Polyamide alloy material, preparation method and application thereof

Abstract

The application belongs to the field of high polymer materials, and particularly relates to a polyamide alloy material and a preparation method and application thereof, in particular, the application discloses a polyamide alloy material, which contains the following components in parts by weight: 65-95 parts of polyamide; 5-30 parts of an anti-fatigue agent; and 1-5 parts of an anti-fatigue synergist; the anti-fatigue agent is selected from a terpolymer composed of acrylamide, 2-acrylamido-2-methyl-1-propane sulfonic acid and sodium p-styrenesulfonate; the polyamide alloy material provided by the application has good anti-fatigue performance and can be used for preparing a flexible polyamide alloy part.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, and specifically relates to a polyamide alloy material, its preparation method, and its application. Background Technology

[0002] Polyamide, as one of the earliest developed synthetic fibers and engineering plastics in the world, has been widely used in machinery, automotive, electronics, aerospace and other fields due to its excellent mechanical strength, wear resistance, oil resistance and chemical corrosion resistance. However, nylon materials also have some inherent drawbacks, such as insufficient flexibility and elastic recovery in certain application scenarios.

[0003] As modern industry develops towards lightweighting, fatigue resistance, and high performance, higher demands are placed on the dynamic mechanical properties of structural materials, especially their fatigue resistance. For example, in applications such as 3D-printed flexible skeletal scaffolds, precision mechanical transmission cables, and flexible robot joints, materials not only need to possess sufficient strength, but also need to be able to quickly recover their original shape after repeated bending and torsional deformation and maintain a long service life.

[0004] Therefore, there is an urgent need in this field to develop a new type of nylon composite material to significantly improve its fatigue resistance, thereby meeting the demand for high-fatigue-resistant materials in high-end industrial fields. Summary of the Invention

[0005] One of the objectives of this invention is to solve the above-mentioned technical problems and provide a polyamide alloy material with good fatigue resistance.

[0006] The second objective of this invention is to provide a method for preparing the aforementioned polyamide alloy material.

[0007] A third objective of this invention is to provide applications of the aforementioned polyamide alloy materials.

[0008] The fourth objective of this invention is to provide a flexible polyamide alloy component.

[0009] This invention is achieved through the following technical solution: A polyamide alloy material, by weight, comprises the following components: 65-95 parts of polyamide; 5-30 parts of anti-fatigue agent; 1-5 parts of anti-fatigue synergist; The anti-fatigue agent is selected from a terpolymer composed of acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, and sodium p-styrenesulfonate.

[0010] The polyamides described in this invention include, but are not limited to, any one of the following types: (a) Homopolymers formed by ring-opening polymerization of one or more lactams, such as PA4, PA6, PA7, PA8, PA9, PA11, PA12, PA13; (b) Polyamides formed by polycondensation of one or more dicarboxylic acids and one or more diamines, including aliphatic polyamides such as PA36, PA46, PA56, PA510, PA511, PA512, PA66, PA69, PA610, PA611, PA612, PA613, PA614, PA1010, PA1012, PA1212, PA1313; and semi-aromatic polyamides such as poly(terephthalamide), such as PA4T, PA5T, PA6T, PA7T, PA8T, PA9T, PA10T, PA11T, PA12T, and copolymers thereof with aliphatic polyamides, such as PA6T / 66, PA6T / 6I, PA6T / XT; (c) Polyamides formed by polycondensation of one or more amino acids, such as PA4, PA6, PA11, and PA12; (d) Copolymers formed by copolymerization of the above-mentioned monomers, such as PA6 / 66, PA6 / 12; and mixtures of any two or more of the above-mentioned polyamides.

[0011] Furthermore, the polyamides described in this invention also include polyamides prepared by other synthetic methods such as interfacial polycondensation, solution polycondensation, and phosphoric acid-catalyzed polycondensation, specifically including: Fully aromatic polyamides, such as poly(p-phenylene terephthalamide) (PPTA) and poly(m-phenylene isophthalamide) (PMIA); Bio-based polyamides refer to polyamides prepared from biologically derived diamines and diacids, such as PA510, PA511, PA512, PA1010, PA1012, and PA10T. Long-chain polyamides, such as PA612, PA613, PA614, PA1010, PA1012, PA1212; Other derivative or modified types of polyamides include transparent polyamides such as polyamides prepared from alicyclic monomers PACM, amorphous or microcrystalline polyamides such as PA6-3-T; high-temperature polyamides such as semi-aromatic or fully aromatic polyamides with high glass transition temperatures and high melting points such as PA4T, PA6T, PA9T, PA10T; and other polyamides with special functions.

