Polyamide composite material, method for producing same, and use thereof

Abstract

The application discloses a polyamide composite material, which comprises the following components in parts by weight: 39-94 parts of polyamide resin; 14-18 parts of phosphinic acid salt flame retardant; 1-3 parts of melamine polyphosphate; 1-6 parts of lanthanum oxide; 2-6 parts of low-melting-point glass powder; 0-50 parts of glass fiber; and the weight ratio of the lanthanum oxide to the low-melting-point glass powder is (0.5-2.5):1. By adding the specific content of the lanthanum oxide and the low-melting-point glass powder in the phosphorus-nitrogen flame retardant system, good flame retardancy, ultraviolet resistance and high surface glossiness can be obtained, and the polyamide composite material is suitable for preparing equipment housings.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a polyamide composite material, its preparation method, and its application. Background Technology

[0002] Nylon materials are widely used due to their excellent mechanical properties, wear resistance, and self-lubricating properties. However, nylon itself is flammable and requires modification by adding flame retardants. Phosphorus-nitrogen flame retardants (halogen-free flame retardants) have become a research hotspot due to their advantages of low toxicity, low smoke, and halogen-free environmental friendliness. However, halogen-free flame-retardant glass fiber reinforced nylon also has its own disadvantages. One is its poor resistance to ultraviolet radiation, which limits its use under light conditions. Another is that phosphorus-nitrogen flame retardants can affect surface gloss.

[0003] In the prior art, weathering agents are often added to improve the UV resistance of nylon materials. However, phosphorus and nitrogen flame retardants are highly acidic, while common weathering agents are alkaline substances. Therefore, weathering additives in phosphorus and nitrogen flame retardant nylon materials often fail to function due to neutralization and cannot play a weathering role.

[0004] Meanwhile, existing methods for improving the surface gloss of nylon materials mainly involve using special additives, which can easily lead to uneven dispersion.

[0005] Therefore, improving the UV resistance and surface gloss of phosphorus-nitrogen flame-retardant nylon materials has great economic value. Summary of the Invention

[0006] The purpose of this invention is to provide a flame-retardant polyamide composite material with excellent flame retardancy, good UV resistance, and high surface gloss, as well as its preparation method and application.

[0007] This invention is achieved through the following technical solution:

[0008] A polyamide composite material, by weight, comprises the following components:

[0009] 39-94 parts of polyamide resin;

[0010] 14-18 parts of phosphonate flame retardant;

[0011] 1-3 parts of melamine polyphosphate;

[0012] Lanthanum oxide 1-6 parts;

[0013] 2-6 parts of low melting point glass powder;

[0014] 0-50 parts glass fiber;

[0015] The weight ratio of lanthanum oxide to low-melting-point glass powder is (0.5-2.5):1.

[0016] Preferably, the weight ratio of lanthanum oxide to low-melting-point glass powder is (1-2):1.

[0017] In the polyamide composite material of the present invention, the content of polyamide resin can be any value or a range between 39 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, and 94 parts; the content of phosphorus-nitrogen flame retardant (phosphinate flame retardant and melamine polyphosphate) can be any value or a range between 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, and 20 parts; the content of lanthanum oxide can be any value or a range between 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, and 6 parts; and the content of low melting point glass powder can be any value or a range between 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, and 6 parts. The weight ratio of lanthanum oxide to low-melting-point glass powder can be any value or a range between 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, and 2.5:1.

[0018] The polyamide resin content ranges from 32.7% to 84 wt% by weight, and the total content of low-melting-point glass powder and lanthanum oxide ranges from 1.8% to 15 wt%.

[0019] The polyamide resin is selected from at least one of aromatic polyamide resin and aliphatic polyamide resin.

[0020] The aliphatic polyamide resin is selected from PA66, PA46, PA610, PA612, PA56, PA510, PA512, PA910, PA912, PA913, PA914, PA915, PA616, PA936, PA1010, PA1012, PA1013, PA1014, PA1210, PA1212, PA1213, PA1214, PA614, PA613, PA615, PA616, etc.

[0021] The semi-aromatic polyamide is selected from PA MXD6, PA10T, PA10T1010, PA10T66, PA6T, PA6T66, PA9T, etc.

[0022] The polylactam is selected from PA5, PA6, PA11, PA12, etc.

[0023] The relative viscosity of the polyamide resin can be 2.0-3.2, and concentrated sulfuric acid with a mass concentration of 96% is used as the solvent according to ISO 307:2007 standard.

[0024] The phosphonate flame retardant is a dialkyl phosphonate, which is selected from one or more of the following: methyl ethyl aluminum phosphonate, diethyl aluminum phosphonate, diethyl zinc phosphonate, and diethyl titanium phosphonate.

[0025] The average particle size of the lanthanum oxide is 1-20 micrometers, preferably 2-15 micrometers, and more preferably 3-10 micrometers.

[0026] The initial melting temperature of the low-melting-point glass powder is not higher than 900℃, and the average particle size is 6-11 micrometers, preferably 380-500℃. The initial melting temperature is tested using an image-based sintering point tester.

