High-performance high-thermal-conductivity PA6 composite material, preparation method and use

Abstract

The application discloses a kind of high-performance high-thermal-conductivity PA6 composite materials, preparation method and use, wherein PA6 composite material is by following component is formed according to weight parts: PA6 80-100, modified PPTA fiber 10-16, antioxidant 0.1-0.5 portion, the modified PPTA fiber is by hydroxylated aluminum boride, polyvinyl alcohol is modified to PPTA fiber and is formed.The boron aluminum of the application is hydroxylated, then hydroxylated aluminum boride is grafted on PVA molecular chain, after grafting, it is coated on the surface of PPTA fiber, forms good heat conduction passage, and heat energy can be quickly transferred along heat conduction passage, and this heat conduction passage significantly reduces the interface thermal resistance of composite material.The modified PPTA fiber of the application can significantly reduce the interface thermal resistance of composite material, improve the thermal conductivity and mechanical properties of PA6.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to a high-performance, high-thermal-conductivity PA6 composite material, its preparation method, and its applications. Background Technology

[0002] Polyamide 6 (PA6) is a widely used polymer resin with good fatigue resistance, good heat resistance, and excellent dimensional stability. It is currently widely used in automotive parts, electronic connectors, and other fields. As high-end equipment such as 5G communication base stations and high-frequency servers develop towards miniaturization and high power density, heat dissipation components face stringent operating conditions: for example, a material thermal conductivity ≥0.5 W / (m·K), while the thermal conductivity of ordinary PA6 is only 0.25 W / (m·K), which cannot meet these requirements.

[0003] Currently, fiber-reinforced PA6 is commonly used to enhance its mechanical strength, but fiber orientation leads to significant anisotropy, resulting in limited thermal conductivity. Metal fillers (such as Al and Cu) are also used to improve thermal conductivity, but this increases material density by 30%-50%, contradicting the trend towards lightweight equipment, and the increased conductivity poses a risk of electromagnetic interference. Summary of the Invention

[0004] To address the aforementioned issues, this invention innovatively synthesizes a high-performance, high-thermal-conductivity PA6 composite material suitable for communication devices and its preparation method. This material possesses excellent physical and thermal properties, thus solving the technical problem of limited physical and thermal properties of PA6 in existing technologies.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A high-performance, high-thermal-conductivity PA6 composite material, which is composed of the following components in parts by weight:

[0007] PA6 80-100 servings

[0008] 10-16 parts modified PPTA fiber

[0009] Antioxidant 0.1-0.5 parts

[0010] The modified PPTA fiber is made by modifying PPTA fiber with hydroxylated aluminum boride and polyvinyl alcohol.

[0011] In a further embodiment, the modified PPTA fiber is prepared using the following steps:

[0012] (1) Add aluminum boride, hydrogen peroxide and boric acid to deionized water and stir to react to obtain solution A;

[0013] (2) Solution A was filtered, washed and dried to obtain aluminum borohydride;

[0014] (3) Add hydroxylated aluminum boride, polyvinyl alcohol (PVA), PPTA fiber and crosslinking agent to deionized water, stir and react at 40-60℃ for 8-10h, filter, wash and dry to obtain modified PPTA fiber.

[0015] In a further step, the mass ratio of aluminum boride, hydrogen peroxide, and boric acid in step (1) is (30-40):(50-60):(40-50);

[0016] The stirring reaction is carried out at a temperature of 30-50℃ for 4-6 hours.

[0017] In a further embodiment, the mass ratio of hydroxylated aluminum boride, polyvinyl alcohol (PVA), PPTA fiber, and crosslinking agent in step (3) is (20-24):(10-16):(20-30):(0.2-0.4);

[0018] The stirring reaction is carried out at a temperature of 40-60℃ for 8-10 hours.

[0019] In a further embodiment, the antioxidant is one or a mixture of several of the following: tris(2,4-di-tert-butyl)phosphite (Irganox 168), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxyphenyl)benzene (Irganox 1330).

[0020] In a further embodiment, the crosslinking agent is epichlorohydrin, N,N-methylenebisacrylamide, or diethylenetriamine.

[0021] A second objective of this invention is to provide a method for preparing the aforementioned PA6 composite material, comprising the following steps:

[0022] (1) Weigh 80-100 parts of PA6, 10-16 parts of modified PPTA fiber, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture;

[0023] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material.

