High-molecular high-strength composite resin wear-resistant environment-friendly material

Abstract

The invention discloses a high-molecular high-strength composite resin wear-resistant environment-friendly material, and relates to a high-molecular material and application thereof, in particular to a high-molecular composite resin material with excellent wear resistance, high mechanical strength, excellent environment-friendly performance and self-repairing capability. The high-molecular high-strength composite resin wear-resistant environment-friendly material is prepared from the following raw materials in parts by weight: 40-60 parts of bio-based epoxy resin; 10 to 20 parts of surface modified aramid chopped fiber; 2 to 5 parts of nano silicon dioxide; 8-12 parts of a polyimide end-sealed modified phenol-free curing agent; 5 to 15 parts of a biomass-based elastic toughening agent; 3-10 parts of a natural functional mineral filler; 2-6 parts of a microcapsule self-repairing agent; and 0.5 to 1.5 parts of a bio-based catalytic promoter. The high-molecular composite resin material has excellent wear resistance, high mechanical strength, excellent environmental protection performance and self-repairing capability, is suitable for occasions with high requirements on wear resistance and environmental friendliness, such as heavy-duty machinery, bridge protection layers, mine conveying equipment, rail traffic parts and the like, and is stable in performance and relatively environment-friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of new polymer materials, in particular to a wear-resistant and environmentally friendly polymer high-strength composite resin material. Background Art

[0002] Polymer high-strength composite resin anti-wear and environmentally friendly materials are composed of polymer resins with good mechanical properties, such as epoxy, polyester, polyurethane, etc., and reinforcing materials such as glass fiber, carbon fiber, nanofillers, etc. It is a new type of engineering material with high strength, wear resistance, low pollution, and sustainability.

[0003] Existing polymer resin materials often face a trade-off between wear resistance, impact strength, and environmental performance. Some thermosetting resins, such as epoxy resins, offer high strength but poor toughness and often contain harmful volatile organic compounds (VOCs). On the other hand, thermoplastic resins, such as polyamides, offer good toughness but insufficient wear resistance. Therefore, developing a wear-resistant, environmentally friendly polymer composite resin material with high strength is of great practical significance. Summary of the Invention

[0004] In order to solve the above technical deficiencies, the present invention adopts a modified technical solution to provide a high-molecular-weight, high-strength composite resin anti-wear and environmentally friendly material, which is composed of the following raw materials in parts by weight:

[0005] Bio-based epoxy resin: 40-60 parts;

[0006] Surface modified aramid chopped fibers: 10-20 parts;

[0007] Nano silicon dioxide: 2-5 parts;

[0008] Polyimide end-blocking modified phenol-free curing agent: 8-12 parts;

[0009] Biomass-based elastic toughening agent: 5-15 parts;

[0010] Natural functional mineral filler: 3-10 parts;

[0011] Microcapsule self-repairing agent: 2-6 parts;

[0012] Bio-based catalyst promoter: 0.5-1.5 parts.

[0013] As a further preferred embodiment of the present invention, the following raw material amounts are also included, wherein:

[0014] Bio-based epoxy resin: 60 parts;

[0015] Surface modified aramid chopped fibers: 20 parts;

[0016] Nano silicon dioxide: 5 parts;

[0017] Polyimide end-blocking modified phenol-free curing agent: 12 parts;

[0018] Biomass-based elastic toughening agent: 15 parts;

[0019] Natural functional mineral filler: 10 parts;

[0020] Microcapsule self-repairing agent: 6 parts;

[0021] Bio-based catalyst promoter: 1.5 parts.

[0022] As a further preferred embodiment of the present invention, the following raw material amounts are also included, wherein:

[0023] Bio-based epoxy resin: 40 parts;

[0024] Surface modified aramid chopped fibers: 10 parts;

[0025] Nano silicon dioxide: 2 parts;

[0026] Polyimide end-blocking modified phenol-free curing agent: 8 parts;

[0027] Biomass-based elastic toughening agent: 5 parts;

[0028] Natural functional mineral filler: 3 parts;

[0029] Microcapsule self-repairing agent: 2 parts;

[0030] Bio-based catalyst promoter: 0.5 parts.

[0031] As a further preferred embodiment of the present invention, the core material of the microcapsule self-healing agent is a polyurea-epoxy block copolymer, and the shell material is a urea-formaldehyde copolymer, with the ratio being 4:1.

[0032] As a further preferred embodiment of the present invention, the natural functional mineral filler is a mixture of kaolin and sodium montmorillonite in a mass ratio of 1:1, and both are ultrafine powders with a particle size of less than 2 μm.

[0033] As a further preferred embodiment of the present invention, the bio-based catalyst promoter is one of triisobutylamine and 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30).

[0034] As a further preferred embodiment of the present invention, the biomass-based elastic toughening agent is polylactic acid grafted ethylene-methacrylate copolymer, with a grafting rate of about 1.5% and a particle size of 0.5 μm.

