Long-carbon-chain nylon low-density glass fiber reinforced material and preparation method thereof

Abstract

The invention belongs to the field of high polymer materials, and particularly relates to a long-carbon-chain nylon low-density glass fiber reinforced material and a preparation method thereof. The long-carbon-chain nylon low-density glass fiber reinforced material provided by the invention is prepared from the following raw materials in parts by mass: 65 to 80 parts of PA12 resin, 0.1 to 0.3 part of a lubricating agent, 0.1 to 0.3 part of a dispersing agent, 0.3 to 0.5 part of a light stabilizer, 5 to 20 parts of hollow glass beads, 10 to 25 parts of glass fibers and 0.1 to 1 part of an antioxidant. The long-carbon-chain nylon low-density glass fiber reinforced material prepared by the invention has low density and excellent mechanical properties, and the actual use effect of the product is excellent.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and specifically relates to a long carbon chain nylon low-density glass fiber reinforced material and a preparation method thereof. Background Art

[0002] In the fields of machinery and aerospace, there is an increasing demand for high-performance composite materials, especially materials with both high strength and low density. Although traditional long-chain nylon materials have good flexibility and chemical resistance, their relatively high density limits their application in lightweight design. For example, Chinese patent CN115960409B discloses a continuous glass fiber reinforced high-density polyethylene / nylon 12 alloy prepreg tape, the raw materials of which include high-density polyethylene, PA12, continuous glass fiber, compatibilizer, antioxidant and toughening agent, and the density of the product is greater than 1.5g / cm 3 .

[0003] Glass fiber reinforced nylon materials can significantly improve their rigidity and strength, but pure glass fiber reinforced nylon still suffers from high density, making it unsuitable for weight-sensitive applications. Furthermore, existing nylon composites on the market often sacrifice some mechanical properties when reducing density, making it difficult to achieve a balance between high strength and low density.

[0004] Therefore, developing a high-performance material that can significantly reduce density while maintaining or even improving mechanical properties has become a technical problem that urgently needs to be solved in the industry. Summary of the Invention

[0005] In order to solve the above technical problems, the first aspect of the present invention provides a long carbon chain nylon low-density glass fiber reinforced material, the raw materials for its preparation, calculated by mass, include: 65-80 parts of PA12 resin, 0.1-0.3 parts of lubricant, 0.1-0.3 parts of dispersant, 0.3-0.5 parts of light stabilizer, 5-20 parts of hollow glass microspheres, 10-25 parts of glass fiber, and 0.1-1 parts of antioxidant.

[0006] As an practicable case, the density of the PA12 resin is 1.0-1.1 g / cm 3 , the tensile modulus is 1600-2100MPa.

[0007] Furthermore, the brand of the PA12 resin is L2000 or UBESTA3012U.

[0008] The present invention selects PA12 rather than PA66 as the base material, mainly because PA12 resin has more advantages in flexibility, chemical resistance and processing performance. PA12 has a lower density, which helps to achieve lightweight materials. At the same time, the chemical resistance of PA12 enables it to maintain stable performance when exposed to various chemicals, so it can also be used normally in complex chemical environments. At the same time, PA12 has better flexibility, with an elongation at break of about 50%, which is significantly higher than the 30% of PA66. This makes it more advantageous when bearing impact loads and is not easy to break. In addition, PA12 exhibits better toughness in low temperature environments, and its glass transition temperature is about -40°C, which is lower than about -30°C of PA66. This allows PA12 to maintain good flexibility and impact strength under low temperature conditions. At the same time, the present invention selects a density of 1.0-1.1g / cm 3 PA12 resin with a tensile modulus of 1600-2100MPa achieves the optimal balance between lightweight and strength. This density makes the material lighter and adapts to the synergistic effect of nylon matrix, glass fiber and hollow glass microspheres to achieve improved product strength, rigidity and toughness.

[0009] As an implementable case, the lubricant includes: one or more of ethylene bisstearamide, polyethylene wax, zinc stearate, calcium stearate, erucamide, oleamide, stearic acid or oleic acid.

[0010] Furthermore, the lubricant is ethylene bisstearamide, purchased from Kao Group.

[0011] The present invention selects ethylene bisstearamide (EBS) as a lubricant primarily due to its compatibility with PA12 resin L2000 and improved processing performance. EBS's excellent lubricity significantly reduces friction between the PA12 resin matrix and the glass fibers and hollow glass microspheres, improving processing fluidity, enabling more uniform blending and extrusion, and reducing energy consumption and equipment wear. It also increases demolding speed, reduces surface defects, enhances the tensile strength and impact strength of the material, and synergizes with other additives to comprehensively enhance material performance.

