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

Abstract

This invention discloses a polyamide composite material, comprising the following components by weight: 70-94 parts polyamide resin; 0.1-1 parts rice bran wax metal salt; and 5-30 parts toughening agent. The polyamide is selected from copolymer polyamide resin, or a blend of copolymer polyamide resin and homopolymer aliphatic polyamide resin, wherein, when copolymer polyamide resin and homopolymer aliphatic polyamide resin are blended, the copolymer polyamide resin accounts for 5-95 wt% of the polyamide resin. This invention utilizes a specific type of polyamide and rice bran wax salt as a nucleating agent to reduce crystal size. The combined effect results in polyamide grains with a size smaller than the visible light wavelength, increasing crystal density and enabling absorption of visible light by the grains. When the polyamide composite material is bent under stress, the resulting micro-voids do not produce light reflection, thus significantly reducing the stress whitening defect of the polyamide composite material. Furthermore, the polyamide composite material of this invention maintains good mechanical properties.

Description

A polyamide composite material, its preparation method and application 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 industrial cable ties are used to bundle and secure cables, wires, and their components. They require properties such as toughness, heat resistance, weather resistance, resistance to repeated bending fatigue, and creep resistance. Driven by increasing demand from industries such as automotive, electronics, and logistics, the global market for plastic cable ties is expected to grow significantly in the coming years. According to authoritative statistics, the average annual compound growth rate is projected to be approximately 5% until 2029, with an annual market size of no less than $1.5 billion. With the advocacy of a green and low-carbon economy, improving the lifespan and durability of industrial consumables has become a key focus. Industrial cable ties inevitably face bending during use. In practice, it has been observed that cable ties turn white during bending, which not only affects appearance but also makes them more susceptible to crack propagation and damage from external factors such as light, heat, and oxygen.

[0003] During tensile deformation, polyamide crystals, whether isotropic or spherulitic, develop into highly oriented fibrous crystals, which then fracture with increasing elongation. Depending on the tensile conditions and sample pretreatment, structural cavitation is frequently observed during the tensile process. This cavitation typically results in a whitish appearance due to the pore size reaching visible light levels and causing visible light scattering. This whitish appearance significantly impacts the product's performance and aesthetics.

[0004] Currently, two typical scenarios are generally considered to lead to cavitation and a whitening appearance. One occurs around the yield point of partially crystalline polymers, which does not require a large strain. The other type of stress-induced whitening occurs in the later stages of tensile stress, resulting in pores caused by defects at the ends of the fibrous structure. The formation of these pores can be utilized, such as by forming microporous membranes. However, in most cases, the formation of pore structures within plastic materials is considered a defect, a precursor to fracture, and the whitening appearance not only affects aesthetics but also indicates the early stage of structural failure. Existing technologies mainly improve stress-induced whitening defects through the following methods:

[0005] CN117178023A discloses a polyamide composition in which 10-50% maleic acid-modified polyolefin is introduced to give the fracture surface a stress whitening zone thickness of not less than 500 micrometers.

[0006] CN117024953A discloses a high-toughness, high-metal-adhesion polyamide composition comprising a long-chain polyamide resin, an elastomer binder, an antioxidant, a color masterbatch, and a light stabilizer. The polyether block polyamide is used as the elastomer binder to improve the material's ability to prevent stress whitening of the busbar sheath after bending.

[0007] CN116063787A uses fully vulcanized powdered rubber and / or oil-extended fully vulcanized powdered rubber as stress-whitening resistant additives to improve stress whitening of thermoplastic composites. Summary of the Invention

[0008] The purpose of this invention is to provide a polyamide composite material that is resistant to stress whitening and has good mechanical properties.

[0009] This invention is achieved through the following technical solution:

[0010] A polyamide composite material, by weight, comprises the following components:

[0011] 70-94 parts of polyamide;

[0012] 0.1-1 part of rice bran wax metal salt;

[0013] Toughening agent 5-30 parts;

[0014] The polyamide is selected from copolyamide resins, blends of copolyamide resins and homopolymer aliphatic polyamide resins, wherein when copolyamide resins and homopolymer aliphatic polyamide resins are blended, the copolyamide resin accounts for 5-95 wt% of the polyamide resin.

[0015] The homopolymer aliphatic polyamide resin is derived from an aliphatic dicarboxylic acid with 4-18 carbon atoms and an aliphatic diamine with 2-16 carbon atoms, or the homopolymer aliphatic polyamide resin is derived from lactams or amino acids (lactams or amino acids have 3-15 carbon atoms).