[0012] It should be noted that there is some overlap in the above classifications. For example, PA10T belongs to semi-aromatic polyamide, bio-based polyamide, and high-temperature polyamide simultaneously. This invention covers all types of polyamides mentioned above, including their homopolymers, copolymers, and mixtures.

[0013] The polyamide melt flow rate described in this invention is 1-100 g / 10 min, and the testing standard is ISO 1133:2005. The test conditions can be selected according to the type of polyamide. For example, PA6 is 260℃ / 2.16 kg, PA66 is 280℃ / 2.16 kg, PA10T is 325℃ / 2.16 kg, PA612 is 260℃ / 2.16 kg, and PA12 is 220℃ / 2.16 kg.

[0014] Preferably, the melt flow rate of the polyamide resin is 15-50 g / 10 min, and the testing standard is ISO1133:2005.

[0015] Preferably, the polyamide is selected from at least one of PA6, PA11, PA12, PA46, PA56, PA66, PA610, PA612, PA6T, PA9T, PA10T, PA1010, and PA1012.

[0016] More preferably, the polyamide is selected from at least one of PA6, PA6T, PA10T, PA612, PA11, and PA12.

[0017] In the polyamide alloy material described in this invention, the weight parts (unit: parts) of the polyamide can be: 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, or a range formed by any two of the above values.

[0018] In the polyamide alloy material described in this invention, the mass content of the polyamide is not less than 50%.

[0019] The melt flow rate of the terpolymer described in this invention is 2-30 g / 10 min, the testing standard is ISO 1133:2005, and the testing conditions are 190℃ and 5 kg.

[0020] The repeating unit structure of the terpolymer is: (acrylamide) m (2-Acrylamido-2-methyl-1-propanesulfonic acid) n (Sodium p-styrenesulfonate) k The total molar number of all structural units in the copolymer is 100%, and the ratio of m:n:k is (50-85):(10-30):(5-20).

[0021] More preferably, when the total molar number of all structural units in the copolymer is 100%, the ratio of m:n:k is (55-80):(15-25):(10-15).

[0022] This invention uses ¹H-NMR spectroscopy to determine the component ratios of a terpolymer. First, the copolymer is dissolved in deuterated dimethyl sulfoxide (DMSO-d6) to prepare a solution of 5-10 mg / mL. The solution is then analyzed using an NMR spectrometer to obtain a spectrum. The characteristic peak positions of each monomer are identified in the spectrum: the chemical shift for acrylamide is 5.4-6.2 ppm, for 2-acrylic acid-2-methylpropanesulfonic acid is 1.2-1.4 ppm, and for sodium p-styrenesulfonate is 6.8-7.8 ppm. The molar ratios of the three monomers are calculated by integrating and normalizing the areas of each characteristic peak.

[0023] The terpolymer described in this invention is connected by covalent bonds.

[0024] The terpolymer described in this invention is a random copolymer.

[0025] The terpolymer described in this invention can be commercially available or homemade. The homemade method is as follows: Place the cleaned flask in a water bath and purge it with nitrogen gas at 85-95°C for 20-40 minutes to ensure complete air removal. Cool the flask to 50-70°C, then mix acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, and sodium p-styrenesulfonate in a molar ratio of (50-85):(10-30):(5-20) until homogeneous. Place this mixture in a constant-pressure dropping funnel and slowly add it dropwise to the flask. Simultaneously, add an aqueous solution of ammonium persulfate to another constant-pressure dropping funnel. After 2 hours of reaction, cool and allow the reaction product to precipitate. Clean the product with ethanol, then dry and pulverize to obtain the terpolymer described in this invention.

[0026] This invention also provides another method for preparing a terpolymer: Span 80, Tween 80, and white oil are weighed in a specific ratio, mixed thoroughly, and placed in a three-necked flask equipped with a stirrer to form an oil phase. Pre-determined amounts of acrylamide, 2-methyl-2-acrylamidopropanesulfonic acid, and sodium p-styrenesulfonate are weighed sequentially and dissolved in distilled water to form an aqueous phase. Under constant temperature and stirring conditions, the aqueous phase is slowly added dropwise to the oil phase using a constant pressure dropping funnel. After the reaction is complete, the product is filtered, dried, and crushed to obtain the terpolymer.

