Polyamide composition as well as preparation method and application thereof

Abstract

The invention provides a polyamide composition as well as a preparation method and application thereof, and the polyamide composition comprises the following components in parts by weight: 55-60 parts of polyamide, 15-20 parts of hollow microspheres, 10-15 parts of a flexibilizer, 5-8 parts of a compatilizer, 0.5-1 part of an antioxidant, 0.5-1 part of a light stabilizer and 1-1.5 parts of a lubricant. The polyamide composition provided by the invention has low density and high impact performance, solves the problem that the density and the impact performance of the existing polyamide material are difficult to coordinate, and can fully meet the urgent requirements of the industries of automobiles, aerospace, electronics and the like on high-performance materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and in particular relates to a polyamide composition, a preparation method and an application thereof. Background Art

[0002] As an important engineering plastic, polyamide has been widely used in numerous fields, including automotive manufacturing, electronics, sports equipment, and aerospace, thanks to its excellent mechanical properties, wear resistance, chemical resistance, and self-lubrication. However, as various industries continue to demand higher performance from materials, traditional polyamide materials are increasingly unable to meet the density and impact resistance requirements of some specialized applications.

[0003] In the automotive lightweighting process, reducing component weight is crucial for lowering energy consumption, reducing emissions, and improving vehicle performance. The aerospace industry places even stricter demands on low-density materials. Every ounce of weight saved effectively reduces aircraft energy consumption, improving flight efficiency and payload capacity. Furthermore, whether a car is navigating complex road conditions or an aerospace aircraft operates in extreme environments, components are subject to various impacts, requiring materials to possess excellent impact resistance to ensure structural integrity and safety.

[0004] To achieve low-density polyamides, a common approach is to add low-density fillers. However, poor interfacial compatibility between the filler and the polyamide matrix often exists. This leads to premature material failure and a significant decrease in impact performance when subjected to external forces. Furthermore, some toughening methods designed to improve polyamide's impact performance often negatively impact other properties, such as rigidity and dimensional stability. This makes it difficult to achieve a balanced optimization of the material's overall performance by simultaneously achieving low density and high impact performance.

[0005] Therefore, developing a polyamide material and a preparation method thereof that can effectively reduce density and significantly improve impact performance has become a key issue that needs to be urgently addressed in this field. Summary of the Invention

[0006] In response to the shortcomings of the prior art, the present invention provides a polyamide composition, a preparation method, and applications thereof. The polyamide composition provided by the present invention exhibits low density and high impact resistance, resolving the difficulty in balancing density and impact resistance in existing polyamide materials. It can fully meet the urgent demand for high-performance materials in industries such as automotive, aerospace, and electronics.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In one aspect, the present invention provides a polyamide composition comprising the following components in parts by weight:

[0009] 55-60 parts of polyamide, 15-20 parts of hollow microspheres, 10-15 parts of toughening agent, 5-8 parts of compatibilizer, 0.5-1 part of antioxidant, 0.5-1 part of light stabilizer and 1-1.5 parts of lubricant.

[0010] The present invention introduces low-density hollow microspheres as a filler into polyamide, thereby significantly reducing the density of the polyamide composition. Simultaneously, a toughening agent and a compatibilizer are introduced, and the synergistic effect of the two can not only increase the compatibility of the hollow microspheres and the polyamide matrix, but also improve the impact resistance of the polyamide composition. When the polyamide composition is impacted, it can better absorb energy and avoid brittle fracture, thereby greatly improving the reliability and safety of the polyamide composition.

[0011] Not only that, the polyamide composition provided by the present invention has low density and high impact resistance while still retaining high tensile strength and flexural strength, as well as good dimensional stability and chemical stability. It can maintain stable performance under different environmental conditions and meet the requirements of various complex application scenarios.

[0012] In the present invention, the polyamide 55-60 parts can be 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, etc., the hollow microspheres 15-20 parts can be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc., the toughening agent 10-15 parts can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc., the compatibilizer 5-8 parts can be 5 parts , 6 parts, 7 parts, 8 parts, etc., the antioxidant 0.5-1 part can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, etc., the light stabilizer 0.5-1 part can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, etc., the lubricant 1-1.5 parts can be 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, etc.