[0016] The copolyamide resin is derived from diacid units and diamine units. The diacid units are selected from at least one of 1,6-adipic acid, isophthalic acid, and terephthalic acid. The diamine units are selected from 2-methyl-pentanediamine and optionally 1,6-hexanediamine, with 2-methyl-pentanediamine accounting for 1-100 mol of the diamine units.

[0017] Optionally, the rice bran wax metal salt is selected from at least one of rice bran wax sodium salt and rice bran wax calcium salt; the average particle size of the rice bran wax metal salt is 10-800 micrometers. The average particle size of the rice bran wax metal salt is obtained by laser particle size analyzer.

[0018] Preferably, when the copolyamide resin is compounded with the homopolymer aliphatic polyamide resin, the copolyamide resin accounts for 35-75 wt% of the polyamide resin.

[0019] In the polyamide composite material of the present invention, the polyamide resin accounts for not less than 65 wt% of the total weight of the composite material.

[0020] Specifically, the copolyamide resin is selected from at least one of the following: polyhexamethylene adipamide / polyisophthaloyl-2-methyl-pentanediamine (PA66 / DI), polyhexamethylene adipamide / polyisophthaloyl-2-methyl-pentanediamine (PA66 / D6), polyisophthaloyl-2-methyl-pentanediamine / polyisophthaloyl-2-methyl-pentanediamine (PADT / DI), polyhexamethylene adipamide / polyisophthaloyl-2-methyl-pentanediamine (PA66 / DT), polyisophthaloyl-2-methyl-pentanediamine / polyisophthaloyl-2-methyl-pentanediamine (PAD6 / DI), and polyisophthaloyl-2-methyl-pentanediamine / polyisophthaloyl-2-methyl-pentanediamine (PAD6 / DT).

[0021] Preferably, the copolyamide resin is selected from at least one of poly(2-methylpentanediamine) / poly(m-benzoyl-2-methylpentanediamine) (PADT / DI), poly(2-methylpentanediamine) / poly(2-methylpentanediamine) (PAD6 / DT), and poly(2-methylpentanediamine) / poly(m-benzoyl-2-methylpentanediamine) (PAD6 / DI).

[0022] In the polyhexamethylene adipamide / polyisophthaloyl-2-methyl-pentanediamine (PA66 / DI), the molar percentage of the polyisophthaloyl-2-methyl-pentanediamine segment is 1-60 mol%, preferably 2-40 mol%, and more preferably 5-25 mol%.

[0023] In polyhexamethylene adipamide / polyhexamethylene adipamide (PA66 / D6), the molar percentage of polyhexamethylene adipamide segments is 1-60 mol%, preferably 3-30 mol%, and more preferably 5-25 mol%.

[0024] In poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine) (PADT / DI), the molar percentage of poly(2-methyl-pentanediamine) is 1-60 mol%, preferably 5-20 mol%; more preferably 8-15 mol%.

[0025] In polyhexamethylene adipamide / poly(2-methyl-pentanediamine) (PA66 / DT), the molar percentage of poly(2-methyl-pentanediamine) is 1-60 mol%, preferably 5-35 mol%; more preferably 10-25 mol%.

[0026] In poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine) (PAD6 / DI), the molar percentage of poly(2-methyl-pentanediamine) is 1-60 mol%, preferably 5-20 mol%; more preferably 8-15 mol%.

[0027] In poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine) (PAD6 / DT), the molar percentage of poly(2-methyl-pentanediamine) is 1-60 mol%, preferably 5-20 mol%, more preferably 8-15 mol%.

[0028] Specifically, the aliphatic dicarboxylic acid with 4-18 carbon atoms is selected from at least one of succinic acid, glutaric acid, 2,2-dimethyl-glutaric acid, adipic acid, 2,4,4-trimethyl-adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecanoic acid; the aliphatic diamine with 2-16 carbon atoms is selected from ethylenediamine, 1-butylethylenediamine, 1,3-propanediamine, 1,2-propanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,1 -Dimethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,4-diethyl -1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,2-dimethyl-1,7-heptanediamine, 1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3 -At least one of dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 1,9-nonanediamine, 5-methyl-1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tetanediamine, 1,14-tetradecanediamine, 1,15-pentadecadecanediamine, and 1,16-hexadecanediamine; wherein the lactam is selected from at least one of β-propiolactam, γ-butyrolactam, δ-valeractam, ε-caprolactam, ω-aminoundecanoic acid, and ω-dodecanolactam.