[0027] In the polyamide alloy material of the present invention, the weight parts (unit: parts) of the fatigue resistance agent can be: 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, or any range formed by any two of the above values.

[0028] In the polyamide alloy material described in this invention, the mass content of the terpolymer is not less than 3%.

[0029] Preferably, the anti-fatigue synergist is selected from trisodium trithiocyanate.

[0030] Preferably, the material further comprises 0.01-40 parts by weight of filler.

[0031] Preferably, the filler is selected from at least one of calcium carbonate, talc, wollastonite, kaolin, mica, glass microspheres, glass fiber, and carbon fiber.

[0032] Preferably, the product also includes 0.01-3 parts by weight of an adjuvant.

[0033] Preferably, the additive is selected from at least one of heat stabilizers, light stabilizers, antioxidants, lubricants, release agents, antistatic agents, plasticizers, nucleating agents, rheology modifiers, filler dispersants, flame retardants, toughening agents, compatibilizers, colorants, antibacterial agents, anti-sticking agents, anti-caking agents, matting agents, coupling agents, metal passivators, odor absorbers, and mildew inhibitors.

[0034] More preferably, the additive is selected from at least one of lubricants or antioxidants.

[0035] Preferably, the antioxidant is at least one of hindered phenolic antioxidants, hindered amine antioxidants, and phosphorus-containing antioxidants.

[0036] This invention provides a method for preparing a polyamide alloy material: all components are mixed evenly according to the specified ratio, and then melt-blended and extruded into granules.

[0037] Preferably, a twin-screw extruder is used for extrusion.

[0038] Preferably, the screw speed of the twin-screw extruder is 300-600 rpm.

[0039] Preferably, the length-to-diameter ratio L / D is 32:1-48:1.

[0040] Preferably, the melting temperature during melt blending is 190-280℃.

[0041] The present invention provides a flexible polyamide alloy part, comprising the above-mentioned polyamide alloy material.

[0042] Preferably, the flexible polyamide alloy component can be: Flexible electronics and consumer electronics components: Particularly suitable for foldable devices, support structures for rollable screens, flexible hinges (spindles), wristbands or housings for smart wearable devices, etc. The material's high resistance to bending fatigue can meet the opening and closing life requirements of tens of thousands of cycles for such products.

[0043] Automotive industrial parts: These can be used to manufacture piping systems that require oil and chemical resistance and a certain degree of flexibility, such as fuel lines, brake system lines (vacuum lines), various fluid delivery pipes in the engine compartment, as well as wiring harness protection sleeves and cable ties. Their flexibility helps absorb vibration and facilitates piping installation in confined spaces.

[0044] Tools and equipment components: Suitable for making flexible handles and protective sleeves for manual or power tools, as well as sports equipment (such as ski buckles and connecting parts for sports protective gear), which can provide a good feel and cushion impact.

[0045] Other industrial equipment and components: can be used for 3D printed flexible bone supports, precision mechanical transmission ropes, robot flexible joints and other mechanical parts that require flexible connections, protective covers for transmission mechanisms, flexible guide rails, etc.

[0046] Compared with the prior art, the present invention has the following advantages: This invention significantly improves the fatigue resistance of nylon materials by introducing a terpolymer composed of acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, and sodium p-styrenesulfonate, making it particularly suitable for preparing flexible polyamide alloy parts that require repeated bending and deformation.

[0047] The combined use of anti-fatigue synergists can produce a synergistic effect, further improving the fatigue resistance of polyamide alloy systems. Detailed Implementation

[0048] 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.

[0049] Sources of raw materials used in this invention: Polyamide 1: PA6, melt flow rate of 20g / 10min (260℃, 2.16kg), grade PA6 HY-2500A, company Haiyang Chemical Fiber.

[0050] Polyamide 2: PA10T, melt flow rate of 25g / 10min (325℃, 2.16 kg), grade VICNYL 600PNC013, company Zhuhai Wantong.

[0051] Polyamide 3: PA612, melt flow rate 40g / 10min (260℃, 2.16kg), grade A120, company Shanghai Yinggu.

[0052] Polyamide 4: PA12, melt flow rate 40 g / 10 min (220 °C, 2.16 kg), grade VESTAMID L1940NC, company Evonik Industries.

