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

Abstract

This invention discloses a polyamide composite material, comprising the following components by weight: 40-55 parts polyamide resin; 15-35 parts brominated polystyrene polymer; 3-8 parts brominated polystyrene oligomer; 3-8 parts antimony-containing flame retardant synergist; 30-60 parts glass fiber; and 5-15 parts potassium titanate whiskers. The weight-average molecular weight of the brominated polystyrene polymer ranges from 180,000 to 240,000, and the weight-average molecular weight of the brominated polystyrene oligomer ranges from 3,000 to 6,000. This invention, through the selection of high / low weight-average molecular weight brominated polystyrene blends and the synergistic reinforcement of potassium titanate whiskers and glass fiber, achieves a good interfacial effect with the polyamide resin and flame retardant after modification, increasing compatibility and forming a stable interfacial structure. This avoids the reduction in weather resistance due to the flame retardant under light and high temperature, improves wear resistance, and achieves V-0 thin-wall flame retardancy.

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 is widely used in engineering materials across various fields. With continuous technological advancements, the variety of products has increased. However, with the development of modern high technology, products requiring durability, abrasion resistance, flame retardancy, and complex structural designs are becoming more common, placing higher demands on the comprehensive performance of materials. Traditional materials can no longer meet market requirements; they must be both abrasion-resistant and flame-retardant. However, the inherent limitations of flame retardants mean that while achieving flame retardancy, the abrasion resistance and weather resistance are reduced, restricting their use in various industries. New solutions are needed to fill this technological gap. Summary of the Invention

[0003] The purpose of this invention is to provide a thin-walled, flame-retardant, wear-resistant, light-stable, and thermally stable polyamide composite material, as well as its preparation method and application.

[0004] This invention is achieved through the following technical solution:

[0005] A polyamide composite material, by weight, comprises the following components:

[0006] 40-55 parts of polyamide resin;

[0007] 15-35 parts of brominated polystyrene polymer;

[0008] 3-8 parts of brominated polystyrene oligomer;

[0009] 3-8 parts of antimony-containing flame retardant synergist;

[0010] 30-60 parts glass fiber;

[0011] 5-15 parts of potassium titanate whiskers;

[0012] The weight-average molecular weight range of the brominated polystyrene polymer is 180,000 to 250,000.

[0013] The weight-average molecular weight range of the brominated polystyrene oligomers is 3000-6000.

[0014] In the polyamide composite material of the present invention, the weight content of polyamide resin can be 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, etc.; the weight content of brominated polystyrene polymer can be 15 parts, 17 parts, 19 parts, 21 parts, 23 parts, 25 parts, 27 parts, 29 parts, 31 parts, 33 parts, 35 parts, etc.; the weight content of brominated polystyrene oligomer can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, etc.; the weight content of antimony-containing flame retardant synergist can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, etc.; the weight content of glass fiber can be 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, etc.; and the weight content of potassium titanate whiskers can be 5 parts, 7 parts, 9 parts, 11 parts, 13 parts, 15 parts, etc.

[0015] Preferably, the composition includes 20-30 parts of brominated polystyrene polymer, 5-7 parts of brominated polystyrene oligomer, 40-50 parts of glass fiber, and 8-12 parts of potassium titanate fiber.

[0016] The glass fibers that can achieve the purpose of this invention have a length range of 2-7 mm and a diameter range of 9-15 micrometers, and the aspect ratio of potassium titanate whiskers ranges from 0.3 to 200.

[0017] The polyamide resin is selected from at least one of aliphatic polyamide resin and semi-aromatic polyamide resin.

[0018] Specifically, 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, PA5, PA6, PA11, PA12, etc.

[0019] The semi-aromatic polyamide is selected from PA MXD6, PA10T, PA10T1010, PA10T66, PA6T, PA6T66, PA9T, etc.

[0020] The length of the potassium titanate whiskers can range from 0.1 to 30 micrometers, and the diameter can range from 0.05 to 3 micrometers; preferably, the length of the potassium titanate whiskers ranges from 0.2 to 20 micrometers, and the diameter ranges from 0.1 to 0.7 micrometers.

[0021] The antimony-containing flame retardant synergist is selected from at least one of antimony trioxide and antimony pentoxide.

[0022] This invention does not limit the average particle size of the antimony-containing flame retardant synergist; preferably, the average particle size range of the antimony-containing flame retardant synergist is 0.1-5 micrometers, as determined by laser particle size analyzer.

[0023] The weight-average molecular weight of brominated polystyrene was determined by gel permeation chromatography.

[0024] Depending on actual needs, 0-3 parts of additives may be added, wherein the additives are selected from at least one of antioxidants, lubricants, UV stabilizers, and silane coupling agents.

