Polyamide composite material and its method of manufacture and use

Abstract

This paper discloses a polyamide composite material comprising 77.2 to 94.8 parts by weight of PAXI / XT, 5 to 20 parts by weight of a semi-crystalline polyamide, and 0.2 to 0.8 parts by weight of a silicone elastomer powder containing methacryloyloxy functional groups, where the semi-crystalline polyamide is at least one selected from the group consisting of PA66, PA610, PA612, PA106, PA1010, and PA1012, and the PAXI / XT is a copolymer of aliphatic diamine X, isophthalic acid I, and terephthalic acid T. This polyamide composite material offers advantages such as high light transmittance, high haze (excellent light scattering properties), and excellent chemical resistance. It is suitable for the manufacture of navigation lights for plant protection drones.

Description

[Technical Field]

[0001] The present invention relates to the technical field of polymeric materials, in particular to polyamide composite materials and their manufacturing methods and uses. [Background technology]

[0002] Light-diffusing materials (LDMs) are materials capable of transmitting light and creating a light diffusion effect. These materials can diffuse incident light, which would otherwise be a point or linear source, into a linear or surface light source through scattering and refraction, significantly increasing the light diffusion area and reducing glare caused by concentrated light. Currently available light-diffusing materials generally consist of a matrix material and light-diffusing particles. Matrix materials include polycarbonate (PC), polyethylene terephthalate (PET), and polymethyl methacrylate (PMMA). Light-diffusing particles include organic, inorganic, and organic-inorganic hybrid materials such as polystyrene (PS), silicon dioxide (SiO2), titanium dioxide (TiO2), and PMMA / SiO2. Light-diffusing particles are incorporated into or on the surface of the matrix, utilizing the reflection and refraction of light between the diffusing particles to achieve light diffusion. However, while the addition of light-diffusing agents to conventional light-diffusing materials improves the haze of the composite, it also significantly reduces the light transmittance of the material.

[0003] Currently, commercially available light diffusion materials are mainly based on PC resin, but PC has poor chemical resistance and is prone to corrosion and cracking when it comes into contact with chemicals. For example, in the case of navigation lights for plant protection drones, there is a high possibility that they will come into contact with various chemicals such as pesticides during use, which will significantly shorten the service life of the PC light diffusion material.

[0004] Transparent nylon resin is an amorphous polyamide material. Compared to PC materials, transparent nylon has superior chemical resistance, making it more suitable for light-scattering materials that are prone to contact with chemicals. However, the chemical resistance of conventional transparent nylon resin is insufficient for direct application, and there are no related patents reported for transparent nylon light-scattering materials. Therefore, special application scenarios require light-scattering materials with better chemical resistance. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a polyamide composite material having advantages such as high transparency, excellent scattering properties, and excellent chemical resistance.

[0006] Another object of the present invention is a method for producing and using polyamide composite materials. [Means for solving the problem]

[0007] The present invention is realized by the following technical solutions:

[0008] 1. A polyamide composite material comprising: The composition comprises 77.2 to 94.8 parts by weight of PAXI / XT, 5 to 20 parts by weight of a semi-crystalline polyamide, and 0.2 to 0.8 parts by weight of a silicone elastomer powder containing a methacryloyloxy functional group, wherein the semi-crystalline polyamide is at least one selected from the group consisting of PA66, PA610, PA612, PA106, PA1010, and PA1012, the PAXI / XT is a copolymer of aliphatic diamine X, isophthalic acid I, and terephthalic acid T, and the aliphatic diamine X is at least one selected from the group consisting of 1,6-hexanediamine and 1,10-decanediamine.

[0009] Preferably, the diamine X of PAXI / XT corresponds to the diamine units of the semi-crystalline polyamide.

[0010] Specifically, the PAXI / XT is at least one selected from the group consisting of PA6I / 6T and PA10I / 10T.