[0027] The average particle size of lanthanum oxide and low-melting-point glass powder was measured using a laser particle size analyzer.

[0028] You may choose to add 0-2 parts of additives according to actual needs. The additives are selected from at least one of the following: release agent, nucleating agent, lubricant, colorant, light stabilizer, ultraviolet light absorber, heat stabilizer, antistatic agent, and antioxidant.

[0029] The lubricant may be at least one of hyperbranched polyester, stearate, ethylene bis-stearamide, and polyethylene wax.

[0030] Heat stabilizers can be phenolic heat stabilizers, thiosulfate esters, aromatic amines, etc.

[0031] The light stabilizer is selected from hindered amine light stabilizers, benzotriazole light stabilizers, or a combination thereof. To improve strength, 0-50 parts of glass fiber may be added.

[0032] The preparation method of the polyamide composite material of the present invention includes the following steps: mixing the components evenly according to the formula, and extruding and granulating them through a twin-screw extruder to obtain the polyamide composite material.

[0033] The polyamide composite material of the present invention is used to manufacture equipment housings.

[0034] The present invention has the following beneficial effects:

[0035] This invention introduces a specific ratio of lanthanum oxide and low-melting-point glass powder into a phosphorus-nitrogen flame-retardant polyamide composite material, which not only effectively improves the UV resistance but also significantly enhances the surface gloss. Detailed Implementation

[0036] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0037] The experimental materials used in this invention are sourced from the following sources:

[0038] PA66: Purchased from Huafeng Group, typical grade EP-158, relative viscosity 2.7;

[0039] PA6: PA6 HY-2800, Haiyang Chemical Fiber Company, relative viscosity 2.8;

[0040] PA66 / 6: PA66 EP26CL, Huafeng Group, relative viscosity 2.6;

[0041] PA66 / 6T: NPD-652, Invista Ltd., relative viscosity 2.3;

[0042] Aluminum diethylphosphinate: OP1230, Klein Company.

[0043] Melamine polyphosphate: budit 3141, supplied by Bode Company.

[0044] Lanthanum oxide was purchased from Ningbo Bohuas Nanotechnology Co., Ltd., and the following raw materials with different average particle sizes were obtained through screening.

[0045] Lanthanum oxide A: average particle size is 1.0 micrometers;

[0046] Lanthanum oxide B: average particle size is 3.0 micrometers;

[0047] Lanthanum oxide (C): average particle size 10.0 micrometers;

[0048] Lanthanum oxide D: average particle size is 120.0 micrometers;

[0049] Low melting point glass powder A: FD56, initial melting temperature 395℃, ampere-nano;

[0050] Low melting point glass powder B: FD61, initial melting temperature 450℃, ampere-nano;

[0051] Low melting point glass powder C: FD86, initial melting temperature 706℃, ampere-nano;

[0052] Low melting point glass powder D: FD106, initial melting temperature 880℃, ampere-micron;

[0053] Fiberglass: sourced from Chongqing Composite Materials, grade ECS301HP-03-H, diameter 10um, length 3mm;

[0054] Hyperbranched polyester: hyper C100, provided by Wuhan Hyperbranching Company.

[0055] Preparation method of polyamide composite material in the examples and comparative examples: The components were mixed evenly according to the specified ratio, and then extruded and granulated using a twin-screw extruder to obtain the polyamide composite material. The maximum temperature of the screw barrel was 20°C above the melting point of the polyamide, and the rotation speed was 300 rpm.

[0056] Test methods:

[0057] (1) Flame retardancy: The flame retardancy performance of the sample was tested according to the relevant standard of UL 94-2015. The sample thickness was 0.8 mm, and the flame retardancy rating was divided into V-0, V-1, V-2 and no rating (NR).

[0058] (2) UV resistance: Tested according to ISO 4892-2:2013 standard, with a cycle of 600h, and the grayscale and color difference values ​​were recorded. The higher the grayscale, the better the weather resistance; the higher the color difference value, the worse the weather resistance.

[0059] (3) Surface gloss: Tested according to GB8807-88 standard and the value at 60° is recorded. The higher the value, the higher the gloss.

[0060] Table 1: Component content and test results of polyamide composites in Examples 1-6

[0061] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PA66 40 65 90 PA6 65 PA66 / 6 65 PA66 / 6T 65 Aluminum diethylphosphinate 14 16 18 16 16 16 melamine polyphosphate 1 3 2 3 3 3 Lanthanum oxide B 1 5 3 5 5 5 Low melting point glass powder B 2 3 5 3 3 3 Fiberglass 0 30 50 30 30 30 Hyperbranched polyester 0.5 Flame retardancy V0 V0 V0 V0 V0 V0 UV resistance, grayscale Level 4 Level 4-5 Level 4 Level 4-5 Level 4-5 Level 4-5 UV resistance, color difference value 2.8 1.6 1.5 1.9 1.8 1.6 Surface gloss (°) 51 58 52 55 57 60

[0062] Table 2: Component content and test results of polyamide composites in Examples 7-12