[0012] The present invention does not further limit the components of the dispersant. Any dispersing aid that can improve the mixing uniformity of the components, enhance the stability of the material, enhance the mechanical properties, improve the processing performance and improve the surface quality can be used. The dispersant specifically selected in the present invention is brand 1507, which is purchased from Brüggemann Chemical Co., Ltd. After using the 1507 dispersant, the overall performance and processing efficiency of the long carbon chain nylon low-density glass fiber reinforced material are significantly improved.

[0013] As an implementable case, the light stabilizer includes one or more of a benzotriazole light stabilizer, a triazine light stabilizer, and a hindered amine light stabilizer.

[0014] As an implementable case, the brands of the benzotriazole light stabilizer include: one or more of Tinuvin 1130, Tinuvin 234, Tinuvin 328, Tinuvin 326, Tinuvin 384, Tinuvin 171, Tinuvin 900, Tinuvin 571, and Tinuvin 928.

[0015] As an implementable case, the brands of the triazine light stabilizer include: one or more of Tinuvin 400, Tinuvin 477, Tinuvin 405, and Tinuvin 479.

[0016] As an implementable case, the brands of the hindered amine light stabilizer include: one or more of Tinuvin 770, Tinuvin 292, Tinuvin 123, Tinuvin 144, and Tinuvin 152.

[0017] Furthermore, the brand of the light stabilizer is Tinuvin 234, purchased from BASF AG.

[0018] In the present invention, a light stabilizer is selected for use in long-carbon-chain nylon low-density glass fiber reinforced materials. Its main function is to inhibit or slow down the aging process of the product in a light radiation environment. In actual use, the product will be exposed to various light sources. The energy of light will trigger photochemical reactions of components such as nylon resin, resulting in deterioration of product performance, such as decreased tensile strength and flexural strength, discoloration and brittleness of the appearance. Light stabilizers can absorb, transfer or quench ultraviolet energy, preventing the breakage and degradation of polymer molecular chains, so that the product can still maintain good physical properties and appearance quality after long-term light exposure, extending the service life of the product and ensuring its stable function in different light environments.

[0019] As an implementable case, the particle size of the hollow glass microspheres is 40-50 μm.

[0020] Furthermore, the hollow glass microspheres are of brand i6m or HL50.

[0021] Hollow glass microspheres have a hollow structure and a very low density of 0.1-0.6g / cm 3When added to long-chain nylon, low-density glass fiber-reinforced materials, it can effectively replace some high-density PA12 resin or glass fiber, significantly reducing the overall weight of the product while maintaining its structural integrity. In terms of physical properties, hollow glass microspheres can disperse stress. When the product is subjected to external forces, the hollow structure can buffer energy, improving performance indicators such as tensile strength, flexural strength, and notched impact strength, thereby enhancing its durability and reliability. In terms of chemical properties, hollow glass microspheres have excellent chemical stability. During the preparation of long-chain nylon, glass fiber-reinforced products, they will not chemically react with other raw materials, ensuring the stability of the product's chemical properties and enabling normal use in different chemical environments.

[0022] Furthermore, the hollow glass microspheres selected in this application have a particle size of 40-50 μm, which allows for uniform dispersion within the material, avoiding stress concentration points that would occur with larger particles and reduce product strength, and preventing agglomeration that would occur with smaller particles and affect the reinforcement effect. Furthermore, limiting their usage to 5-20 parts per part reduces product density while dispersing stress due to the hollow structure, improving toughness and ensuring a lightweight product while maintaining excellent mechanical properties to meet practical application requirements.

[0023] As an implementable case, the length of the glass fiber is 3-5 mm.

[0024] Furthermore, the length of the glass fiber is 3 mm, and the brand is 301HP or 568H.

[0025] The glass fiber of 3mm length selected in the present invention can be evenly dispersed in the product, effectively enhancing the mechanical properties of the product. As a reinforcing material, the length of the glass fiber affects the stress transfer efficiency. The 3mm length enables it to be tightly combined with the PA12 resin, and when the product is subjected to external force, it can efficiently transfer stress, thereby improving the tensile strength, bending strength and bending modulus of the product. If the length is too short, the contact area between the glass fiber and the resin is small, the stress transfer effect is poor, and the reinforcement effect is not obvious; if the length is too long, agglomeration is likely to occur, forming defects inside the product, reducing the impact performance of the product, and causing the product to have a rough appearance.