[0013] Preferably, the polyamide includes polyamide 612, and at least one of polyamide 66, polyamide 12 or polyamide 6.

[0014] Preferably, the polyamide 612 accounts for 15-30% of the total mass of the polyamide, for example, 15%, 16%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, etc.

[0015] In the present invention, by selecting PA612 as part of the polyamide, the density of the obtained polyamide composition can be lowered while also having higher impact resistance.

[0016] Preferably, the hollow microspheres include hollow glass microspheres and / or hollow ceramic microspheres.

[0017] Preferably, the hollow microspheres have a particle size of 2-130 μm, such as 2 μm, 10 μm, 20 μm, 40 μm, 50 μm, 60 μm, 80 μm, 100 μm, 120 μm, 130 μm, etc., a compressive strength of 100-150 MPa, such as 100 MPa, 110 MPa, 120 MPa, 130 MPa, 140 MPa, 150 MPa, etc., and a true density of 0.55-0.65 g / cm 3 , for example 0.55g / cm 3 , 0.56g / cm 3 , 0.58g / cm 3 、0.60g / cm 3 , 0.62g / cm 3 , 0.64g / cm 3 , 0.65g / cm 3 wait.

[0018] The present invention selects hollow microspheres within the above range, which can reduce the density of the polyamide composition as much as possible and improve its impact resistance.

[0019] Preferably, the toughening agent comprises POE-g-MAH and / or EAA-g-MAH, preferably POE-g-MAH.

[0020] Preferably, the compatibilizer comprises PP-g-MAH and / or EPDM-g-MAH, preferably EPDM-g-MAH.

[0021] Preferably, the mass ratio of POE-g-MAH to EPDM-g-MAH is 2:1.

[0022] The present invention selects a specific toughening agent and a compatibilizer, and the two work together to enhance the effectiveness, thereby improving the impact performance of the polyamide composition when more hollow microsphere fillers are introduced.

[0023] Preferably, the antioxidant is selected from any one of Antioxidant 1010, Antioxidant 168 or AddWorks LXR 568, or a combination of at least two thereof, preferably AddWorks LXR 568.

[0024] Preferably, the light stabilizer is selected from any one of light stabilizer 770, ultraviolet absorber UV-531 or BRUGGOLEN L11, or a combination of at least two thereof, preferably BRUGGOLEN L11.

[0025] Preferably, the lubricant is selected from calcium stearate or ethylene bisstearamide (EBS).

[0026] Preferably, a nucleating agent and a silane coupling agent are also included.

[0027] Preferably, the weight portion of the nucleating agent is 0.1-0.2 weight portion, for example, 0.1 weight portion, 0.15 weight portion, 0.2 weight portion, etc.

[0028] Preferably, the nucleating agent is selected from BRUGGOLEN P22.

[0029] Preferably, the weight portion of the silane coupling agent is 0.2-0.5 weight portion, for example, 0.2 weight portion, 0.25 weight portion, 0.3 weight portion, 0.35 weight portion, 0.4 weight portion, 0.45 weight portion, 0.5 weight portion, etc.

[0030] In the present invention, by introducing antioxidants and light stabilizers, the thermal oxidative degradation of the polymer and the generation of undesirable colors can be reduced. At the same time, by matching the nucleating agents, the molding cycle can be shortened, the dimensional stability of the composition can be improved, the post-production shrinkage of the product can be reduced, and stress cracking of the product can be prevented, thereby improving production efficiency.

[0031] Preferably, the silane coupling agent is selected from any one of KH550, KH560 or KH570, or a combination of at least two thereof.

[0032] In a second aspect, the present invention provides a method for preparing the polyamide composition according to the first aspect, the preparation method comprising:

[0033] The components in the formula are mixed, and the mixture is melt-extruded and pelletized in a twin-screw extruder to obtain the polyamide composition.

[0034] Preferably, the mixing temperature is 80-100°C, such as 80°C, 85°C, 90°C, 95°C, 100°C, etc., and the mixing time is 10-20 min, such as 10 min, 12 min, 15 min, 18 min, 20 min, etc.