[0053] Anti-fatigue agent 1: Self-made, melt flow rate 4g / 10min; place the cleaned flask in a water bath, purge with nitrogen at 90℃ for 30min to ensure air removal, then cool to 60℃. Mix acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, and sodium p-styrenesulfonate according to a predetermined ratio, transfer to a constant pressure dropping funnel, and slowly add to the flask. Simultaneously, place an aqueous solution of ammonium persulfate in another constant pressure dropping funnel and slowly add it. After 2 hours of reaction, cool and precipitate the reaction product, wash it with ethanol, dry and pulverize it to obtain an acrylamide / 2-acrylamido-2-methyl-1-propanesulfonic acid / sodium p-styrenesulfonate terpolymer. The molar ratio of the corresponding structural units of acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, and sodium p-styrenesulfonate in the obtained terpolymer is 50:30:20.

[0054] Anti-fatigue agent 2: self-made, melt flow rate 13g / 10min; the self-made method of anti-fatigue agent 2 is the same as the preparation method of anti-fatigue agent 1, and the molar ratio of the corresponding structural units of acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid and sodium p-styrenesulfonate in the obtained terpolymer is 70:15:15.

[0055] Anti-fatigue agent 3: self-made, melt flow rate of 25 g / 10 min. The self-made method of anti-fatigue agent 3 is the same as that of anti-fatigue agent 1. The molar ratio of the corresponding structural units of acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid and sodium p-styrenesulfonate in the obtained terpolymer is 85:10:5.

[0056] Anti-fatigue agent 4: self-made, melt flow rate of 14 g / 10 min. The self-made method of anti-fatigue agent 4 is the same as that of anti-fatigue agent 1. The molar ratio of the corresponding structural units of acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid and sodium p-styrenesulfonate in the obtained terpolymer is 60:30:10.

[0057] Anti-fatigue agent 5: self-made, melt flow rate 8 g / 10 min. The method for making anti-fatigue agent 5 is as follows: Weigh out a ratio of Span 80, Tween 80, and white oil, mix thoroughly, and place in a three-necked flask equipped with a stirrer to form an oil phase. Sequentially weigh out predetermined amounts of acrylamide, 2-methyl-2-acrylamidopropanesulfonic acid, and sodium p-styrenesulfonate, dissolve in distilled water to form an aqueous phase. Under constant temperature and stirring conditions, slowly add the aqueous phase dropwise to the oil phase using a constant pressure dropping funnel. After the reaction is complete, filter, dry, and crush the product to obtain a terpolymer. The molar ratio of the corresponding structural units of acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, and sodium p-styrenesulfonate in the obtained terpolymer is 60:20:20.

[0058] Anti-fatigue synergist: trisodium trithiocyanate, JHXC, Hubei Jiahuixingcheng Biotechnology Co., Ltd.

[0059] Filler 1: Talc powder, TYT-777A, Guangzhou Tianyuan Chemical Co., Ltd.

[0060] Filler 2: Glass fiber, ECS10-03-568H, China Jushi Co., Ltd.

[0061] Additives: Pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and ethylene bis-stearamide are mixed in a 1:1 mass ratio and are commercially available.

[0062] Other anti-fatigue agents: maleic anhydride-grafted ethylene octene copolymer, N493, DuPont.

[0063] Test methods: Fatigue resistance test: The alloy materials prepared in each example and comparative example were injection molded into 200*10*2mm strips. After being repeatedly bent 20 times at 90° along their length, they were placed flat on a table. After the shape of the strips stabilized, the bending angle of the strips was measured. The closer the angle is to 180°, the stronger the fatigue resistance.

[0064] The embodiments of the present invention are obtained by the following methods: All components were mixed evenly according to the specified ratio, and then melt-blended and extruded into granules using a twin-screw extruder. The twin-screw extruder had a screw speed of 450 rpm, a screw diameter of 35 mm, an L / D ratio of 40:1, a melt temperature of 210℃ during melt blending, and an extrusion temperature of 230℃.

[0065] Table 1. Weight parts and test results of each component in Examples 1-12

[0066] Table 2. Weight parts of each component and test results for Comparative Examples 1-5

[0067] As can be seen from Examples 1-12, the fatigue resistance of the polyamide alloy material provided in the embodiments of the present invention is ≥160°, which shows that the polyamide alloy material provided in the present invention has excellent fatigue resistance.

