Nylon composition as well as preparation method and application thereof

Abstract

The invention discloses a nylon composition as well as a preparation method and application thereof, and belongs to the technical field of high polymer materials. The nylon composition provided by the invention is prepared from the following components in parts by mass: 28 to 62 parts of first nylon resin, 3 to 17 parts of second nylon resin, 18 to 32 parts of glass fiber, 13 to 22 parts of brominated flame retardant, 3 to 10 parts of flame-retardant synergist, 0.05 to 2 parts of antioxidant and 0.1 to 2 parts of light stabilizer, the first nylon resin comprises at least one of PA6 and PA66; the second nylon resin is prepared from at least one of PA MXD6, PA6I / 6T and PA MXD10; the light stabilizer comprises at least one of a hindered amine light stabilizer and a triazine light stabilizer. According to the nylon composition provided by the invention, the components in proper parts by mass are selected, and the components are matched with one another, so that the obtained product has good flame retardant property, mechanical property and weather resistance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and particularly relates to a nylon composition, its preparation method and application. Background Technology

[0002] Brominated modified polyamide materials are widely used in industries such as home appliances, industrial motor systems, and low-voltage electronics due to their excellent flame retardant properties, mechanical strength, and high glow wire properties. These materials are typically gray-white and are used extensively in outdoor applications. However, under ultraviolet light, brominated flame retardants readily produce bromine free radicals and generate other acidic substances such as hydrogen bromide. Both bromine free radicals and acidic substances catalyze the degradation of nylon, causing yellowing and color loss in light-colored materials. Furthermore, because brominated modified polyamide materials are frequently used outdoors and require high weather resistance, improving their outdoor weather resistance is a hot research topic. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a nylon composition with good flame retardant properties, mechanical properties, UV mechanical stability and anti-yellowing properties, as well as its preparation method and application.

[0004] To achieve the above objectives, in a first aspect, the present invention provides a nylon composition comprising the following components in parts by weight: 28-62 parts of first nylon resin, 3-17 parts of second nylon resin, 18-32 parts of glass fiber, 13-22 parts of brominated flame retardant, 3-10 parts of flame retardant synergist, 0.05-2 parts of antioxidant, and 0.1-2 parts of light stabilizer; The first nylon resin includes at least one of PA6 and PA66; The second nylon resin includes at least one of PA MXD6, PA6I / 6T, and PA MXD10; The light stabilizer includes at least one of hindered amine light stabilizers and triazine light stabilizers.

[0005] The nylon composition provided by this invention, by selecting appropriate mass parts of the components and combining them with each other, yields a product with good flame retardant properties, mechanical properties, and weather resistance.

[0006] Specifically, in the first aspect, the first nylon resin selected in this invention possesses superior mechanical strength and toughness, while the second nylon resin exhibits good stability and heat resistance. Blending the two in specific proportions effectively enhances the product's mechanical properties and UV resistance. Furthermore, the second nylon resin exhibits a certain tendency to form char, allowing it to be combined with brominated flame retardants and flame retardant synergists to improve the product's flame retardancy. In the second aspect, the light stabilizer selected in this invention includes at least one of hindered amine light stabilizers and triazine light stabilizers. These two types of light stabilizers demonstrate better compatibility with the components in the system of this invention and exhibit better UV resistance in the brominated flame retardant system, thereby effectively reducing color difference changes in the product before and after UV irradiation.

[0007] For example, the first nylon resin can be any point value or any two-point range value between 28 and 62 parts, such as 30-60 parts, or 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, etc.; the second nylon resin can be any point value or any two-point range value between 3 and 17 parts, such as 5-15 parts, or The components can be 3, 5, 6, 7, 8, 10, 12, 14, 15, 16, 17 parts, etc.; the glass fiber can be any point value or any two-point range value between 18 and 32 parts, for example, 20-30 parts, or 18, 20, 22, 24, 26, 28, 30, 32 parts, etc.; the brominated flame retardant can be any point value or any two-point range value between 13 and 22 parts, for example, 15-20 parts, or 1... 3 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 22 parts, etc.; the flame retardant synergist can be any point value or any two-point range value between 3 and 10 parts, for example, it can be 5-8 parts, or it can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.; the antioxidant can be any point value or any two-point range value between 0.05 and 2 parts, for example, it can be 0.1-1.8 parts, or it can be 0.05 parts, 0.1 parts, 0... 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, etc.; the light stabilizer can be any point value or any two-point range value between 0.1 and 2 parts, for example, it can be 0.2-1.8 parts, or it can be 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, etc.