[0025] The preparation method of the polyamide composite material of the present invention includes the following steps: mixing all components except glass fiber uniformly according to parts by weight, extruding and granulating through a twin-screw extruder, with glass fiber side-fed, to obtain the polyamide composite material. The screw length-to-diameter ratio is 40~48:1, the barrel temperature is 230~260℃, and the screw speed is 200~550rpm.

[0026] The polyamide composite material of the present invention is applicable to gears and machine tool parts.

[0027] The present invention has the following beneficial effects:

[0028] This invention utilizes a blend of high / low weight-average molecular weight brominated polystyrene, reinforced with potassium titanate whiskers and glass fibers. After modification, it can form a good interface with polyamide resin and flame retardant, increasing compatibility and forming a stable interface structure. This avoids the reduction in weather resistance caused by the flame retardant under light and high temperature, and achieves V-0 thin-wall flame retardancy. Detailed Implementation

[0029] 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.

[0030] The raw materials used in this invention are sourced from the following sources:

[0031] PA66: PA66 EPR27, Shenma Group;

[0032] PA6: PA6 HY-2800A, marine chemical fiber;

[0033] PA10T: VICNYL 6100P, Zhuhai Wantong Special Engineering Plastics Co., Ltd.;

[0034] PA1010: PA1010 G150, Shandong Guangyin New Materials Co., Ltd.;

[0035] Brominated polystyrene A: BPS 7010, Shandong Tianyi, weight-average molecular weight approximately 190,000;

[0036] Brominated polystyrene B: XZ-6700, Shandong Brothers, weight-average molecular weight approximately 240,000;

[0037] Brominated polystyrene C: FR-803P, ICL, with a weight-average molecular weight of approximately 600,000.

[0038] Brominated polystyrene D: SR-3010, Shandong Xurui, with a weight-average molecular weight of approximately 0.4 million;

[0039] Brominated polystyrene E: Phalmoon-103L, Taizhou Baili Chemical Co., Ltd., with a weight-average molecular weight of approximately 0.4 million;

[0040] Decabromodiphenyl ethane: SAYTEX 8010, Albemarle Industries;

[0041] Brominated epoxy: CXB-2000 WOOJIN COPOLYMER, weight average molecular weight approximately 2000;

[0042] Antimony trioxide: S-05N, Shanxing Antimony Industry;

[0043] Fiberglass: ECS10-3.0-T435N, Taishan Group;

[0044] Potassium titanate whiskers A: length 10-20μm, diameter 0.3-0.6μm, TISMON, Otsuka Chemical Co., Ltd.

[0045] Potassium titanate whiskers B: length 0.2-8μm, diameter 0.1-2μm, mPTW, Shanghai Fengzhu Composite Materials Technology Co., Ltd.

[0046] Potassium titanate whiskers C: length 0.6-1.0μm, diameter <0.1μm, Nptw, Nantong Aoxin Electronic Technology Co., Ltd.;

[0047] Silane coupling agent: KH560, Nanjing Shuguang Chemical Plant;

[0048] Preparation method of polyamide composite material in examples and comparative examples: All components except glass fiber were mixed uniformly according to weight parts, and then extruded and granulated using a twin-screw extruder with glass fiber side-fed to obtain the polyamide composite material. The screw length-to-diameter ratio was 40~48:1, the barrel temperature was 230~260℃, and the screw speed was 200~550 rpm.

[0049] Test methods:

[0050] (1) Light resistance: A 100*100*2mm square plate was injection molded using a 280T injection molding machine at 50% of its rated speed and 60 bar pressure. After conditioning at 23℃ and 50% humidity for 48 hours, the plate was exposed to sunlight for 3 months. The ΔE value of the square plate was tested before and after the exposure. The smaller the value, the better the light resistance.

[0051] (2) Flame retardancy: The flame retardancy rating of the material was tested using UL-94, which is divided into V-0, V-1 and V-2, with a sample thickness of 0.8 mm.

[0052] (3) Abrasion resistance: The test was conducted on a color fastness abrasion tester with a 226N weight applied and 80-mesh coarse sandpaper used as the abrasion surface. The test was conducted at a frequency of 1 time / s, with a cycle distance of 100mm and 5000 cycles. The wear rate of the test sample was measured. The wear rate test method is as follows:

[0053] Wear rate = (sample weight before test - sample weight after test) / sample weight before test * 100%.

[0054] Table 1: Content (parts by weight) and test results of each component in the flame-retardant polyamide materials of Examples 1-7

[0055] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 PA66 48 48 48 48 PA6 40 PA10T 55 PA1010 48 Brominated polystyrene A 15 25 35 15 20 30 Brominated polystyrene B 33 Brominated polystyrene D 8 8 3 4 3 5 7 Antimony trioxide 3 5 8 4 5 5 5 Fiberglass 30 45 60 40 30 40 50 Potassium titanate whiskers A 5 10 15 13 5 8 12 Silane coupling agents 0.3 0.7 1 0.5 0.7 0.7 0.7 Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 Wear rate, % 2.5 2.6 3.5 3.2 2.6 2.5 2.6 ΔE 3.6 3.4 4.3 3.9 3.6 3.3 3.4

[0056] As can be seen from Examples 2 / 5-8, the wear rate and ΔE are lower when the content of each component is optimized.