[0035] Preferably, the parameters of the twin-screw extruder include: zone 1: 200-210°C, for example, 200°C, 202°C, 204°C, 205°C, 206°C, 208°C, 210°C, etc.; zone 2: 220-230°C, for example, 220°C, 222°C, 224°C, 225°C, 226°C, 228°C, 230°C, etc.; zone 3: 240-250°C, for example, 240°C, 242°C, 244°C, 245°C, 246°C, 248°C, 250°C, etc.; zone 4: 250-260°C, for example, 250°C, 252°C, 254°C, 255°C, 256°C, 258°C, 260°C, etc.; zone 5 : 250-260℃, for example, 250℃, 252℃, 254℃, 255℃, 256℃, 258℃, 260℃, etc., Extrusion temperature: 240-250℃, for example, 240℃, 242℃, 244℃, 245℃, 246℃, 248℃, 250℃, etc., Screw speed: 200-300r / min, for example, 200r / min, 210r / min, 220r / min, 230r / min, 240r / min, 250r / min, 260r / min, 270r / min, 280r / min, 290r / min, 300r / min, etc.

[0036] The preparation method provided by the present invention utilizes a conventional twin-screw extruder for melt blending, resulting in a simple and easy-to-control process suitable for large-scale industrial production. Compared with currently available complex processes, the preparation method provided by the present invention can effectively reduce production costs and improve production efficiency, and has promising application prospects.

[0037] Preferably, the screw combination parameters of the twin-screw extruder include: the lead of zones 1-4 is 56-64 mm, for example, 56 mm, 57 mm, 58 mm, 59 mm, 60 mm, 61 mm, 62 mm, 63 mm, 64 mm, etc., dispersed tablets are selected in zones 5-6, and the lead of zones 7-9 is 32-44 mm, for example, 32 mm, 34 mm, 36 mm, 38 mm, 40 mm, 42 mm, 44 mm, etc.

[0038] In the preparation method provided by the present invention, by selecting a specific screw combination, the destruction of the hollow microspheres can be avoided to a great extent. Among them, the large lead plasticizing and conveying is selected in zones 1-4, which can reduce the residence time of the hollow microspheres and avoid the screw from damaging the hollow microspheres. The introduction of dispersible tablets in zones 5-6 can make the toughening agent, compatibilizer and hollow microspheres more evenly distributed. Then, the small lead is used in the compression zone of zones 7-8 to remove small molecules in the material, so that the composition has a higher density.

[0039] Preferably, the preparation method comprises:

[0040] After polyamide and silane coupling agent are mixed, hollow microspheres, toughening agent, compatibilizer, antioxidant, light stabilizer, lubricant and nucleating agent are added and mixed, and the mixture is melt-extruded and pelletized in a twin-screw extruder to obtain the polyamide composition.

[0041] In a third aspect, the present invention provides a use of the polyamide composition as described in the first aspect in automobile manufacturing, electronic appliances, sports equipment or aerospace.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] (1) The present invention greatly reduces the density of the polyamide composition by introducing hollow microspheres. Compared with traditional polyamide materials, the density can be reduced by 15-25% to 0.8-1.0 g / cm 3 ;

[0044] (2) The present invention introduces a toughening agent and a compatibilizer to work synergistically, which can make the material maintain high tensile strength and flexural strength while having better impact resistance. Among them, the cantilever beam notched impact strength is increased by 30-50% compared with traditional polyamide, reaching 10-20kJ / m 2 , tensile strength is 40-60MPa, flexural strength is 60-80MPa;

[0045] (3) The preparation method provided by the present invention is simple and easy to implement, and the preparation method provided by the present invention can avoid the destruction of the hollow microspheres as much as possible, so that the final polyamide composition has a lower density. DETAILED DESCRIPTION

[0046] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0047] Unless otherwise specified, the raw materials involved in the following specific embodiments of the present invention are all conventional materials in the art and can be purchased from commercial products. Some raw material information is as follows:

[0048] Polyamide 66: purchased from Shenma, model PA66 EPR27;