[0008] Preferably, in the nylon composition, the mass percentage of the first nylon resin is ≥24%.

[0009] More preferably, the mass percentage of the first nylon resin in the nylon composition is 30-52%.

[0010] As a preferred embodiment of the nylon composition of the present invention, the nylon composition comprises the following components in parts by weight: 40-50 parts of first nylon resin, 8-10 parts of second nylon resin, 24-26 parts of glass fiber, 16-18 parts of brominated flame retardant, 4-6 parts of flame retardant synergist, 0.4-0.6 parts of antioxidant, and 0.4-0.6 parts of light stabilizer.

[0011] The present invention has found that the mass fraction of a component in a nylon composition affects the overall performance of the composition. When the mass fraction of the component is further selected within the above-mentioned range, the overall performance of the resulting nylon composition is even better.

[0012] In a preferred embodiment of the nylon composition of the present invention, the relative viscosity of the first nylon resin is 2.1-2.7.

[0013] For example, the relative viscosity of the first nylon resin can be any point value between 2.1 and 2.7 or a range between any two points, such as 2.2-2.6, 2.2-2.4, 2.4-2.6, or 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, etc.

[0014] It should be noted that the relative viscosity of the first nylon resin was tested according to ISO 307:2019, with 96% sulfuric acid as solvent and a temperature of 25°C.

[0015] The present invention has found that further selecting the relative viscosity of the first nylon resin within the above-mentioned range can result in better compatibility with other components, improve the dispersion effect of the components, and thus make the overall performance of the obtained product better.

[0016] It should be noted that the present invention does not have any particular requirements for the relative viscosity of the second nylon resin. For example, the relative viscosity of the second nylon resin may be 1.5-2.5.

[0017] It should be noted that the relative viscosity of the second nylon resin was tested according to ISO 307:2019, with 96% sulfuric acid as solvent and a temperature of 25°C.

[0018] In a preferred embodiment of the nylon composition of the present invention, the mass ratio of the first nylon resin to the second nylon resin is (2-12):1.

[0019] For example, the mass ratio of the first nylon resin and the second nylon resin can be any point value or any two points within the range of (2-12):1, such as (2-5.7):1, (5.7-9.6):1, (2-9.6):1, (9.6-12):1, etc., or it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, etc.

[0020] Preferably, the mass ratio of the first nylon resin to the second nylon resin is (5.5-10):1.

[0021] This application research found that the mass ratio of the first nylon resin and the second nylon resin affects the interaction between them. It is preferred to compound them within the above-mentioned mass ratio range to achieve excellent mechanical properties, flame retardant properties and weather resistance of the product.

[0022] In a preferred embodiment of the nylon composition of the present invention, the glass fiber has an average diameter of 10-18 μm.

[0023] For example, the average diameter of the glass fiber can be any point value or a range between any two points between 10-18 μm, such as 11-17 μm, 11-13 μm, 13-17 μm, etc., or 10 μm, 11 μm, 13 μm, 15 μm, 17 μm, 18 μm, etc.

[0024] It should be noted that the average diameter of the glass fiber is tested according to Method A in ISO 1888:2022.

[0025] This invention has found that when the average diameter of glass fibers is within the above-mentioned range, they can be better dispersed within the system to form a dense reinforcing network, which helps to improve the mechanical properties of the product. At the same time, it can also reduce interface defects, improve humid heat stability, and enhance the weather resistance of the product. In addition, it can also improve the flame retardant stability of the product.

[0026] As a preferred embodiment of the nylon composition of the present invention, the brominated flame retardant includes at least one of brominated polystyrene, decabromodiphenyl ethane, and brominated epoxy.