[0026] As an implementable case, the antioxidant includes a hindered phenol antioxidant or a phosphite antioxidant.

[0027] As an implementable case, the brands of the hindered phenol antioxidant include: one or more of antioxidant 1010, antioxidant 1076, antioxidant 2246 or antioxidant 1098.

[0028] Furthermore, the brand of the antioxidant is antioxidant 1098.

[0029] A second aspect of the present invention provides a method for preparing a long carbon chain nylon low-density glass fiber reinforced material, comprising:

[0030] S1. Add PA12 resin, lubricant, dispersant, light stabilizer, and antioxidant into a mixer and pre-mix to obtain a mixture;

[0031] S2. Add the hollow glass microspheres and the mixture into a twin-screw extruder, perform blending and extrusion, strip drawing, cooling, drying, and pelletizing to obtain a long carbon chain nylon low-density glass fiber reinforced material.

[0032] Furthermore, the preparation method of the long carbon chain nylon low-density glass fiber reinforced material comprises:

[0033] S1. Add PA12 resin, lubricant, dispersant, light stabilizer, and antioxidant into a mixer and pre-mix to obtain a mixture;

[0034] S2, adding hollow glass microspheres to the No. 2 side feed scale of the extruder;

[0035] S3. Add the mixture to the No. 1 main feed loss-in-weight scale, add the glass fiber to the No. 3 side feed loss-in-weight scale, then continuously open the main feed loss-in-weight scale and the side feed loss-in-weight scale, add the mixture to the twin-screw extruder, and obtain the long carbon chain nylon low-density glass fiber reinforced material through blending and extrusion, belt drawing, cooling, drying, and pelletizing.

[0036] As an implementable case, in the step S3, the temperature of the blending extrusion is 240 to 250°C, the screw speed is 300 to 400 rpm, and the vacuum degree is -0.1 to -0.05 MPa.

[0037] Beneficial effects

[0038] (1) The present invention achieves a lightweight design of the product by introducing hollow glass microspheres into the long carbon chain nylon low-density glass fiber reinforced material, effectively reducing the density of the material itself. The density of the long carbon chain nylon low-density glass fiber reinforced material can reach 1.0g / cm 3 the following.

[0039] (2) Despite the reduced density, the physical properties of the long carbon chain nylon low-density glass fiber reinforced material provided by the present invention, such as tensile strength, flexural strength and flexural modulus, remain at a high level. The tensile strength of the product is greater than 100 MPa, and the flexural strength is greater than 165 MPa.

[0040] (3) In the present invention, after adding an appropriate amount of hollow glass microspheres and glass fiber, the product can still maintain good toughness without significantly sacrificing the impact resistance of the product. The notched impact strength can reach 20kJ / m 2Therefore, the product is not easily damaged when subjected to external impact, which broadens the application range of the product.

[0041] (IV) The present invention adopts a specific raw material combination and processing technology, premixes PA12 resin with various additives, and then blends and extrudes it with glass fiber, hollow glass microspheres, etc. in a twin-screw extruder, and determines appropriate process parameters such as extrusion temperature, screw speed and vacuum degree, so that the entire production process can proceed smoothly, ensuring the quality stability of the product, and improving production efficiency, which is conducive to large-scale industrial production.

[0042] (5) Taking into account various factors such as the density, mechanical properties and processing performance of the product, the present invention achieves the optimal balance between low density and high rigidity, high strength, high toughness and good processing performance; the balance of comprehensive performance enables the product to meet the dual needs of lightweight materials and high performance in different scenarios in many application fields, such as automobiles, electronics, aerospace, etc., and has high market competitiveness and application value. DETAILED DESCRIPTION

[0043] Example 1

[0044] The first aspect of this example provides a long carbon chain nylon low-density glass fiber reinforced material, the raw materials for its preparation are, in parts by mass, specifically: 70 parts of PA12 resin, 0.1 parts of lubricant, 0.3 parts of dispersant, 0.3 parts of light stabilizer, 5 parts of hollow glass microspheres, 25 parts of glass fiber, and 0.2 parts of antioxidant.

[0045] The PA12 resin is of the brand L2000, purchased from Wanhua Chemical.

[0046] The lubricant is ethylene bisstearamide, purchased from Kao Group.

[0047] The dispersant is of brand 1507, purchased from Brueggemann Chemical Co., Ltd.

[0048] The light stabilizer is Tinuvin 234, purchased from BASF.