[0049] Polyamide 12: purchased from Aimans, model PA12 TR90;

[0050] Polyamide 612: purchased from Evonik, model number PA612 D16;

[0051] Hollow glass microspheres 1: purchased from Saint-Light Hollow Microsphere New Materials Co., Ltd., model HL60S, particle size 35 μm, compressive strength 124 MPa / 18000 Psi, true density 0.55-0.65 g / cm 3 ;

[0052] Hollow glass microspheres 2: purchased from Henan Conch, model A1000, particle size 85 μm, compressive strength 90 MPa / 12000 Psi, true density 0.65-0.85 g / cm 3 ;

[0053] Hollow ceramic microspheres: purchased from Zhongke Huaxing New Materials, model D4000, particle size 2-130μm, compressive strength 120MPa, true density 0.2-0.76g / cm 3 ;

[0054] POE-g-MAH: purchased from Coase Chemical, model W1A;

[0055] EPDM-g-MAH: purchased from Coase Chemical, model W1P-2;

[0056] PP-g-MAH: purchased from Coase Chemical, model B1;

[0057] EAA-g-MAH: purchased from Arkema, model 4700;

[0058] Examples 1-11, Comparative Examples 1-4

[0059] This embodiment provides a polyamide composition and a preparation method thereof. The formula of the polyamide composition is shown in Table 1-2:

[0060] Table 1

[0061]

[0062]

[0063] Table 2

[0064]

[0065] The preparation method is:

[0066] (1) The polyamide is vacuum dried at 100°C for 6 hours to remove moisture and then mixed with a silane coupling agent (if any);

[0067] (2) placing the hollow glass microspheres, toughening agent, compatibilizer, antioxidant, light stabilizer, lubricant and nucleating agent in a high-speed mixer and mixing at 100° C. for 15 minutes to ensure that all components are fully mixed;

[0068] (3) The mixed materials were added to a twin-screw extruder. The temperature of each section of the twin-screw extruder was set as follows: 210°C for zone 1, 230°C for zone 2, 250°C for zone 3, 260°C for zone 4, and 260°C for zone 5. The die head was set at 250°C. The screw speed was 300 r / min. The screw combination parameters included: the lead of zones 1-4 was (64 / 64, 56 / 56), the dispersed tablets (45 / 5 / 36L, SME / 44) were selected for zones 5-6, and the lead of zones 7-9 was (44 / 44, 32 / 32).

[0069] (4) After the materials are melt-blended and extruded, they are pelletized through a water-cooled pelletizing system to obtain polyamide composition pellets.

[0070] Performance Testing

[0071] The performance tests of the samples provided in the examples and comparative examples were carried out as follows:

[0072] (1) Density: Tested in accordance with ISO 1183-1-2019;

[0073] (2) Izod notched impact strength: Notched impact strength was measured according to ISO 180-2019; notch type: Type A;

[0074] (3) Tensile strength: tested according to ISO 527-2:2012, 1A specimen;

[0075] (4) Flexural strength: tested according to ISO 178, 80 mm * 10 mm * 4 mm specimen;

[0076] The test results are shown in Table 1:

[0077] Table 1

[0078]

[0079]

[0080] It can be seen from the examples and performance tests that the present invention can greatly reduce the density of the polyamide composition while ensuring that it still has excellent impact resistance by introducing hollow microspheres, toughening agents and compatibilizers.

[0081] From the comparison between Example 1 and Examples 3-6, it can be seen that the introduction of a certain amount of PA612 into polyamide can both reduce the density of the material and ensure its impact resistance. From the comparison between Example 1 and Example 7, it can be seen that the introduction of hollow microspheres within the preferred range can ensure that the density is reduced while avoiding the loss of mechanical properties. From the comparison between Example 1 and Examples 8-9, it can be seen that in the present invention, it is preferred to introduce POE-g-MAH and EPDM-g-MAH with a mass ratio of 2:1 as toughening agents and compatibilizers, which has a better effect. From the comparison between Example 1 and Example 10, it can be seen that in the present invention, antioxidants, light stabilizers and nucleating agents are preferably compounded, which can shorten the molding cycle, improve dimensional stability, reduce post-product shrinkage, prevent product stress cracking, and improve production efficiency. From the comparison between Example 1 and Example 12, it can be seen that the present invention can reduce the shear force of the screw by adjusting the screw arrangement and combination, thereby reducing the damage to the hollow glass microspheres and playing a role in reducing density.

