano-layered double hydroxide, and the other components and preparation method are consistent with those of Example 2.

[0037] Comparative Example 4-Comparative Example 12 The difference from Example 2 is that among the components of the PA material, the nano-layered double hydroxide and zinc borate are replaced with melamine cyanurate and magnesium hydroxide. The other components and preparation method are consistent with those of Example 2, as follows: Performance testing The PA materials corresponding to Examples 1-4 and Comparative Examples 1-12 were subjected to the following performance tests. The standards cited for the tests and the experimental data obtained are shown in Tables 1, 2, and 3 below: Table 1: Test data obtained in Examples 1-4 Table 2: Test data obtained from comparative examples 1-6 Table 3: Test data obtained from comparative examples 7-12 As can be seen from Examples 1-4, the PA material of the present invention not only retains the mechanical properties of the material under normal conditions, but also meets the requirement of being non-ignitable at a 750°C glow wire, having a brighter appearance, and being resistant to precipitation of red phosphorus.

[0038] Comparison between Example 2 and Comparative Example 1 shows that, in the absence of microencapsulated red phosphorus, the flame retardancy of the PA material decreases and the glow-wire ignites at 750°C, indicating that microencapsulated red phosphorus can improve the flame retardancy of the PA material. Comparison between Example 2 and Comparative Example 2 shows that, in the absence of melamine-formaldehyde resin microcapsule-coated red phosphorus, the resulting PA material has a whitish appearance, indicating that red phosphorus easily precipitates (after precipitation, red phosphorus is oxidized to white phosphorus pentoxide in the air). This further demonstrates that melamine-formaldehyde resin microcapsule-coated red phosphorus can make the PA material resistant to red phosphorus precipitation and give the PA material product a bright appearance.

[0039] From the comparison between Example 2 and Comparative Example 3, it can be seen that the use of nano-layered double hydroxide not only retains the mechanical properties of the material under normal conditions, but also allows the material to meet the requirement of non-ignition of the glow wire at 750°C.

[0040] From comparative examples 4-12, it can be seen that when the addition amount of melamine cyanurate and magnesium hydroxide is small, the glow-wire temperature cannot reach the requirement of 750°C. As the addition amount of melamine cyanurate and magnesium hydroxide increases, the glow-wire temperature gradually increases, but the mechanical properties of the material decrease significantly.

[0041] The embodiments of the present invention are described in detail above, but the present invention is not limited to the described embodiments. It is apparent to those skilled in the art that various changes, modifications, substitutions, and variations of these embodiments may be made without departing from the principles and spirit of the present invention, and the changes still fall within the scope of protection of the present invention.

Claims

1. A glass fiber reinforced red phosphorus flame retardant high heat PA material, characterized by: The invention comprises the following components in parts by weight: 41.2-67.4 parts of PA6 resin, 20-30 parts of glass fiber, 8-15 parts of microencapsulated red phosphorus, 2-5 parts of nano-layered double hydroxide, 1-3 parts of zinc borate, 0.3-0.8 parts of antioxidant, 0.3-1 parts of lubricant and 1-4 parts of toughening agent.

2. The glass fiber reinforced red phosphorus flame retardant high heat PA material according to claim 1, characterized in that: The microencapsulated red phosphorus is red phosphorus coated with melamine formaldehyde resin microcapsules, and the mass ratio of melamine formaldehyde resin to red phosphorus is 30-40:60-70.

3. The glass fiber reinforced red phosphorus flame retardant high heat PA material according to claim 1, characterized in that: The nano-layered double hydroxide is one or more of magnesium-aluminum-based layered double hydroxide, zinc-aluminum-based layered double hydroxide, and montmorillonite layered double hydroxide.

4. The glass fiber reinforced red phosphorus flame retardant high heat PA material according to claim 1, characterized in that: The antioxidant is one or more of 1010, 168, and 1098.

5. The glass fiber reinforced red phosphorus flame retardant high heat PA material according to claim 1, characterized in that: The lubricant is one or more of pentaerythritol stearate, zinc stearate, calcium stearate, and silicone powder.

6. The glass fiber reinforced red phosphorus flame retardant high heat PA material according to claim 1, characterized in that: The toughening agent is one or two of POE grafted maleic anhydride and ethylene propylene rubber.

7. The glass fiber reinforced red phosphorus flame retardant high heat PA material according to claim 1, characterized in that: The PA6 resin has an intrinsic viscosity of 2.4-2.5 dl / g and a melt flow rate of 50-80 g / (10 min) under the test conditions of 250° C. / 2.16 kg.

8. The glass fiber reinforced red phosphorus flame retardant high heat PA material according to claim 1, characterized in that: The diameter of the glass fiber is 8-16 μm.

9. A method for preparing a glass fiber reinforced red phosphorus flame retardant high-heat PA material, characterized by: The preparation method is used to prepare a glass fiber reinforced red phosphorus flame retardant high-heat PA material according to any one of claims 1 to 8, and the preparation method comprises the following steps: 1) Melamine formaldehyde resin and red phosphorus are stirred at 30-50 rpm for 3 minutes in a mass ratio of 30-40:60-70. After mixing evenly, the mixture is melt-blended and extruded to obtain microencapsulated red phosphorus. 2) adding the PA6 resin, the microencapsulated red phosphorus prepared in step 1), the nano-layered double hydroxide, zinc borate, an antioxidant, a lubricant, and a toughening agent into a blender, and mixing and stirring uniformly to obtain a mixture; 3) The mixture and glass fiber are fed into a twin-screw extruder, heated until melted and extruded, thereby producing the glass fiber reinforced red phosphorus flame retardant high-scorching PA material.

10. The method for preparing a glass fiber reinforced red phosphorus flame retardant high-heat PA material according to claim 9, characterized in that: In step 3), the temperature of the melt extrusion is 220-250° C., and the screw speed of the twin-screw extruder is 300-550 r / min.

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