[0029] The copolymer polyamide resin and homopolymer aliphatic polyamide resin of the present invention can be commercially available products or can be prepared in-house. The preparation method is the conventional polymerization method for polyamides as follows:

[0030] In a pressure vessel equipped with a magnetically coupled stirrer, condenser, gas inlet, feed inlet, and pressure explosion-proof port, the reactants (diamine and diacid) are added in a specific ratio. Next, benzoic acid, sodium hypophosphite (as a catalyst), and deionized water are added. The amount of benzoic acid is 2-3% of the total mass of the diamine and diacid, the weight of sodium hypophosphite is 0.05-0.15% of the other reactants excluding deionized water, and the weight of deionized water is 20-40% of the total reactants. Under stirring, a vacuum is first created, and then high-purity nitrogen is used as a protective gas to raise the temperature to 215-225°C over 1.5-2.5 hours. The reaction mixture is stirred at 215-225°C for 0.5-2 hours, and then stirring continues to raise the temperature to 255-265°C. The reaction is then carried out at a constant temperature and constant pressure of 2.1-2.3 MPa for 1.5-3 hours, maintaining pressure stability by continuously removing the generated water. After the reaction is complete, the product is discharged. The prepolymer was vacuum dried at 75-85℃ to obtain the prepolymer product. Then, the prepolymer product was solid-phase thickened under vacuum conditions of 225-235℃ and 40-60Pa for 8-12 hours to finally obtain polyamide.

[0031] The relative viscosity of the homopolymer aliphatic polyamide resin and the copolymer polyamide resin that can achieve the purpose of this invention is 1.8-2.8. The relative viscosity test method for polyamide is as follows: Referring to GB12006.1-89, the relative viscosity of polyamide with a concentration of 0.25 g / dl is measured in 98% concentrated sulfuric acid at 25 ± 0.01℃.

[0032] The melting point range of the homopolymer aliphatic polyamide resin and the copolymer polyamide resin that can achieve the purpose of this invention is 170-340℃. The test method is to use a differential scanning calorimeter for testing, referring to GB / T 19466.1-2004.

[0033] The toughening agent is selected from rubber or rubber grafted with active groups. The rubber is selected from at least one of polyolefin rubber, polyacrylonitrile rubber, polyacrylic rubber, and polyester rubber, and the active group is selected from maleic anhydride or GMA. The polyacrylonitrile rubber is selected from at least one of butadiene-acrylonitrile rubber, hydrogenated butadiene-acrylonitrile rubber, acrylonitrile isoprene rubber, and acrylonitrile-butadiene-styrene copolymer. The polyolefin rubber is selected from at least one of saturated polyolefin rubber and unsaturated polyolefin rubber. The saturated polyolefin rubber is selected from ethylene-octene copolymer, polyethylene rubber, polypropylene rubber, polyisobutylene rubber, ethylene-propylene rubber, and linear low-density polyethylene. Rubber, ethylene-butene rubber, vinyl chloride rubber; unsaturated polyolefin rubbers are selected from at least one of ethylene propylene diene monomer (EPDM) rubber, butadiene-styrene rubber, styrene-ethylene-butadiene-styrene block copolymer, ethylene-propylene-butadiene rubber, styrene-butadiene-styrene copolymer, and styrene-isoprene copolymer; polyacrylic acid rubbers are selected from at least one of ethylene-acrylic acid polymers and ethylene-acrylic acid ionomers; polyester rubbers are selected from at least one of ethylene-acrylate rubber, ethylene-vinyl acetate polymer, butadiene-acrylate rubber, ethylene-n-butyl acrylate-glycidyl methacrylate, and methacrylate-butadiene-styrene core / shell elastomers.

[0034] Depending on actual needs, 0-30 parts of additives may be added. These additives are selected from at least one of the following: colorants, lubricants, light stabilizers, UV absorbers, heat stabilizers, antioxidants, flame retardants, flame retardant synergists, anti-dripping agents, flow modifiers, release agents, antistatic agents, fluorescent whitening agents, and antibacterial agents. The content ranges for antioxidants, lubricants, and colorants.

[0035] 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.

[0036] An industrial nylon cable tie prepared from a polyamide composite material according to the present invention.

[0037] The present invention has the following beneficial effects:

[0038] This invention utilizes the crystallization characteristics of specific types of polyamides and employs rice bran wax salt as a nucleating agent to reduce crystal size. Through this combined action, the polyamide grain size becomes smaller than the wavelength of visible light, increasing crystal density and enabling the grains to absorb visible light. When the polyamide composite material is subjected to bending stress, the tiny voids created by the separation of the toughening agent from the polyamide resin matrix do not produce light reflection, thus significantly reducing the stress whitening defect of the polyamide composite material. Furthermore, the polyamide composite material of this invention maintains good mechanical properties. Attached Figure Description

[0039] Figure 1: Spline diagram of stress whitening test results. The left side is level 1, where the spline is almost completely whitened; the right side is level 8, where the whitening is not obvious. Detailed Implementation

[0040] 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.