[0027] In a preferred embodiment of the nylon composition of the present invention, the flame retardant synergist includes at least one of antimony white and zinc borate.

[0028] In a preferred embodiment of the nylon composition of the present invention, the antioxidant includes at least one of hindered phenolic antioxidants and phosphite antioxidants.

[0029] For example, the hindered phenolic antioxidants include antioxidant 1010, antioxidant 1076, antioxidant 264, etc.; the phosphite antioxidants include antioxidant 168, antioxidant 626, antioxidant 618, etc.

[0030] In a preferred embodiment of the nylon composition of the present invention, the hindered amine light stabilizer includes at least one selected from (2,2,6,6-tetramethyl-4-hydroxypiperidine) benzoate, bis(2,2,6,6-tetramethyl-4-hydroxypiperidine) sebacate, tris(1,2,2,6,6-pentamethyl-4-hydroxypiperidine) phosphite, bis(1,2,2,6,6-pentamethyl-4-hydroxypiperidine) sebacate, and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine.

[0031] As a preferred embodiment of the nylon composition of the present invention, the triazine light stabilizer includes at least one of 2,4,6-tris(2′-hydroxy-4′-n-butoxyphenyl) and 2,4-di(2-hydroxy-4-alkoxy)phenyl-6-(4-biphenyl)-1,3,5-triazine.

[0032] In a preferred embodiment of the nylon composition of the present invention, the light stabilizer includes hindered amine light stabilizers and triazine light stabilizers.

[0033] Preferably, the mass ratio of the hindered amine light stabilizer to the triazine light stabilizer is 1:(0.8-4.2).

[0034] For example, the mass ratio of the hindered amine light stabilizer to the triazine light stabilizer can be any point value between 1:(0.8-4.2) or a range between any two points, such as 1:(1-4), or 1:0.8, 1:1, 1:2, 1:3, 1:4, 1:4.2, etc.

[0035] In a second aspect of the invention, the invention provides a method for preparing the nylon composition, the method comprising the following steps: mixing the components uniformly and then performing melt kneading, followed by extrusion granulation to obtain the nylon composition.

[0036] In a preferred embodiment of the preparation method described in this invention, the temperature of the melt mixing is 80-270℃, and the screw speed during the melt mixing is 300-400 r / min.

[0037] In a third aspect, the present invention provides the use of the nylon composition in the manufacture of electronic and electrical appliances.

[0038] For example, the electronic appliances include home appliances, industrial motors, new energy three-electric systems, electronic components, connectors, etc.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows: The nylon composition provided by this invention, by selecting appropriate mass parts of the components and coordinating the components with each other, can achieve good mechanical properties, flame retardant properties and weather resistance. Detailed Implementation

[0040] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0041] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch.

[0042] First Nylon Resin 1: PA66, relative viscosity 2.4, PA66 EPR24, Shenzhen Shenma Chemical Co., Ltd.; First Nylon Resin 2: PA66, relative viscosity 2.2, PA66 U2501, Invista Nylon Chemicals (China) Co., Ltd.; First Nylon Resin 3: PA66, relative viscosity 2.6, PA66 EPR27, Shenzhen Shenma Chemical Co., Ltd.; First Nylon Resin 4: PA6, relative viscosity 2.4, PA6 M2400, Guangdong Xinhui Meida Nylon Co., Ltd.; First Nylon Resin 5: PA612, relative viscosity 2.4, PA612 A170, Shandong Guangyin New Material Co., Ltd.; Second nylon resin 1: PA6I / 6T, TI1207, Shandong Guangyin New Material Co., Ltd.; Second nylon resin 2: PA MXD6, Shanghai Yinggu Chemical Co., Ltd.; Second nylon resin 3: PA MXD10, Shanghai Yinggu Chemical Co., Ltd.; Glass fiber 1: average diameter 11μm, ECS11-4.5-560A, Jushi Group; Glass fiber 2: average diameter 17μm, E7CS17-2400-362H, Jushi Group; Glass fiber 3: average diameter 13μm, E7CS13-03-508A, Jushi Group; Brominated flame retardant: brominated polystyrene, commercially available; Flame retardant synergist: Antimony white, commercially available; Antioxidant: A mixture of antioxidant 1010 and antioxidant 168 in a 1:1 mass ratio; Light stabilizer 1: A mixture of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and 2,4-bis(2-hydroxy-4-alkoxy)phenyl-6-(4-biphenyl)-1,3,5-triazine in a 1:1 mass ratio; Light stabilizer 2: A mixture of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and 2,4-bis(2-hydroxy-4-alkoxy)phenyl-6-(4-biphenyl)-1,3,5-triazine in a mass ratio of 1:4; Light stabilizer 3: N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine, commercially available; Light stabilizer 4: 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, commercially available.