[0035] As a further preferred embodiment of the present invention, the method comprises the following steps:

[0036] S1, aramid fiber pretreatment: Aramid chopped fibers were dried at 80°C for 2 hours, then soaked in a 1 wt% silane coupling agent solution (ethanol / water = 95 / 5, pH adjusted to 4.5) for 30 minutes, and then vacuum dried for later use;

[0037] S2, resin matrix dispersion: at a constant temperature of 80 ° C, nano-SiO2 was slowly added to the bio-based epoxy resin using a high shear disperser. After dispersion for 20 minutes, the compound mineral filler and biomass-based elastic toughening agent were added in sequence. The shear stirring was continued for 20 minutes to form a uniform slurry.

[0038] S3, reinforcing component mixing: slowly add the aramid staple fibers and self-repairing microcapsules treated in step 1 to the slurry obtained in step 2, and stir under reduced pressure (-0.08 MPa) for 10 minutes to avoid shear damage to the microcapsule structure;

[0039] S4, preparation of curing system: premix the polyimide end-capping modified curing agent and the tertiary amine accelerator in proportion, add dropwise to the main system, stir for 10 minutes, and finally perform vacuum degassing treatment at 0.1 MPa, 60°C, for 10-15 minutes;

[0040] S5, Molding and Curing: The prepared mixture is injected into a metal mold coated with a release agent, pre-cured at 80°C for 2 hours, then heated to 120°C and kept for 4 hours to complete the curing. After demolding, it is left to stand at room temperature for 24 hours to complete the stress release.

[0041] S6, post-processing and testing: The cured samples are cut to size, polished, and subjected to mechanical properties, wear tests and aging test quality control procedures.

[0042] Beneficial effects

[0043] The present invention uses surface-modified aramid chopped fibers and nano-SiO2 as reinforcing phases, which significantly improves the tensile strength, flexural modulus and impact toughness of the material. The material has good mechanical stability and structural integrity and is suitable for applications under high load or friction environments. The introduction of microcapsule self-healing agents has the function of in-situ self-healing of microcracks, which improves the service life and reliability of the material, effectively repairs micro-damage, and reduces maintenance costs. Bio-based epoxy resins and biomass-based elastic toughening agents are used to replace traditional petrochemical-based materials, reducing carbon footprint, low VOC emission, and being more environmentally friendly. Polyimide end-capped modified phenol-free curing agent is used, which has strong thermal stability and low residual stress after curing. In addition, the material has a good cross-linking structure after pre-curing at 80°C and final curing at 120°C, making it suitable for high-temperature working conditions. DETAILED DESCRIPTION

[0044] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0045] The present invention provides a technical solution: a high-molecular-weight, high-strength composite resin anti-wear and environmentally friendly material, which is composed of the following raw materials in parts by weight:

[0046] Bio-based epoxy resin: 40-60 parts;

[0047] Surface modified aramid chopped fibers: 10-20 parts;

[0048] Nano silicon dioxide: 2-5 parts;

[0049] Polyimide end-blocking modified phenol-free curing agent: 8-12 parts;

[0050] Biomass-based elastic toughening agent: 5-15 parts;

[0051] Natural functional mineral filler: 3-10 parts;

[0052] Microcapsule self-repairing agent: 2-6 parts;

[0053] Bio-based catalyst promoter: 0.5-1.5 parts.

[0054] Microcapsule self-healing agent, the core material is polyurea-epoxy block copolymer, and the shell material is urea formaldehyde copolymer, the ratio is 4:1.

[0055] The natural functional mineral filler is a mixture of kaolin and sodium montmorillonite in a mass ratio of 1:1, and both are ultrafine powders with a particle size of less than 2 μm.

[0056] The bio-based catalyst promoter is one of triisobutylamine and 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30).

[0057] The biomass-based elastic toughening agent is polylactic acid grafted ethylene-methacrylate copolymer, with a grafting rate of about 1.5% and a particle size of 0.5 μm.

[0058] The specific production includes the following steps:

[0059] S1, aramid fiber pretreatment: Aramid chopped fibers were dried at 80°C for 2 hours, then soaked in a 1 wt% silane coupling agent solution (ethanol / water = 95 / 5, pH adjusted to 4.5) for 30 minutes, and then vacuum dried for later use;

[0060] S2, resin matrix dispersion: at a constant temperature of 80 ° C, nano-SiO2 was slowly added to the bio-based epoxy resin using a high shear disperser. After dispersion for 20 minutes, the compound mineral filler and biomass-based elastic toughening agent were added in sequence. The shear stirring was continued for 20 minutes to form a uniform slurry.

[0061] S3, reinforcing component mixing: slowly add the aramid staple fibers and self-repairing microcapsules treated in step 1 to the slurry obtained in step 2, and stir under reduced pressure (-0.08 MPa) for 10 minutes to avoid shear damage to the microcapsule structure;

[0062] S4, preparation of curing system: premix the polyimide end-capping modified curing agent and the tertiary amine accelerator in proportion, add dropwise to the main system, stir for 10 minutes, and finally perform vacuum degassing treatment at 0.1 MPa, 60°C, for 10-15 minutes;

[0063] S5, Molding and Curing: The prepared mixture is injected into a metal mold coated with a release agent, pre-cured at 80°C for 2 hours, then heated to 120°C and kept for 4 hours to complete the curing. After demolding, it is left to stand at room temperature for 24 hours to complete the stress release.