[0024] In a further embodiment, the extruder in step (2) is a twin-screw extruder, which includes six temperature zones arranged in sequence: zone 1 temperature 200-220℃, zone 2 temperature 260-280℃, zone 3 temperature 260-280℃, zone 4 temperature 260-280℃, zone 5 temperature 260-280℃, zone 6 temperature 260-280℃, die head temperature 260-280℃, and screw speed 200-280r / min.

[0025] The PA6 composite material of the present invention can be used as a raw material for communication equipment.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] This application involves hydroxylating aluminum boride, then grafting the hydroxylated aluminum boride onto the PVA molecular chain, and finally coating it onto the surface of PPTA fibers to form a good thermal conductivity pathway. Heat energy can be quickly transferred through the thermal conductivity pathway. This thermal conductivity pathway significantly reduces the interfacial thermal resistance of the composite material and improves the thermal conductivity of PA6.

[0028] PPTA fiber is a high-performance synthetic fiber with alternating benzene rings inside its molecules and a rigid rod-like molecular chain structure. It is highly oriented and crystalline inside. Adding modified PPTA fiber to PA6 improves the mechanical properties of PA6.

[0029] The PA6 composite material prepared in this application has significantly improved thermal conductivity and physical properties, and has great potential for widespread application. Detailed Implementation

[0030] To facilitate understanding of the present invention, a more comprehensive description of the invention will be provided 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. Rather, these embodiments are provided to enable a more thorough and complete understanding of the disclosure of the present invention.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0032] The raw materials used in the following examples are as follows:

[0033] PA6 (model IM), Guppy, Russia; PPTA fiber, DuPont, USA; hydrogen peroxide, Jinan Kunfeng Chemical Co., Ltd.; aluminum boride, Shanghai Xiaohuang Nanotechnology Co., Ltd.; polyvinyl alcohol (PVA), Guangzhou Hongzhou Chemical Co., Ltd.; deionized water, Jinan Hairuibao Chemical Co., Ltd.; epichlorohydrin, Jinan Rongguang Chemical Co., Ltd.; antioxidants (models Irganox 168, Irganox 1010, Irganox 1330), BASF, Germany.

[0034] Preparation Example 1

[0035] (1) Weigh 300g aluminum boride, 500g hydrogen peroxide, 400g boric acid and 800g deionized water, place them in a reactor dish, stir and react at 30℃ for 4h to obtain solution A;

[0036] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 60°C for 6 hours to obtain aluminum borohydride.

[0037] (3) Weigh 200g of hydroxylated aluminum boride, 100g of polyvinyl alcohol (PVA), 200g of PPTA fiber, 2g of crosslinking agent epichlorohydrin, and 700g of deionized water, place them in a reactor dish, stir and react at 40℃ for 8h, filter, wash and dry to obtain modified PPTA fiber M1.

[0038] Example 1

[0039] (1) Weigh 80 parts of PA6, 10 parts of modified PPTA fiber M1, and 0.1 parts of antioxidant Irganox1010, mix and stir evenly to obtain a mixture;

[0040] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material P1.

[0041] The twin-screw extruder includes six temperature zones arranged in sequence: zone 1 (200℃), zone 2 (260℃), zone 3 (260℃), zone 4 (260℃), zone 5 (260℃), zone 6 (260℃), and the die head temperature (260℃); the screw speed is 200 r / min.

[0042] Preparation Example 2

[0043] (1) Weigh 400g aluminum boride, 600g hydrogen peroxide, 500g boric acid and 900g deionized water, place them in a reactor dish, stir at 50℃ for 6h to obtain solution A.

[0044] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 80°C for 8 hours to obtain aluminum borohydride.

[0045] (3) Weigh 240g of hydroxylated aluminum boride, 160g of polyvinyl alcohol (PVA), 300g of PPTA fiber, 4g of crosslinking agent epichlorohydrin, and 900g of deionized water, place them in a reactor dish, stir and react at 60℃ for 10h, filter, wash and dry to obtain modified PPTA fiber M2.

[0046] Example 2

[0047] (1) Weigh 100 parts of PA6, 16 parts of modified PPTA fiber M2, 0.1 parts of Irganox1010, 0.2 parts of Irganox168, and 0.2 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0048] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material P2.

[0049] The twin-screw extruder includes six temperature zones arranged in sequence: zone 1 (220℃), zone 2 (280℃), zone 3 (280℃), zone 4 (280℃), zone 5 (280℃), zone 6 (280℃), and the die head temperature (280℃); the screw speed is 280 r / min.