[0043] Examples 1-16 and Comparative Examples 1-5 The present invention provides a nylon composition in the embodiments and comparative examples, wherein the component content (parts by weight) of the nylon composition is shown in Tables 1-2; Table 1 Table 2 The method for preparing the nylon composition provided in Example 1 is as follows: After the components are mixed evenly, they are added to a twin-screw extruder for melt mixing. There are a total of 8 stages. The temperatures of the first to the eighth stages are 80℃, 270℃, 260℃, 250℃, 210℃, 210℃, 240℃, and 260℃, respectively. The screw speed is 400 r / min. After melt mixing, the mixture is extruded and granulated to obtain a nylon composition.

[0044] The preparation methods of the nylon compositions provided in Examples 2-16 and Comparative Examples 1-5 are consistent with those in Example 1, except that the relevant components are not required.

[0045] Example of effect The performance of the nylon compositions prepared in the examples and comparative examples of this invention is verified by the following aspects: 1. Flame retardant performance test: The flame retardant performance of the injection molded strips was tested according to the relevant standards of UL 94-2015. The sample thickness was 0.8mm, and the flame retardant rating was divided into V-0, V-1, V-2 and no rating (NR). 2. Tensile strength: Tested according to ISO 527-2012; tensile rate: 10 mm / min; 3. Cantilever beam notched impact strength: Tested according to ISO 180-2000, type A notch; 4. Color Difference: A 60mm × 60mm × 2mm color sample was injection molded. The L, a, and b values ​​were tested according to CIE 2000, where L represents lightness / darkness, a represents red / green, and b represents yellow / blue. These values ​​were recorded as L1, a1, and b1. Then, the color sample underwent a 200-hour UV test according to ISO 4892-3:2024, using period 1, a UV wavelength of 340nm, and an irradiance of 0.76W / m². 2 Then, take out the test values ​​L, a, and b, and record them as L2, a2, and b2. The color difference ΔE can be calculated using the following formula: ΔE = ((L2 - L1)) 2 +(a2-a1) 2 +(b2-b1) 2 ) 0.5 ; 5. Weather resistance: According to ISO 4892-3, after 1000h of UV testing, the product is placed at 120℃ for 12h to dry the moisture. The retention rate of tensile strength and cantilever beam notched impact strength after the placement is calculated compared with that before the aging test. The results of the above tests are shown in Table 3. Table 3 As can be seen from Table 3, when the technical solution of the present invention is adopted, the obtained nylon composition has excellent flame retardant properties, mechanical properties, and weather resistance; specifically, the obtained products all have a flame retardant rating of V-0, a tensile strength of over 131 MPa, and a cantilever beam notched impact strength of 8.0 kJ / m. 2 Above, the color difference is below 7.01, the cantilever beam notched impact strength retention rate is above 87%, and the tensile strength retention rate is above 90%; As can be seen from Examples 1, 4-6 and Comparative Example 1, the types of the first nylon resin and the second nylon resin affect the overall performance of the product. When the type of the first nylon resin in Comparative Example 1 is not within the range given in this invention, the flame retardant performance of the obtained product is significantly reduced, and the notched impact strength and tensile strength of the cantilever beam also show a certain degree of decreasing trend. As can be seen from Examples 1 and Comparative Examples 2-3, the first nylon resin and the second nylon resin have a good compounding effect. When the second nylon resin is not added in Comparative Example 2, the flame retardant performance of the obtained product is significantly reduced, and the weather resistance of the obtained product is also reduced. This is reflected in the significant increase in color difference after ultraviolet irradiation, and the retention rate of cantilever beam notched impact strength and tensile strength are reduced to a certain extent. When the first nylon resin is not added in Comparative Example 3, the cantilever beam notched impact strength of the obtained product is significantly reduced, and the weather resistance of the obtained product is also reduced, as reflected in the obvious downward trend of tensile strength retention rate. As can be seen from Examples 1-3 and Comparative Example 4, the mass fraction of the components also affects the overall performance of the product. When the mass fraction of the first nylon resin and the second nylon resin in Comparative Example 4 is not within the range given in this invention, the cantilever beam notched impact strength and tensile strength of the obtained product show a downward trend, and the weather resistance of the obtained product also decreases, which is reflected in the obvious downward trend of tensile strength retention rate and cantilever beam notched impact strength retention rate. As can be seen from Examples 1, 15-16 and Comparative Example 5, the type of light stabilizer affects the overall performance of the product. When the light stabilizer selected in Comparative Example 5 is not the type given in this invention, the weather resistance of the obtained product decreases significantly, the color difference after ultraviolet irradiation increases significantly, the impact strength retention rate also decreases to a certain extent, and the tensile strength of the obtained product also shows a certain downward trend.