[0057] Table 2: Content (parts by weight) of each component and test results of flame-retardant polyamide materials in Examples 8-11

[0058] Example 8 Example 9 Example 10 Example 11 PA66 48 48 48 48 Brominated polystyrene A 35 25 25 25 Brominated polystyrene D 8 8 8 Brominated polystyrene E 8 Antimony trioxide 5 5 5 5 Fiberglass 60 45 45 45 Potassium titanate whiskers A 15 10 Potassium titanate whiskers B 10 Potassium titanate whiskers C 10 Silane coupling agents 0.7 0.7 0.7 0.7 Flame retardancy V-0 V-0 V-0 V-0 Wear rate, % 3.1 3.0 3.4 2.5 ΔE 3.8 3.7 4.2 3.5

[0059] As can be seen from Examples 2 / 9 / 10, the wear rate and ΔE of the polyamide composite material are lower when the preferred potassium titanate whisker length and diameter are selected.

[0060] As can be seen from the above embodiments, the polyamide composite material of the present invention has V-0 flame retardancy, wear rate of less than 4%, and ΔE of less than 5.

[0061] Table 3: Content (parts by weight) and test results of each component in comparative flame-retardant polyamide materials

[0062] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 PA66 48 48 48 48 48 48 48 Brominated polystyrene A 33 22 25 25 Brominated polystyrene C 25 Brominated polystyrene D 8 11 8 8 decabromodiphenyl ethane 33 Brominated epoxy 33 Antimony trioxide 5 5 5 5 5 5 5 Fiberglass 45 45 45 55 35 45 45 Potassium titanate whiskers A 10 10 10 0 20 10 10 Silane coupling agents 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Flame retardancy V-1 V-2 V-1 V-1 V-1 V-1 V-2 Wear rate, % 5.7 5.0 6.2 5.8 5.5 6.5 6.8 ΔE 7.5 7.8 8.2 9.3 6.8 7.8 8.6

[0063] As shown in Comparative Example 1, when brominated polystyrene oligomers are not present, the flame retardancy, abrasion resistance, and light resistance are all significantly reduced.

[0064] As shown in Comparative Example 2, when the weight-average molecular weight of brominated polystyrene polymer is too high, it will also cause a significant reduction in flame retardancy, abrasion resistance, and light resistance.

[0065] As shown in Comparative Example 3, when the content of brominated polystyrene oligomers is too high, the flame retardancy, abrasion resistance, and light resistance are not high.

[0066] As can be seen from Comparative Example 4 / 5, when there is no potassium titanate whisker or the content of potassium titanate whisker is too high, the flame retardancy, wear resistance and light resistance are insufficient.

[0067] As can be seen from Comparative Examples 6 / 7, when other types of brominated flame retardants are used to replace the brominated polystyrene of this invention, the flame retardancy does not reach V-0, and the wear is severe and the light resistance is poor.

Claims

1. A polyamide composite material, characterized in that, By weight, it includes the following components: 40-55 parts of polyamide resin; 15-35 parts of brominated polystyrene polymer; 3-8 parts of brominated polystyrene oligomer; 3-8 parts of antimony-containing flame retardant synergist; 30-60 parts glass fiber; 5-15 parts of potassium titanate whiskers; The weight-average molecular weight range of the brominated polystyrene polymer is 180,000 to 250,000. The weight-average molecular weight range of the brominated polystyrene oligomers is 3000-6000.

2. The polyamide composite material according to claim 1, characterized in that, The composition includes 20-30 parts of brominated polystyrene polymer, 5-7 parts of brominated polystyrene oligomer, 40-50 parts of glass fiber, and 8-12 parts of potassium titanate fiber.

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

4. The polyamide composite material according to claim 1, characterized in that, The potassium titanate whiskers have a length range of 0.2-20 micrometers and a diameter range of 0.1-0.7 micrometers.

5. The polyamide composite material according to claim 1, characterized in that, The antimony-containing flame retardant synergist is selected from at least one of antimony trioxide and antimony pentoxide.

6. The polyamide composite material according to claim 1, characterized in that, The product comprises 0-3 parts by weight of additives, wherein the additives are selected from at least one of antioxidants, lubricants, UV stabilizers, and silane coupling agents.

7. A method for preparing the polyamide composite material according to any one of claims 1-6, characterized in that, The process includes the following steps: mixing all components except glass fiber evenly by weight, extruding and granulating the mixture through a twin-screw extruder, with glass fiber side-fed, to obtain a polyamide composite material.

8. The application of the polyamide composite material according to any one of claims 1-6, characterized in that, Suitable for gears and machine tool parts.