[0050] Preparation Example 3

[0051] (1) Weigh 350g aluminum boride, 550g hydrogen peroxide, 450g boric acid and 850g deionized water, place them in a reactor dish, stir and react at 40℃ for 5h to obtain solution A.

[0052] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 70°C for 7 hours to obtain aluminum borohydride.

[0053] (3) Weigh 220g of hydroxylated aluminum boride, 130g of polyvinyl alcohol (PVA), 250g of PPTA fiber, 3g of crosslinking agent epichlorohydrin, and 800g of deionized water, place them in a reactor dish, stir and react at 50°C for 9h, filter, wash and dry to obtain modified PPTA fiber M3.

[0054] Example 3

[0055] (1) Weigh 90 parts of PA6, 13 parts of modified PPTA fiber M3, 0.1 parts of Irganox168, and 0.2 parts of Irganox1010, mix and stir evenly to obtain a mixture;

[0056] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material P3.

[0057] The twin-screw extruder includes six temperature zones arranged in sequence: zone 1 (210℃), zone 2 (270℃), zone 3 (270℃), zone 4 (270℃), zone 5 (270℃), zone 6 (270℃), and the die head temperature (270℃); the screw speed is 240 r / min.

[0058] Preparation Example 4

[0059] (1) Weigh 385g aluminum boride, 555g hydrogen peroxide, 480g boric acid and 855g deionized water, place them in a reactor dish, stir and react at 35℃ for 4h to obtain solution A.

[0060] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 75°C for 6 hours to obtain aluminum borohydride.

[0061] (3) Weigh 235g of hydroxylated aluminum boride, 155g of polyvinyl alcohol (PVA), 295g of PPTA fiber, 3.5g of crosslinking agent epichlorohydrin, and 885g of deionized water, place them in a reactor dish, stir and react at 55℃ for 9h, filter, wash and dry to obtain modified PPTA fiber M4.

[0062] Example 4

[0063] (1) Weigh 85 parts of PA6, 15 parts of modified PPTA fiber M4, and 0.1 parts of Irganox1010, mix and stir evenly to obtain a mixture;

[0064] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material P4.

[0065] The twin-screw extruder includes six temperature zones arranged in sequence: zone 1 temperature 215℃, zone 2 temperature 270℃, zone 3 temperature 270℃, zone 4 temperature 270℃, zone 5 temperature 270℃, zone 6 temperature 270℃, and die head temperature 270℃; the screw speed is 250 r / min.

[0066] Preparation Example 5

[0067] (1) Weigh 225g aluminum boride, 595g hydrogen peroxide, 425g boric acid and 875g deionized water, place them in a reactor dish, stir and react at 45℃ for 6h to obtain solution A.

[0068] (2) Solution A was filtered, washed, and dried in a vacuum drying oven at 75°C for 7 hours to obtain aluminum borohydride.

[0069] (3) Weigh 215g of hydroxylated aluminum boride, 155g of polyvinyl alcohol (PVA), 285g of PPTA fiber, 2.5g of crosslinking agent epichlorohydrin, and 865g of deionized water, place them in a reactor dish, stir and react at 550℃ for 8h, filter, wash and dry to obtain modified PPTA fiber M5.

[0070] Example 5

[0071] (1) Weigh 85 parts of PA6, 14 parts of modified PPTA fiber M5, and 0.1 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0072] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material P5.

[0073] The twin-screw extruder includes six temperature zones arranged in sequence: zone 1 temperature 205℃, zone 2 temperature 275℃, zone 3 temperature 275℃, zone 4 temperature 275℃, zone 5 temperature 275℃, zone 6 temperature 275℃, die head temperature 275℃, and screw speed 245r / min.

[0074] Comparative Example 1

[0075] (1) Weigh 85 parts of PA6 and 0.1 parts of Irganox1330, mix and stir evenly to obtain a mixture;

[0076] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material D1.

[0077] The twin-screw extruder includes six temperature zones arranged in sequence: zone 1 temperature 205℃, zone 2 temperature 275℃, zone 3 temperature 275℃, zone 4 temperature 275℃, zone 5 temperature 275℃, zone 6 temperature 275℃, die head temperature 275℃, and screw speed 245r / min.

[0078] Comparative Example 2

[0079] (1) Weigh 85 parts of PA6, 14 parts of PPTA fiber, and 0.1 parts of Irganox 1330, mix and stir evenly to obtain a mixture;

[0080] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material D2.