[0041] The raw materials used in this invention are sourced from the following sources:

[0042] PA66: EPR24, Pingdingshan Shenma, relative viscosity 2.4, melting point 264℃;

[0043] PA1012: PA1012, Shandong Guangyin, relative viscosity 2.4, melting point 178℃;

[0044] PA56: ECOPENT 1273 Resin, Kaisai Biotechnology, melting point 254℃, relative viscosity 2.3;

[0045] PA510: ECOPENT E-3102, Kaisai Biotechnology, melting point 214℃, relative viscosity 2.2;

[0046] PA6: HY-2500A, Jiangsu Haiyang Chemical Fiber, relative viscosity 2.4, melting point 222℃;

[0047] PA11: BMNO, Arkema, relative viscosity 2.4, melting point 188℃;

[0048] PA10T: Vicnyl 700, Kingfa Science & Technology, relative viscosity 2.2, melting point 316℃;

[0049] PA6T / 66: Kingfa Science & Technology's PA6T / 66, relative viscosity 2.3, 6T content 45 mol%;

[0050] PA6T / 6I: PA6T / 6I, Kingfa Science & Technology, relative viscosity 2.3;

[0051] The following polyamides are self-made raw materials:

[0052] PA66 / DI: Samples without a distinct melting point have a melting range of 230~260℃;

[0053] PA66 / DI Grade DI Content (mol%) Melting Point (°C) Relative Viscosity A1 26 0 2.4 B2 25 6 2.4 C5 24 8 2.4 D2 5 24 0 2.4 E4 0 23 5 2.4 F5 0-2.4 G6 0-2.4 surface

[0054] PA66 / D6: Samples without a distinct melting point have a melting range of 230~260℃;

[0055] PA66 / D6 Grade, D6 Content (mol%), Melting Point (°C), Relative Viscosity: A1 26 32.0, B3 25 82.0, C5 25 22.0, D2 5 24 32.0, E3 0 23 82.0, F5 0 23 02.0, G6 0 - 2.0 surface

[0056] PADT / DI: Samples without a distinct melting point have a melting range of 280~320℃;

[0057] PADT / DI designation; DI content (mol%); Melting point (°C); Relative viscosity: A1-2.4; B5-2.4; C8-2.4; D15-2.4; E20-2.4; F50-2.4; G60-2.4. surface

[0058] PA66 / DT:

[0059] PA66 / DT designation; DT content (mol%); melting point (°C); relative viscosity: A1 265 2.5; B5 268 2.5; C1 10 267 2.5; D2 5 270 2.5; E3 5 275 2.5; F5 0 278 2.5; G6 0 285 2.5. surface

[0060] PAD6 / DI: Samples without a distinct melting point have a melting range of 230~270℃;

[0061] PAD6 / DI designation; DI content (mol%); melting point (°C); relative viscosity: A1-2.4; B5-2.4; C8-2.4; D15-2.4; E20-2.4; F50-2.4; G60-2.4. surface

[0062] PAD6 / DT: Samples without a distinct melting point have a melting range of 240~300℃;

[0063] PAD6 / DT designation; DT content (mol%); melting point (°C); relative viscosity: A1-2.4; B5-2.4; C8-2.4; D15-2.4; E20-2.4; F50-2.4; G60-2.4. surface

[0064] Sodium rice bran wax: R301, Chongqing Hecai Chemical Technology;

[0065] Rice bran wax calcium salt: R502, Chongqing Hecai Chemical Technology;

[0066] Sodium lignite: LICOMONT NAV101, Clariant;

[0067] Other nucleating agent A: HTPultra 5L, imifab;

[0068] Other nucleating agent B: CHB-3C, Chenghe Technology;

[0069] Toughening agent: Fusabond N493, maleic anhydride-grafted ethylene octene copolymer, Dow;

[0070] Lubricant: Ethylene-acrylic acid copolymer wax powder, A-C540A, purchased from ExxonMobil;

[0071] Antioxidants: Antioxidant 1098 and antioxidant PEP-36, mixed in a 1:1 ratio, purchased from Adico;

[0072] Organic black dye: provided by Kingfa Science & Technology, CAS#12237-22-8;

[0073] Preparation method of polyamide composite materials 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 highest temperature of the screw barrel was the melting point of the polyamide +20-25°C. The addition of organic black dye in the examples and comparative examples of this invention is for testing stress whitening resistance and is not mandatory.