[0046] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A nylon composition, characterized in that, The nylon composition comprises the following components in parts by weight: 28-62 parts of first nylon resin, 3-17 parts of second nylon resin, 18-32 parts of glass fiber, 13-22 parts of brominated flame retardant, 3-10 parts of flame retardant synergist, 0.05-2 parts of antioxidant, and 0.1-2 parts of light stabilizer; The first nylon resin includes at least one of PA6 and PA66; The second nylon resin includes at least one of PA MXD6, PA6I / 6T, and PA MXD10; The light stabilizer includes at least one of hindered amine light stabilizers and triazine light stabilizers.

2. The nylon composition according to claim 1, characterized in that, The nylon composition comprises the following components in parts by weight: 40-50 parts of first nylon resin, 8-10 parts of second nylon resin, 24-26 parts of glass fiber, 16-18 parts of brominated flame retardant, 4-6 parts of flame retardant synergist, 0.4-0.6 parts of antioxidant, and 0.4-0.6 parts of light stabilizer.

3. The nylon composition according to claim 1, characterized in that, The relative viscosity of the first nylon resin is 2.1-2.

7.

4. The nylon composition according to claim 1, characterized in that, The mass ratio of the first nylon resin to the second nylon resin is (2-12):

1.

5. The nylon composition according to claim 1, characterized in that, The average diameter of the glass fiber is 10-18 μm.

6. The nylon composition according to claim 1, characterized in that, The brominated flame retardant includes at least one of brominated polystyrene, decabromodiphenyl ethane, and brominated epoxy. And / or, the flame retardant synergist includes at least one of antimony white and zinc borate; And / or, the antioxidant includes at least one of hindered phenolic antioxidants and phosphite antioxidants.

7. The nylon composition according to claim 1, characterized in that, The hindered amine light stabilizers include at least one of the following: (2,2,6,6-tetramethyl-4-hydroxypiperidine) benzoate, bis(2,2,6,6-tetramethyl-4-hydroxypiperidine) sebacate, tris(1,2,2,6,6-pentamethyl-4-hydroxypiperidine) phosphite, bis(1,2,2,6,6-pentamethyl-4-hydroxypiperidine) sebacate, and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine. And / or, the triazine light stabilizer includes at least one of 2,4,6-tris(2′-hydroxy-4′-n-butoxyphenyl) and 2,4-di(2-hydroxy-4-alkoxy)phenyl-6-(4-biphenyl)-1,3,5-triazine.

8. The method for preparing the nylon composition according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: The components are mixed evenly and then melt-blended, followed by extrusion granulation to obtain a nylon composition.

9. The use of the nylon composition according to any one of claims 1-7 in the manufacture of electronic and electrical appliances.

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