[0063] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 PA66 65 65 65 65 65 65 Aluminum diethylphosphinate 16 16 16 16 16 16 melamine polyphosphate 3 3 3 3 3 3 Lanthanum oxide label A C D B B B Lanthanum oxide content 5 5 5 5 5 5 Low melting point glass powder grade B B B A C D Low melting point glass powder content 3 3 3 3 3 3 Fiberglass 30 30 30 30 30 30 Flame retardancy V0 V0 V0 V0 V0 V0 UV resistance, grayscale Level 4-5 Level 4-5 Level 4-5 Level 4-5 Level 4 Level 4 UV resistance, color difference value 1.8 1.7 1.8 1.9 2.5 2.9 Surface gloss (°) 52 65 53 55 57 55

[0064] As can be seen from Examples 2 / 7-9, the higher the surface gloss of lanthanum oxide with a preferred average particle size, the better its UV resistance.

[0065] As can be seen from Examples 2 / 10-12, the better the UV resistance, the lower the melting point of the glass powder with the preferred initial melting temperature.

[0066] Table 3: Component content and test results of polyamide composites in Examples 13-16

[0067] Example 13 Example 14 Example 15 Example 16 PA66 65 65 65 65 Aluminum diethylphosphinate 16 16 16 16 melamine polyphosphate 3 3 3 3 Lanthanum oxide B 2.7 4 5.3 5.7 Low melting point glass powder B 5.3 4 2.7 2.3 Fiberglass 30 30 30 30 Flame retardancy V0 V0 V0 V0 UV resistance, grayscale Level 4-5 Level 4-5 Level 4-5 Level 4-5 UV resistance, color difference value 1.8 1.5 1.5 1.7 Surface gloss (°) 54 58 65 58

[0068] As can be seen from Examples 2-13-16, the higher the surface gloss and the better the UV resistance when the preferred ratio of lanthanum oxide / low melting point glass powder is used.

[0069] The polyamide composite material of the present invention has a flame retardancy of not less than V1, a gray level of not less than 4 after UV resistance test, a color difference of not more than 3.0, and a surface gloss of more than 50°.

[0070] Table 4: Component content and test results of comparative polyamide composite materials

[0071] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PA66 65 65 65 65 Aluminum diethylphosphinate 16 16 16 16 melamine polyphosphate 3 3 3 3 Lanthanum oxide B 8 7 1.3 0 Low melting point glass powder B 0 1 6.7 8 Fiberglass 30 30 30 30 Flame retardancy V1 V0 V0 V0 UV resistance, grayscale Level 3-4 Level 3-4 Level 4 Level 4 UV resistance, color difference value 3.7 3.5 3.0 3.5 Surface gloss (°) 48 45 45 45

[0072] As can be seen from Comparative Examples 1-4, when the ratio of lanthanum oxide to low-melting-point glass powder is not within the scope of protection of this invention, it is impossible to simultaneously achieve the technical effects of good UV resistance and high surface gloss.

Claims

1. A polyamide composite material, characterized in that, By weight, it includes the following components: 39-94 parts of polyamide resin; 14-18 parts of phosphonate flame retardant; 1-3 parts of melamine polyphosphate; Lanthanum oxide 1-6 parts; 2-6 parts of low melting point glass powder; 0-50 parts glass fiber; The weight ratio of lanthanum oxide to low-melting-point glass powder is (0.5-2.5):

1.

2. The polyamide composite material according to claim 1, characterized in that, The weight ratio of lanthanum oxide to low-melting-point glass powder is (1-2):

1.

3. The polyamide composite material according to claim 1, characterized in that, The phosphonate flame retardant is a dialkyl phosphonate, which is selected from one or more of the following: methyl ethyl aluminum phosphonate, diethyl aluminum phosphonate, diethyl zinc phosphonate, and diethyl titanium phosphonate.

4. The polyamide composite material according to claim 1, characterized in that, The average particle size of the lanthanum oxide is 1-20 micrometers, preferably 2-15 micrometers, and more preferably 3-10 micrometers.

5. The polyamide composite material according to claim 1, characterized in that, The initial melting temperature of the low melting point glass powder is not higher than 900℃, preferably 380-900℃, and more preferably 380-500℃.

6. The polyamide composite material according to claim 1, characterized in that, The polyamide resin is selected from at least one of aromatic polyamide resin and aliphatic polyamide resin, and the relative viscosity of the polyamide resin is 2.0-3.

2.

7. The polyamide composite material according to claim 1, characterized in that, The product also includes 0-2 parts by weight of additives, wherein the additives are selected from one or more of the following: release agents, nucleating agents, lubricants, colorants, light stabilizers, ultraviolet absorbers, heat stabilizers, antistatic agents, and antioxidants.

8. A method for preparing the polyamide composite material according to any one of claims 1-7, characterized in that, The process includes the following steps: mixing the components evenly according to the formula, and granulating them by extrusion through a twin-screw extruder to obtain a polyamide composite material.

9. The application of the polyamide composite material according to any one of claims 1-7, characterized in that, Used to manufacture equipment housings.