[0082] From the comparison between Example 1 and Comparative Examples 1-4, it can be seen that in the composition provided by the present invention, the hollow microspheres, the toughening agent and the compatibilizer are indispensable.

[0083] The applicant declares that the present invention is illustrated by the above-described embodiments, but the present invention is not limited to the above-described embodiments. This does not mean that the present invention must rely on the above-described embodiments in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for raw materials in the present invention, additions of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A polyamide composition, characterized in that In parts by weight, it comprises the following components: 55-60 parts of polyamide, 15-20 parts of hollow microspheres, 10-15 parts of toughening agent, 5-8 parts of compatibilizer, 0.5-1 part of antioxidant, 0.5-1 part of light stabilizer and 1-1.5 parts of lubricant.

2. The polyamide composition according to claim 1, characterized in that The polyamide includes polyamide 612, and at least one of polyamide 66, polyamide 12 or polyamide 6; Preferably, the polyamide 612 accounts for 15-30% of the total mass of the polyamide.

3. The polyamide composition according to claim 1 or 2, characterized in that The hollow microspheres include hollow glass microspheres and / or hollow ceramic microspheres; Preferably, the hollow microspheres have a particle size of 2-130 μm, a compressive strength of 100-150 MPa, and a true density of 0.55-0.65 g / cm 3 .

4. The polyamide composition according to any one of claims 1 to 3, characterized in that The toughening agent includes POE-g-MAH and / or EAA-g-MAH, preferably POE-g-MAH; Preferably, the compatibilizer comprises PP-g-MAH and / or EPDM-g-MAH, preferably EPDM-g-MAH; Preferably, the mass ratio of POE-g-MAH to EPDM-g-MAH is 2:

1.

5. The polyamide composition according to any one of claims 1 to 4, characterized in that The antioxidant is selected from any one of antioxidant 1010, antioxidant 168 or AddWorks LXR 568 or a combination of at least two thereof, preferably AddWorks LXR 568; Preferably, the light stabilizer is selected from any one of light stabilizer 770, ultraviolet absorber UV-531 or BRUGGOLEN L11, or a combination of at least two thereof, preferably BRUGGOLEN L11.

6. The polyamide composition according to any one of claims 1 to 5, characterized in that The lubricant is selected from calcium stearate or ethylene bisstearamide.

7. The polyamide composition according to any one of claims 1 to 6, characterized in that Also included are nucleating agents and silane coupling agents; Preferably, the weight portion of the nucleating agent is 0.1-0.2 weight portion; Preferably, the nucleating agent is selected from BRUGGOLEN P22; Preferably, the weight portion of the silane coupling agent is 0.2-0.5 weight portion; Preferably, the silane coupling agent is selected from any one of KH550, KH560 or KH570, or a combination of at least two thereof.

8. A method for preparing a polyamide composition according to any one of claims 1 to 7, characterized in that: The preparation method comprises: The components in the formula are mixed, and the mixture is melt-extruded and pelletized in a twin-screw extruder to obtain the polyamide composition.

9. The preparation method according to claim 8, characterized in that The mixing temperature is 80-100°C and the mixing time is 10-20 minutes; Preferably, the parameters of the twin-screw extruder include: zone 1: 200-210°C, zone 2: 220-230°C, zone 3: 240-250°C, zone 4: 250-260°C, zone 5: 250-260°C, extrusion temperature: 240-250°C, screw speed: 200-300r / min; Preferably, the screw combination parameters of the twin-screw extruder include: the lead of zones 1-4 is 56-64 mm, dispersed slices are selected in zones 5-6, and the lead of zones 7-9 is 32-44 mm.

10. Use of the polyamide composition according to any one of claims 1 to 7 in automobile manufacturing, electronic appliances, sports equipment or aerospace.

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