[0011] When PAXI / XT is PA6I / 6T, the molar ratio of 6I units to 6T units is 65:35 to 75:25, preferably 69:31 to 71:29, and when PAXI / XT is PA10I / 10T, the molar ratio of 10I to 10T is 75:25 to 85:15, preferably 79:21 to 81:19. If the ratio of XI to XT in PAXI / XT is outside the above range, the crystallinity becomes high and transparency is lost.

[0012] In order not to significantly reduce light transmittance, the average particle size is set to 0.1 to 8 μm. Preferably, the average particle size of the silicone elastomer powder containing methacryloyloxy functional groups is in the range of 0.1 to 3 μm.

[0013] The polyamide composite has a light transmittance of greater than 73% and a haze of greater than 65%.

[0014] Depending on the actual needs, it may be determined whether to add 0 to 2 parts by weight of an auxiliary agent, and the auxiliary agent may be at least one selected from the group consisting of an antioxidant, a lubricant, and an ultraviolet inhibitor.

[0015] The method for producing a polyamide composite material of the present invention includes the steps of uniformly mixing the components in a compounding ratio, then extruding the mixture using a twin-screw extruder at a temperature of 200 to 280°C and a rotation speed of 200 to 400 rpm to granulate the mixture, thereby obtaining a polyamide composite material.

[0016] A use of the polyamide composite material of the present invention is to manufacture navigation lights for plant protection drones. [Effects of the Invention]

[0017] The present invention has the following beneficial effects:

[0018] In the present invention, transparent polyamide PAXI / XT and semi-crystalline polyamide are combined at a specific content. Preferably, when these two polyamide resins have the same diamine structure, significant transesterification reactions occur easily during the melt processing process, resulting in a uniform system and the formation of a "microcrystalline" structure. The dense crystalline regions of the "microcrystalline" structure can further improve the chemical resistance of the material without significantly reducing light transmittance. Furthermore, by using a silicone elastomer powder with a specific particle size containing methacryloyloxy functional groups, the dense crystalline regions of the "microcrystalline" structure can significantly improve the light scattering properties of the polyamide composite (higher transparency, higher haze, better light scattering properties), with only a small reduction in light transmittance. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in detail below with reference to specific examples. The following examples are provided for the purpose of providing a better understanding of the present invention to those skilled in the art, and are not intended to limit the present invention in any way. Those skilled in the art may make some modifications and improvements without departing from the spirit of the present invention, and all such modifications and improvements are within the scope of the present invention.

[0020] The experimental materials used in the present invention are obtained as follows.

[0021] The polymerization method for self-preparing polyamide is as follows: Diamine and dicarboxylic acid monomers are charged into a pressure cooker in a molar ratio, followed by benzoic acid, sodium hypophosphite (catalyst), and deionized water. The amount of benzoic acid is 2.5% of the total amount of diamine and dicarboxylic acid, the weight of sodium hypophosphite is 0.1% of the total weight of the other materials charged, excluding deionized water, and the weight of deionized water is 30% of the total weight of the materials charged. Next, a vacuum is applied and high-purity nitrogen is filled as a protective gas. The temperature is increased to 220°C within 2 hours while stirring. The reaction mixture is stirred at 220°C for 1 hour, and then the temperature is increased to 230°C while stirring. The reaction is continued for 2 hours at a constant temperature of 230°C and a constant pressure of 2.2 MPa. The pressure is maintained constant by removing the produced water. After the reaction is complete, the materials are discharged, and the prepolymer is vacuum-dried at 80°C for 24 hours to obtain the prepolymer product. The prepolymer product is subjected to solid phase thickening treatment at 250°C and a vacuum of 50 Pa for 10 hours to obtain a polyamide having the corresponding structure. The relative viscosity is measured in accordance with ASTM D 789-2006.