[0074] Test methods:

[0075] (1) Tensile strength: Tested according to ISO527-2:2012, with a tensile rate of 50 mm / min.

[0076] (2) Stress whitening: A universal testing machine with video recording attachment was used to test the tensile specimen at a tensile rate of 50 mm / min according to ISO 527-2:2012. The appearance under different strains during the tensile process was recorded. Images of the appearance at the initial state, 25% (when the specimen's fracture strain is less than 50%), and 50% (when the specimen's fracture strain is greater than 50%) were used for image processing. Using J graphics processing software, the image was converted to 8-bit format. The grayscale of the spline located in the middle of the extensometer was analyzed, and the average grayscale value GV (0~255) was recorded. The difference between the average grayscale value of the target strain and the initial state, ΔGV, was calculated. When ΔGV≤10, the stress whitening resistance level is 8; when 10<ΔGV≤20, the stress whitening resistance level is 7; when 20<ΔGV≤30, the stress whitening resistance level is 6; when 30<ΔGV≤40, the stress whitening resistance level is 5; when 40<ΔGV≤50, the stress whitening resistance level is 4; when 50<ΔGV≤60, the stress whitening resistance level is 3; when 60<ΔGV≤80, the stress whitening resistance level is 2; when ΔGV>80, the stress whitening resistance level is 1. The higher the level, the better the stress whitening resistance performance. As shown in Figure 1, the spline on the left is level 1, the spline on the right is level 8, level 4 is qualified, and level 8 is optimal.

[0077] Table 1: Weight contents and test results of each component in the polyamide composites of Examples 1-6

[0078] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Homopolymer Aliphatic Polyamide Type PA66 PA1012 PA56 PA510 PA6 PA11 Homopolymer Aliphatic Polyamide Content 322336323232 PA66 / DI-A484754484848 Sodium Rice Bran Wax Salt 0.50.110.5 Calcium Rice Bran Wax Salt 0.40.7 Toughening Agent 181230241020 Antioxidant 0.5 Lubricant 0.20.20.3 Organic Black Dye 0.80.80.80.80.80.8 Stress Whitening Grade 555555 Tensile Strength, MPa 57.833.641.540.754.827.0 surface

[0079] Table 2: Weight contents and test results of each component in the polyamide composites of Examples 7-10

[0080] Example 7 Example 8 Example 9 Example 10 Homopolymer Aliphatic Polyamide Type PA66 PA66 PA66 PA66 Homopolymer Aliphatic Polyamide Content 7652204 PA66 / DI-A4286076 Rice Bran Wax Sodium Salt 0.5 0.5 0.5 0.5 Toughening Agent 1818 1818 Organic Black Dye 0.8 0.8 0.8 0.8 Stress Whitening, Grade 4554 Tensile Strength, MPa 54.65 8.05 7.65 6.9 surface

[0081] As can be seen from Examples 1 / 7-10, the optimal ratio of homopolymer aliphatic polyamide to PA66 / DI results in better stress whitening resistance.

[0082] Table 3: Weight content and test results of each component in the polyamide composites of Examples 11-16

[0083] Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 PA66323232323232 PA66 / DI No. BCDEFG PA66 / DI Content 484848484848 Rice bran wax sodium salt 0.50.50.50.50.50.5 Toughening agent 181818181818 Organic black dye 0.80.80.80.80.80.8 Stress whitening, grade 677654 Tensile strength, MPa 54.555.255.656.057.358.4 surface

[0084] As can be seen from Examples 1 / 11-16, the stress whitening resistance is better when the preferred PA66 / DI repeating unit ratio is used.

[0085] Table 4: Weight content and test results of each component in the polyamide composites of Examples 17-23

[0086] Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 PA101232323232323232 PA66 / D6 No. ABCDEFG PA66 / D6 Content 48484848484848 Rice bran wax sodium salt 0.50.50.50.50.50.50.5 Toughening agent 18181818181818 Organic black dye 0.80.80.80.80.80.8 Stress whitening, grade 5677654 Tensile strength, MPa 29.7 29.8 30.0 30.2 30.4 31.2 31.5 surface

[0087] As can be seen from Examples 17-23, the stress whitening resistance is better when the preferred PA66 / D6 repeating unit ratio is used.