[0049] The hollow glass microspheres have a specification of 40-50 μm, a brand name of i6m, and are purchased from 3M Company of the United States.

[0050] The glass fiber has a length of 3 mm, a brand of 301HP, and is purchased from Chongqing Composite Materials International Co., Ltd.

[0051] The brand of the antioxidant is antioxidant 1098, which was purchased from BASF.

[0052] The second aspect of this example provides a method for preparing a long carbon chain nylon low-density glass fiber reinforced material, specifically:

[0053] S1. Add PA12 resin, lubricant, dispersant, light stabilizer, and antioxidant into a mixer and pre-mix to obtain a mixture;

[0054] S2, add the hollow glass microspheres to the No. 2 side feed scale of the extruder,

[0055] S3. Add the mixture to the No. 1 main feed loss-in-weight scale, add the glass fiber to the No. 3 side feed loss-in-weight scale, then continuously open the main feed loss-in-weight scale and the side feed loss-in-weight scale, add the mixture to the twin-screw extruder, and obtain a long carbon chain nylon low-density glass fiber reinforced material through blending and extrusion, strip drawing, cooling, drying, and pelletizing; wherein the blending and extrusion temperature is 245°C, the screw speed is 350rpm, and the vacuum degree is -0.07MPa.

[0056] Example 2

[0057] The specific implementation method of this example is the same as that of Example 1, except that the raw materials are prepared in parts by mass, specifically: 70 parts of PA12 resin, 0.1 parts of lubricant, 0.3 parts of dispersant, 0.3 parts of light stabilizer, 10 parts of hollow glass microspheres, 20 parts of glass fiber, and 0.2 parts of antioxidant.

[0058] Example 3

[0059] The specific implementation method of this example is the same as that of Example 1, except that the raw materials are prepared in parts by mass, specifically: 70 parts of PA12 resin, 0.1 parts of lubricant, 0.3 parts of dispersant, 0.3 parts of light stabilizer, 20 parts of hollow glass microspheres, 10 parts of glass fiber, and 0.2 parts of antioxidant.

[0060] Example 4

[0061] The specific implementation of this example is the same as that of Example 3, except that the hollow glass microspheres are replaced with ordinary glass microspheres (model: iM16K, supplied by 3M Company) of equal mass.

[0062] Example 5

[0063] The specific implementation of this example is the same as that of Example 3, except that the PA12 resin is replaced with an equal mass portion of PA66 resin; wherein the PA66 resin model is EPR27 (commonly available on the market).

[0064] Example 6

[0065] The specific implementation method of this example is the same as that of Example 3, except that the preparation raw materials do not include glass fiber. The preparation raw materials are calculated by weight as follows: 70 parts of PA12 resin, 0.1 parts of lubricant, 0.3 parts of dispersant, 0.3 parts of light stabilizer, 30 parts of hollow glass microspheres, and 0.2 parts of antioxidant.

[0066] Example 7

[0067] The specific implementation of this example is the same as that of Example 3, except that the brand of the PA12 resin is replaced with UBESTA3012U, which is purchased from Ube Chemicals Co., Ltd. of Japan.

[0068] Example 8

[0069] The specific implementation of this example is the same as that of Example 3, except that the brand of the glass fiber is replaced with 568H, which is purchased from Qingdao Shanchuan Materials Co., Ltd.; wherein the length of the 568H glass fiber is 3 mm.

[0070] Example 9

[0071] The specific implementation of this example is the same as that of Example 3, except that the brand of the hollow glass microspheres is replaced with HL50, which is purchased from Zhengzhou Shenglait Hollow Microsphere New Materials Co., Ltd.; wherein the particle size of HL50 is 50 μm.

[0072] Example 10

[0073] The specific implementation of this example is the same as that of Example 3, except that the raw materials are prepared in parts by mass as follows: 60 parts of PA12 resin, 0.1 parts of lubricant, 0.3 parts of dispersant, 0.3 parts of light stabilizer, 30 parts of

[0074] Hollow glass microspheres, 10 parts glass fiber, 0.2 parts antioxidant.

[0075] Example 11

[0076] The specific implementation of this example is the same as that of Example 3, except that the raw materials are prepared in parts by mass as follows: 70 parts of PA12 resin, 0.1 parts of lubricant, 0.3 parts of dispersant, 0.3 parts of light stabilizer, 30 parts of

[0077] Glass fiber, 0.2 parts antioxidant.

[0078] Performance evaluation

[0079] Test sample: long carbon chain nylon low-density glass fiber reinforced material prepared in Examples 1-11.