[0081] The twin-screw extruder includes six temperature zones arranged in sequence: zone 1 temperature 205℃, zone 2 temperature 275℃, zone 3 temperature 275℃, zone 4 temperature 275℃, zone 5 temperature 275℃, zone 6 temperature 275℃, die head temperature 275℃, and screw speed 245r / min.

[0082] Comparative Example 3

[0083] (1) Weigh 85 parts of PA6, 8 parts of PPTA fiber, 6 parts of aluminum boride, and 0.1 parts of Irganox 1330, mix and stir evenly to obtain a mixture;

[0084] (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material D3.

[0085] The twin-screw extruder includes six temperature zones arranged in sequence: zone 1 temperature 205℃, zone 2 temperature 275℃, zone 3 temperature 275℃, zone 4 temperature 275℃, zone 5 temperature 275℃, zone 6 temperature 275℃, die head temperature 275℃, and screw speed 245r / min.

[0086] The performance data of the PA6 composite materials of Examples 1-5 and Comparative Examples 1-2 are shown in the table below:

[0087]

[0088] As can be seen from the table above, the physical and thermal properties of the PA6 composite materials P1-P5 prepared in Examples 1-5 of this application are superior to those of D1-D3. Comparing P5 and D2, it is found that the thermal conductivity of P5 is significantly improved due to the addition of modified PPTA fibers. Comparing P5 and D3, it is found that although D3 contains the same amount of PPTA fibers and aluminum boride, the thermal conductivity and mechanical properties of the material are inferior to those of P5. This indicates that the PA6 composite material prepared by this invention has better physical and thermal properties.

[0089] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0090] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. 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, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A high-performance, high-thermal-conductivity PA6 composite material, characterized in that: It is composed of the following components in parts by weight: PA6 80-100 servings 10-16 parts modified PPTA fiber Antioxidant 0.1-0.5 parts The modified PPTA fiber is made by modifying PPTA fiber with hydroxylated aluminum boride and polyvinyl alcohol.

2. The PA6 composite material according to claim 1, characterized in that: The modified PPTA fiber is prepared using the following steps: (1) Add aluminum boride, hydrogen peroxide and boric acid to deionized water and stir to react to obtain solution A; (2) Solution A was filtered, washed and dried to obtain aluminum borohydride; (3) Add hydroxylated aluminum boride, polyvinyl alcohol, PPTA fiber and crosslinking agent to deionized water, stir and react at 40-60℃ for 8-10h, filter, wash and dry to obtain modified PPTA fiber.

3. The PA6 composite material according to claim 2, characterized in that: The mass ratio of aluminum boride, hydrogen peroxide, and boric acid in step (1) is (30-40):(50-60):(40-50); The stirring reaction is carried out at a temperature of 30-50℃ for 4-6 hours.

4. The PA6 composite material according to claim 2, characterized in that: The mass ratio of hydroxylated aluminum boride, polyvinyl alcohol, PPTA fiber, and crosslinking agent in step (3) is (20-24):(10-16):(20-30):(0.2-0.4); The stirring reaction is carried out at a temperature of 40-60℃ for 8-10 hours.

5. The PA6 composite material according to claim 1, characterized in that: The antioxidant is one or a mixture of several of the following: tris(2,4-di-tert-butyl)phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxyphenyl)benzene.

6. The PA6 composite material according to claim 1, characterized in that: The crosslinking agent is epichlorohydrin, N,N-methylenebisacrylamide, or diethylenetriamine.

7. The method for preparing the PA6 composite material according to any one of claims 1-6, characterized in that: Includes the following steps: (1) Weigh 80-100 parts of PA6, 10-16 parts of modified PPTA fiber, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture; (2) The mixture obtained in step (1) is extruded from the extruder and granulated to obtain PA6 composite material.

8. The preparation method according to claim 7, characterized in that: In step (2), the extruder is a twin-screw extruder, which includes six temperature zones arranged in sequence: zone 1 temperature 200-220℃, zone 2 temperature 260-280℃, zone 3 temperature 260-280℃, zone 4 temperature 260-280℃, zone 5 temperature 260-280℃, zone 6 temperature 260-280℃, die head temperature 260-280℃, and screw speed 200-280r / min.

9. The use of the PA6 composite material according to any one of claims 1-6, characterized in that: The PA6 composite material is used as a raw material for communication equipment.

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