[0088] Table 5: Weight content and test results of each component in the polyamide composites of Examples 24-30

[0089] Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 PA5632323232323232 PADT / DI No. ABCDEFGPADT / DI Content 48484848484848 Rice Bran Wax Sodium Salt 0.50.50.50.50.50.50.5 Toughening Agent 18181818181818 Organic Black Dye 0.80.80.80.80.80.8 Stress Whitening, Grade 6788765 Tensile Strength, MPa 49.850.250.951.651.852.853.0 surface

[0090] As can be seen from Examples 24-30, the stress whitening resistance is better when the PADT / DI repeating unit ratio is preferred.

[0091] Table 6: Weight content and test results of each component in the polyamide composites of Examples 31-37

[0092] Example 31 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 PA51032323232323232 PA66 / DT No. ABCDEFG PA66 / DT Content 48484848484848 Rice bran wax sodium salt 0.50.50.50.50.50.50.5 Toughening agent 18181818181818 Organic black dye 0.80.80.80.80.80.8 Stress whitening, grade 5677654 Tensile strength, MPa 43.6 43.9 44.4 45.0 45.3 45.9 46.2 surface

[0093] As can be seen from Examples 31-37, the stress whitening resistance is better when the preferred PA66 / DT repeating unit ratio is used.

[0094] Table 7: Weight content and test results of each component in the polyamide composites of Examples 38-44

[0095] Example 38 Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 PA51032323232323232 PAD6 / DI No. ABCDEFGPAD6 / DI Content 48484848484848 Rice Bran Wax Sodium Salt 0.50.50.50.50.50.50.5 Toughening Agent 18181818181818 Organic Black Dye 0.80.80.80.80.80.8 Stress Whitening, Grade 6788765 Tensile Strength, MPa 40.440.841.642.043.643.844.5 surface

[0096] As can be seen from Examples 38-44, the stress whitening resistance is better when the preferred repeating unit ratio of PAD6 / DI is used.

[0097] Table 8: Weight content and test results of each component in the polyamide composites of Examples 45-51

[0098] Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 Example 51 PA632323232323232 PAD6 / DT No. ABCDEFGPAD6 / DT Content 48484848484848 Rice bran wax sodium salt 0.50.50.50.50.50.50.5 Toughening agent 18181818181818 Organic black dye 0.80.80.80.80.80.80.8 Stress whitening, grade 6788765 Tensile strength, MPa 49.149.450.450.751.251.852.0 surface

[0099] As can be seen from Examples 45-51, the stress whitening resistance is better when the preferred repeating unit ratio of PAD6 / DT is used.

[0100] Table 9: Weight content and test results of each component in the polyamide composites of Examples 52-57

[0101] Example 52 Example 53 Example 54 Example 55 Example 56 Example 57 PA66 / DI-A80 PA66 / D6-A80 PADT / DI-A80 PA66 / DT-A80 PAD6 / DI-A80 PAD6 / DT-A80 Rice bran wax sodium salt 0.5 0.5 0.5 0.5 0.5 0.5 Toughening agent 18 18 18 18 18 18 Organic black dye 0.8 0.8 0.8 0.8 0.8 Stress whitening, grade 55 6 5 6 6 6 Tensile strength, MPa 55.6 54.9 58.3 56.8 54.0 56.2 surface

[0102] As can be seen from Examples 1 / 7-10 / 52, the stress whitening resistance is better when the ratio of homopolymer aliphatic polyamide to PA66 / DI and the single block copolymer polyamide resin are preferred.

[0103] Table 10: Weight content and test results of each component in the polyamide composites of Comparative Examples 1-7

[0104] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Homopolymer Aliphatic Polyamide Type PA66 PA66 PA66 PA66 PA66 PA10 12 PA6 Homopolymer Aliphatic Polyamide Content 32 32 32 32 80 80 80 PA66 / DI-A 48 48 48 48 Rice Bran Wax Sodium Salt 0 0.5 0.5 0.5 Sodium Lignite 0.5 Other Nucleating Agent A 0.5 Other Nucleating Agent B 0.5 Toughening Agent 18 18 18 18 18 18 Organic Black Dye 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Stress Whitening, Grade 11 11 11 11 Tensile Strength, MPa 53.9 54.8 58.9 58.7 54.2 39.0 50.3 surface

[0105] As can be seen from Comparative Examples 1-4, without rice bran wax sodium salt nucleating agent, or other nucleating agents, the crystal density and crystal grain size of the resin matrix of the present invention cannot be achieved. Therefore, the stress whitening resistance is not improved.

[0106] As can be seen from Comparative Examples 5-7, aliphatic polyamides have insufficient resistance to stress whitening.