[0080] Test items:

[0081] 1. Tensile strength (MPa): Refer to ASTM D638-2014;

[0082] 2. Flexural strength (MPa): Refer to ASTM D790-2007;

[0083] 3. Flexural modulus (MPa): refer to ASTM D790-2007;

[0084] 4. Notched impact strength (kJ / m 2 ): Refer to ASTM D756-1993.

[0085] The experimental results are shown in Table 1.

[0086] Table 1

[0087]

[0088]

[0089] From the experimental data in Table 1, it can be seen that the density of the long carbon chain nylon low-density glass fiber reinforced material provided by the present invention is less than 0.9 g / cm 3 , while the tensile strength is greater than 100MPa, the flexural strength is greater than 165MPa, the flexural modulus is greater than 5000MPa, and the notched impact strength is greater than 20kJ / m 2 , while ensuring low density and excellent mechanical properties, the product has a wide range of practical applications.

[0090] In Example 4, since the hollow glass microspheres were replaced with ordinary glass microspheres in equal parts by mass, the density of the product was increased, but the notched impact strength was significantly reduced.

[0091] In Example 5, the density of the product is improved because the PA12 resin is replaced with an equal mass portion of PA66 resin.

[0092] In Example 6, since glass fiber is not added, the density and mechanical properties of the product are significantly affected, and the practicality is reduced.

[0093] In Example 10, since the amount of PA12 resin added is small and the amount of hollow glass microspheres added is large, the tensile strength, flexural strength, flexural modulus, and notched impact strength of the product will all decrease.

[0094] In Example 11, since hollow glass microspheres are not added but glass fibers are added in excess, the density of the product is significantly improved.

Claims

1. A long carbon chain nylon low density glass fiber reinforced material, characterized in that: The raw materials for preparation include, by weight, 65-80 parts of PA12 resin, 0.1-0.3 parts of lubricant, 0.1-0.3 parts of dispersant, 0.3-0.5 parts of light stabilizer, 5-20 parts of hollow glass microspheres, 10-25 parts of glass fiber, and 0.1-1 parts of antioxidant.

2. The long carbon chain nylon low density glass fiber reinforced material according to claim 1, characterized in that: The lubricant comprises one or more of ethylene bisstearamide, polyethylene wax, zinc stearate, calcium stearate, erucamide, oleamide, stearic acid or oleic acid.

3. The long carbon chain nylon low density glass fiber reinforced material according to claim 1, characterized in that: The light stabilizer includes one or more of benzotriazole light stabilizers, triazine light stabilizers or hindered amine light stabilizers.

4. The long carbon chain nylon low density glass fiber reinforced material according to claim 3, characterized in that: The brands of the benzotriazole light stabilizers include one or more of Tinuvin 1130, Tinuvin 234, Tinuvin 328, Tinuvin 326, Tinuvin 384, Tinuvin 171, Tinuvin 900, Tinuvin 571 or Tinuvin 928.

5. The long carbon chain nylon low density glass fiber reinforced material according to claim 1, characterized in that: The density of the PA12 resin is 1.0-1.1 g / cm 3 , the tensile modulus is 1600-2100MPa.

6. The long carbon chain nylon low density glass fiber reinforced material according to claim 1, characterized in that: The particle size of the hollow glass microspheres is 40-50 μm.

7. The long carbon chain nylon low density glass fiber reinforced material according to claim 1, characterized in that: The length of the glass fiber is 3-5 mm.

8. The long carbon chain nylon low density glass fiber reinforced material according to any one of claims 1 to 7, characterized in that: The antioxidant includes hindered phenol antioxidant or phosphite antioxidant.

9. A method for preparing a long carbon chain nylon low-density glass fiber reinforced material according to any one of claims 1 to 8, characterized in that: include: S1. Add PA12 resin, lubricant, dispersant, light stabilizer, and antioxidant into a mixer and pre-mix to obtain a mixture; S2. Add the hollow glass microspheres and the mixture into a twin-screw extruder, perform blending and extrusion, strip drawing, cooling, drying, and pelletizing to obtain a long carbon chain nylon low-density glass fiber reinforced material.

10. The method for preparing a long carbon chain nylon low-density glass fiber reinforced material according to claim 9, characterized in that: In the step S3, the temperature of the blending extrusion is 240 to 250° C., the screw speed of the twin-screw extruder is 300 to 400 rpm, and the vacuum degree is -0.1 to -0.05 MPa.

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