[0068] As can be seen from Comparative Examples 1-5, the fatigue resistance of the polyamide alloy material in the comparative examples is <145°.

[0069] Comparative Example 1 represents the case without the addition of an anti-fatigue synergist. The anti-fatigue agent improves the anti-fatigue performance of the polyamide alloy material, but its improvement effect is far less than that of Example 3.

[0070] Comparative Example 2 further verified the synergistic effect of anti-fatigue agents and anti-fatigue synergists. In the absence of anti-fatigue agents, even in the presence of anti-fatigue synergists, the improvement in anti-fatigue performance is limited.

[0071] In Comparative Example 3, the amount of anti-fatigue agent added was less than 5 parts, which had a certain effect on improving the fatigue resistance of polyamide alloy materials, but could not reach 160°.

[0072] Comparative Example 4 used other anti-fatigue agents. Compared with Example 2, it is obvious that other anti-fatigue agents cannot achieve the anti-fatigue effect of the terpolymer provided by the present invention.

[0073] Comparative Example 5 further verified the synergistic effect of the anti-fatigue agent and the anti-fatigue synergist. Under the condition of ensuring the same total amount, the lack of the anti-fatigue synergist resulted in a less effective improvement in anti-fatigue performance than in Example 3 where both were present.

[0074] It should be noted that Comparative Example 6 provides a case without fillers. In this system, even without fillers, the anti-fatigue agent and anti-fatigue synergist can still achieve good anti-fatigue effects. This shows that fillers do not have a significant effect on anti-fatigue.

[0075] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polyamide alloy material, characterized in that, By weight, it contains the following components: 65-95 parts of polyamide; 5-30 parts of anti-fatigue agent; Anti-fatigue synergist 1-5 parts; The anti-fatigue agent is selected from a terpolymer composed of acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, and sodium p-styrenesulfonate.

2. The polyamide alloy material according to claim 1, characterized in that, The polyamide has a melt flow rate of 1-100 g / 10 min and is tested according to ISO 1133:2005. The polyamide is selected from at least one of PA6, PA11, PA12, PA46, PA56, PA66, PA610, PA612, PA6T, PA9T, PA10T, PA1010, and PA1012, preferably at least one of PA6, PA6T, PA10T, PA612, PA11, and PA12.

3. The polyamide alloy material according to claim 1, characterized in that, The melt flow rate of the terpolymer is 2-30 g / 10 min, the testing standard is ISO 1133:2005, and the testing conditions are 190℃ and 5 kg.

4. The polyamide alloy material according to claim 1, characterized in that, The repeating unit structure of the terpolymer is: (acrylamide) m (2-Acrylamido-2-methyl-1-propanesulfonic acid) n (Sodium p-styrenesulfonate) k The total molar number of all structural units in the copolymer is 100%, and the ratio of m:n:k is (50-85):(10-30):(5-20).

5. The polyamide alloy material according to claim 1, characterized in that, The anti-fatigue synergist is selected from trisodium trithiocyanate.

6. The polyamide alloy material according to claim 1, characterized in that, The product also includes 0.01-40 parts by weight of filler, wherein the filler is selected from at least one of calcium carbonate, talc, wollastonite, kaolin, mica, glass microspheres, glass fiber, and carbon fiber.

7. The polyamide alloy material according to claim 1, characterized in that, The product also includes 0.01-3 parts by weight of additives; the additives are preferably selected from at least one of the following: heat stabilizers, light stabilizers, antioxidants, lubricants, release agents, antistatic agents, plasticizers, nucleating agents, rheology modifiers, filler dispersants, flame retardants, toughening agents, compatibilizers, colorants, antibacterial agents, anti-sticking agents, anti-caking agents, matting agents, coupling agents, metal passivators, odor absorbers, and mildew inhibitors, preferably at least one of antioxidants or lubricants.

8. A method for preparing the polyamide alloy material according to any one of claims 1-7, characterized in that, The process includes the following steps: mixing all components evenly according to the specified ratio, followed by melt blending, extrusion, and granulation.

9. The application of the polyamide alloy material according to any one of claims 1-7, characterized in that, Used to manufacture flexible polyamide alloy parts.

10. A flexible polyamide alloy component, characterized in that, The polyamide alloy material comprising any one of claims 1-7.

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