[0107] Table 11: Weight content and test results of each component in the polyamide composites of Comparative Examples 8-13

[0108] Comparative Example 8, Comparative Example 9, Comparative Example 10, Comparative Example 11, Comparative Example 12, Comparative Example 13: PA10T3280PA6T / 66, PA6T / 6I3280PA66 / DI-A484848; Rice Bran Wax Sodium Salt 0.5; Toughening Agent 181818181818; Organic Black Dye 0.8; Stress Whitening, Grade 121111; Tensile Strength, MPa: 54.85; 0.45; 3.55; 2.04; 9.55; 1.8 surface

[0109] As can be seen from Comparative Examples 8-13, polyamide resins not specified in claim 1 cannot achieve the effects of the present invention.

Claims

1. A polyamide composite material, characterized in that, By weight, it includes the following components: 70-94 parts of polyamide resin; Rice bran wax metal salt 0.1-1 parts; toughening agent 5-30 parts; the polyamide is selected from copolyamide resin, a blend of copolyamide resin and homopolymer aliphatic polyamide resin, wherein, when the copolyamide resin and homopolymer aliphatic polyamide resin are blended, the copolyamide resin accounts for 5-95 wt% of the polyamide resin; the homopolymer aliphatic polyamide resin is derived from an aliphatic dicarboxylic acid with 4-18 carbon atoms and an aliphatic diamine with 2-16 carbon atoms, or the homopolymer aliphatic polyamide resin is derived from lactam or amino acid; the copolyamide resin is derived from a diacid unit and a diamine unit, the diacid unit is selected from at least one of 1,6-adipic acid, isophthalic acid, and terephthalic acid, the diamine unit is selected from 2-methyl-pentanediamine and optionally 1,6-hexanediamine, and 2-methyl-pentanediamine accounts for 1-100% of the diamine unit. mol%; the copolyamide resin is selected from at least one of the following: hexamethylene adipamide / polyisophthaloyl-2-methyl-pentanediamine, hexamethylene adipamide / polyisophthaloyl-2-methyl-pentanediamine, polyisophthaloyl-2-methyl-pentanediamine / polyisophthaloyl-2-methyl-pentanediamine, hexamethylene adipamide / polyisophthaloyl-2-methyl-pentanediamine, polyisophthaloyl-2-methyl-pentanediamine / polyisophthaloyl-2-methyl-pentanediamine, and polyisophthaloyl-2-methyl-pentanediamine / polyisophthaloyl-2-methyl-pentanediamine.

2. The polyamide composite material according to claim 1, characterized in that, The rice bran wax metal salt is selected from at least one of rice bran wax sodium salt and rice bran wax calcium salt; the average particle size of the rice bran wax metal salt is 10-800 micrometers.

3. The polyamide composite material according to claim 1, characterized in that, When copolyamide resin is compounded with homopolymer aliphatic polyamide resin, the copolyamide resin accounts for 35-75 wt% of the polyamide resin.

4. The polyamide composite material according to claim 1, characterized in that, The copolyamide resin is selected from at least one of poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine), poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine), and poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine).

5. The polyamide composite material according to claim 1, characterized in that, In the aforementioned polyhexamethylene adipamide / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) segment is 1-60 mol; in the aforementioned polyhexamethylene adipamide / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) segment is 1-60 mol; in the aforementioned poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) segment is 1-60 mol. In polyhexamethylene adipamide / poly(2-methylpentanediamine), the molar percentage of poly(2-methylpentanediamine) is 1-60 mol; in poly(2-methylpentanediamine) / poly(isophthaloyl-2-methylpentanediamine), the molar percentage of poly(2-methylpentanediamine) is 1-60 mol; in poly(2-methylpentanediamine) / poly(2-methylpentanediamine), the molar percentage of poly(2-methylpentanediamine) is 1-60 mol.

6. The polyamide composite material according to claim 5, characterized in that, In the aforementioned polyhexamethylene adipamide / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) segment is 2-40 mol; in the polyhexamethylene adipamide / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) segment is 3-30 mol; in the poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) segment is 5-20 mol%. In polyhexamethylene adipamide / poly(2-methylpentanediamine), the molar percentage of poly(2-methylpentanediamine) is 5-35 mol; in poly(2-methylpentanediamine) / poly(isophthaloyl-2-methylpentanediamine), the molar percentage of poly(2-methylpentanediamine) is 5-20 mol; in poly(2-methylpentanediamine) / poly(2-methylpentanediamine), the molar percentage of poly(2-methylpentanediamine) is 5-20 mol.