[0022] transparent polyamide PA6I / 6T-1:6I / 6T=70 / 30, relative viscosity 2.2, homemade PA6I / 6T-2: 6I / 6T=65 / 35, relative viscosity 2.2, homemade PA6I / 6T-3: 6I / 6T=75 / 25, relative viscosity 2.2, homemade PA6I / 6T-4: 6I / 6T=80 / 20, relative viscosity 2.1, homemade PA6I / 6T-5: 6I / 6T=60 / 40, relative viscosity 2.3, homemade PA10I / 10T-1:10I / 10T=80 / 20, relative viscosity 2.2, homemade PA10I / 10T-2: 10I / 10T=75 / 25, relative viscosity 2.2, homemade PA10I / 10T-3: 10I / 10T=85 / 15, relative viscosity 2.2, homemade PA10I / 10T-4: 10I / 10T=70 / 30, relative viscosity 2.3, homemade PA10I / 10T-5: 10I / 10T=90 / 10, relative viscosity 2.2, homemade

[0023] Semicrystalline Polyamide PA610: Relative viscosity 2.4, Vicnyl 2300 NC003, manufactured by Jinfa Science and Technology Co., Ltd. PA1010: Relative viscosity 2.4, Vicnyl 2100 NC003, manufactured by Jinfa Science and Technology Co., Ltd. PA66: Relative viscosity 2.7, PA66 EPR27, manufactured by Pingtan Shenma Group, China PA612: Relative viscosity 2.4, Vicnyl 2800 NC003, manufactured by Jinfa Science and Technology Co., Ltd. PA106: Relative viscosity 2.4, Vicnyl 2300 NC006, manufactured by Jinfa Science and Technology Co., Ltd. PA1012: Relative viscosity 2.4, Vicnyl 2600 NC003, manufactured by Jinfa Science and Technology Co., Ltd. PA11: Relative viscosity 2.4, Rislan BMN G8, manufactured by Arkema, France Silicone elastomer powder-1 containing methacryloyloxy functional groups (abbreviated as component E1 in the table): average particle size 2 μm, DOWSIL 30-424, manufactured by Dow Chemical Company Silicone elastomer powder-2 containing methacryloyloxy functional groups (abbreviated as component E2 in the table): average particle size 5 μm, SL-500M(G), manufactured by Samsung Electronics, Korea Other silicone elastomers: Average particle size 3 μm, DOWSIL EP-5518, manufactured by Dow Chemical Company Light scattering agent: acrylic acid light diffusing agent, AL-206D, manufactured by Samsung Electronics, Korea, average particle size 10 μm. Antioxidant: RIANOX 1098, the same antioxidant was used in parallel tests. The polyamide composite material in the examples and comparative examples was produced as follows: The components were uniformly mixed according to the blending ratio, then extruded in a twin-screw extruder and granulated to obtain a polyamide composite material. The screw temperatures were set at 200-220-240-280-270-260-250-240-230-220-210-200°C, and the rotation speed was set to 200-400 rpm.

[0024] Test method for each item (1) Light transmittance and haze: The polyamide composite material is heated and melted at 200-280°C, and then injection molded into a 2mm thick square plate. The light transmittance and haze data are measured using a haze meter in accordance with the national standard GB / T 2410-2008. (2) Evaluation of chemical resistance: The polyamide composite material is heated and melted at 200 to 280°C, and then injection-molded into a square plate 2 mm thick. The square plate is then immersed in a 99.6% ethanol solution for 5 minutes, removed, and measured using a haze meter to obtain the light transmittance.

[0025] [Table 1] Content (parts by weight) of each component of the polyamide composite material of the example and test results JPEG2025533003000001.jpg91152

[0026] As can be seen from the examples, within the scope of the present invention, the light transmittance reaches 73% or more, the haze reaches 65% or more, and the chemical resistance is also excellent. Specifically, the higher the content of silicone elastomer powder containing methacryloyloxy functional groups, the higher the haze (the better the scattering properties).

[0027] From Examples 2 and 5, it can be seen that the particle size of the silicone elastomer powder containing methacryloyloxy functional groups is directly related to light transmittance and haze (scattering properties), and an average particle size of 0.1 to 3 μm is preferred because it results in higher transparency.

[0028] [Table 1 (continued)] JPEG2025533003000002.jpg91161

[0029] As can be seen from Examples 2, 6 and 7, the molar ratio of 6I units to 6T units in PA6I / 6T is preferably 65:35 to 75:25, which further increases the light transmittance and further improves the chemical resistance.