7. The polyamide composite material according to claim 6, characterized in that, In the aforementioned polyhexamethylene adipamide / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) chain segment is 5-25 mol; in the aforementioned polyhexamethylene adipamide / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) chain segment is 5-25 mol; in the aforementioned poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) chain segment is 8-15 mol; in the aforementioned poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine), the molar percentage of the poly(2-methyl-pentanediamine) chain segment is 10-25 mol. mol%; In poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine), the molar percentage of poly(2-methyl-pentanediamine) is 8-15 mol%; In poly(2-methyl-pentanediamine) / poly(2-methyl-pentanediamine), the molar percentage of poly(2-methyl-pentanediamine) is 8-15 mol%.

8. The polyamide composite material according to claim 1, characterized in that, The toughening agent is selected from rubber or rubber grafted with active groups; the rubber is selected from at least one of polyolefin rubber, polyacrylonitrile rubber, polyacrylic rubber, and polyester rubber; the polyacrylonitrile rubber is selected from at least one of butadiene-acrylonitrile rubber, hydrogenated butadiene-acrylonitrile rubber, acrylonitrile isoprene rubber, and acrylonitrile-butadiene-styrene copolymer; the polyolefin rubber is selected from at least one of saturated polyolefin rubber and unsaturated polyolefin rubber; the saturated polyolefin rubber is selected from ethylene-octene copolymer, polyethylene rubber, polypropylene rubber, polyisobutylene rubber, ethylene-propylene rubber, and ethylene... - Butene rubber, vinyl chloride rubber; unsaturated polyolefin rubbers are selected from at least one of ethylene propylene diene monomer (EPDM) rubber, butadiene-styrene rubber, styrene-ethylene-butadiene-styrene block copolymer, ethylene-propylene-butadiene rubber, and styrene-isoprene copolymer; polyacrylic rubbers are selected from at least one of ethylene-acrylic acid polymers and ethylene-acrylic acid ionomers; polyester rubbers are selected from at least one of core / shell elastomers of the type of ethylene-acrylate rubber, ethylene-vinyl acetate polymer, butadiene-acrylate rubber, ethylene-n-butyl acrylate-glycidyl methacrylate, and methacrylate-butadiene-styrene.

9. The polyamide composite material according to claim 1, characterized in that, The toughening agent is selected from rubber, and the rubber is selected from polyolefin rubber; the polyolefin rubber is selected from at least one of saturated polyolefin rubber and unsaturated polyolefin rubber; the saturated polyolefin rubber is selected from linear low-density polyethylene rubber; the unsaturated polyolefin rubber is selected from styrene-butadiene-styrene copolymer.

10. The polyamide composite material according to claim 1, characterized in that, The aliphatic dicarboxylic acid with 4-18 carbon atoms is selected from at least one of succinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2,4,4-trimethyl-adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecanoic acid; the aliphatic diamine with 2-16 carbon atoms is selected from ethylenediamine, 1-butylethylenediamine, 1,3-propanediamine, 1,2-propanediamine, 1,3-butanediamine, 1,4-butanediamine, and 1,1-dimethylethylenediamine. 1,4-Butanediamine, 1,2-Dimethyl-1,4-Butanediamine, 1,3-Dimethyl-1,4-Butanediamine, 1,4-Dimethyl-1,4-Butanediamine, 2,3-Dimethyl-1,4-Butanediamine, 1-Ethyl-1,4-Butanediamine, 1,5-Pentanediamine, 2-Methyl-1,5-Pentanediamine, 1,6-Hexanediamine, 2,5-Dimethyl-1,6-Hexanediamine, 2,4-Dimethyl-1,6-Hexanediamine, 3,3-Dimethyl-1,6-Hexanediamine, 2,2-Dimethyl-1,6-Hexanediamine, 2,4-Diethyl-1 6-Hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,2-dimethyl-1,7-heptanediamine, 1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3- At least one of dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 1,9-nonanediamine, 5-methyl-1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tetanediamine, 1,14-tetradecanediamine, 1,15-pentadecadecanediamine, and 1,16-hexadecanediamine; wherein the lactam is selected from at least one of β-propiolactam, γ-butyrolactam, δ-valeractam, ε-caprolactam, ω-aminoundecanoic acid, and ω-dodecanolactam.

11. The polyamide composite material according to claim 1, characterized in that, The product also includes 0-30 parts by weight of additives, wherein the additives are selected from at least one of colorants, lubricants, light stabilizers, heat stabilizers, antioxidants, flame retardants, flame retardant synergists, anti-dripping agents, flow modifiers, release agents, antistatic agents, fluorescent whitening agents, and antibacterial agents.

12. A method for preparing the polyamide composite material according to any one of claims 1-10, 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.

13. A nylon industrial cable tie prepared using the polyamide composite material according to any one of claims 1-10.

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