[0030] As can be seen from Examples 8 to 10, the molar ratio of 10I to 10T in PA10I / 10T is preferably 75:25 to 85:15.

[0031] [Table 1 (continued)] JPEG2025533003000003.jpg91152

[0032] As can be seen from Examples 2, 11-15, it is preferred that the diamine X in PAXI / XT matches the diamine units of the semi-crystalline polyamide.

[0033] [Table 2] Content (parts by weight) of each component of the polyamide composite material of the comparative example and test results JPEG2025533003000004.jpg102157

[0034] Comparative Examples 1 to 4 show that when the molar ratio of repeating units of PA6I / 6T and PA10I / 10T is not within the range of the present invention, the light transmittance is very low.

[0035] From Comparative Example 5, it was found that when semi-crystalline polyamide was not added, not only was the chemical resistance poor, but the haze was also relatively low.

[0036] [Table 2 (continued)] JPEG2025533003000005.jpg102153

[0037] As can be seen from Comparative Example 6, other silicone elastomers have low light transmittance even when their average particle size is 3 μm. As can be seen from Comparative Example 7, light scattering agents commonly used in this field significantly reduce light transmittance and also have poor chemical resistance.

[0038] As can be seen from Comparative Examples 8 and 9, when the proportion of semi-crystalline polyamide in the ratio of transparent polyamide to semi-crystalline polyamide is too high, the light transmittance is low, and when the proportion of semi-crystalline polyamide is too low, the light transmittance is high, but the haze and chemical resistance are also very low.

[0039] As can be seen from Comparative Example 10, although PA11 is also a long-chain polyamide, its degree of crystallinity is high, resulting in an excessively low light transmittance.

Claims

1. 1. A polyamide composite material comprising: A polyamide composite material comprising, as components, 77.2 to 94.8 parts by weight of PAXI / XT, 5 to 20 parts by weight of a semi-crystalline polyamide, and 0.2 to 0.8 parts by weight of a silicone elastomer powder containing a methacryloyloxy functional group, wherein the semi-crystalline polyamide is at least one selected from the group consisting of PA66, PA610, PA612, PA106, PA1010, and PA1012, the PAXI / XT is a copolymer of aliphatic diamine X, isophthalic acid I, and terephthalic acid T, and the aliphatic diamine X is at least one selected from the group consisting of 1,6-hexanediamine and 1,10-decanediamine.

2. 2. The polyamide composite of claim 1, wherein the diamine X of PAXI / XT corresponds to the diamine units of the semi-crystalline polyamide.

3. 2. The polyamide composite material according to claim 1, wherein when the PAXI / XT is PA6I / 6T, the molar ratio of 6I units to 6T units is from 65:35 to 75:25, preferably from 69:31 to 71:29, and when the PAXI / XT is PA10I / 10T, the molar ratio of 10I to 10T is from 75:25 to 85:15, preferably from 79:21 to 81:

19.

4. 2. The polyamide composite material according to claim 1, wherein the average particle size of the silicone elastomer powder containing methacryloyloxy functional groups is in the range of 0.1 to 8 μm, preferably 0.1 to 3 μm.

5. 10. The polyamide composite of claim 1, wherein the polyamide composite has a light transmission greater than 73% and a haze greater than 65%.

6. The polyamide composite material according to any one of claims 1 to 5, further comprising 0 to 2 parts by weight of an auxiliary agent, the auxiliary agent being at least one selected from the group consisting of an antioxidant, a lubricant, and an ultraviolet inhibitor.

7. 7. A method for producing a polyamide composite material according to claim 1, comprising the steps of: uniformly mixing the components in a compounding ratio; and then extruding the mixture using a twin-screw extruder at a temperature of 200 to 280°C and a rotation speed of 200 to 400 rpm to granulate the mixture, thereby obtaining a polyamide composite material.

8. 10. Use of the polyamide composite material according to any one of claims 1 to 6 for the manufacture of navigation lights for plant protection drones.

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