[0064] S6, post-processing and testing: The cured samples are cut to size, polished, and subjected to mechanical properties, wear tests and aging test quality control procedures.

[0065] Example 1:

[0066] Bio-based epoxy resin: 60 parts, surface modified aramid short fiber: 20 parts, nano-silica: 5, polyimide end-capped modified phenol-free curing agent: 12 parts, biomass-based elastic toughening agent (PLA-g-EMA, grafting rate 1.5%, particle size 0.5μm): 15 parts, natural mineral filler (kaolin and montmorillonite 1:1, particle size <2μm): 10 parts, microcapsule self-healing agent (core-shell mass ratio 4:1): 6 parts, bio-based catalytic promoter (triisobutylamine): 1.5 parts.

[0067] The aramid short fibers were dried at 80°C for 2 hours, then immersed in a 1wt% silane coupling agent solution, ethanol / water = 95 / 5, pH adjusted to 4.5, for 30 minutes, taken out and vacuum dried for use; Resin matrix dispersion: Under a constant temperature of 80°C, nano-SiO2 was slowly added to the bio-based epoxy resin using a high shear disperser. After dispersing for 20 minutes, the compound mineral filler and biomass-based elastic toughening agent were added in turn, and shearing and stirring were continued for 20 minutes to form a uniform slurry; Reinforcement component mixing: The treated aramid short fibers and self-repairing microcapsules were slowly added to the resulting slurry, and stirred under reduced pressure conditions of -0.08MPa for 10 minutes to form a uniform slurry. Avoid shear damage to the microcapsule structure; Preparation of curing system: Premix the polyimide end-capping modified curing agent and tertiary amine accelerator in proportion, add them dropwise to the main system, stir for 10 minutes, and finally use vacuum degassing treatment at 0.1MPa, 60℃, for 15 minutes; Molding and curing: Inject the prepared mixture into a metal mold coated with a release agent, pre-curing conditions are 80℃ for 2h, then heat to 120℃ and keep warm for 4h to complete curing, and let it stand at room temperature for 24 hours after demolding to complete stress release; Post-processing and testing: The cured samples are cut to size, polished, and subjected to mechanical properties, wear testing and aging test quality control procedures.

[0068] Example 2:

[0069] Bio-based epoxy resin: 50 parts, surface modified aramid chopped fiber: 12 parts, nano-silica: 3, polyimide end-capped modified phenol-free curing agent: 10 parts, biomass-based elastic toughening agent: 10 parts, natural mineral filler: 6 parts, microcapsule self-healing agent: 5 parts, bio-based catalytic promoter (DMP-30): 1.0 part.

[0070] The aramid short fibers were dried at 80°C for 2 hours, then immersed in a 1wt% silane coupling agent solution, ethanol / water = 95 / 5, pH adjusted to 4.5, for 30 minutes, taken out and vacuum dried for use; Resin matrix dispersion: Under a constant temperature of 80°C, nano-SiO2 was slowly added to the bio-based epoxy resin using a high shear disperser. After dispersing for 20 minutes, the compound mineral filler and biomass-based elastic toughening agent were added in turn, and shearing and stirring were continued for 20 minutes to form a uniform slurry; Reinforcement component mixing: The treated aramid short fibers and self-repairing microcapsules were slowly added to the resulting slurry, and stirred under reduced pressure conditions of -0.08MPa for 10 minutes to form a uniform slurry. Avoid shear damage to the microcapsule structure; Preparation of curing system: Premix the polyimide end-capping modified curing agent and tertiary amine accelerator in proportion, add them dropwise to the main system, stir for 10 minutes, and finally use vacuum degassing treatment at 0.1MPa, 60℃, for 12 minutes; Molding and curing: Inject the prepared mixture into a metal mold coated with a release agent, pre-curing conditions are 80℃ for 2h, then heat to 120℃ and keep warm for 4h to complete curing, and let it stand at room temperature for 24 hours after demolding to complete stress release; Post-processing and testing: The cured samples are cut to size, polished, and subjected to mechanical properties, wear testing and aging test quality control procedures.

[0071] Example 3

[0072] Bio-based epoxy resin: 40 parts; surface modified aramid chopped fiber: 10 parts; nano-silica: 2-5 parts; polyimide end-capped modified phenol-free curing agent: 8 parts; biomass-based elastic toughening agent: 5 parts; natural functional mineral filler: 3 parts; microcapsule self-healing agent: 2 parts; bio-based catalytic promoter: 0.5.

[0073] The aramid short fibers were dried at 80°C for 2 hours, then immersed in a 1wt% silane coupling agent solution, ethanol / water = 95 / 5, pH adjusted to 4.5, for 30 minutes, taken out and vacuum dried for use; Resin matrix dispersion: Under a constant temperature of 80°C, nano-SiO2 was slowly added to the bio-based epoxy resin using a high shear disperser. After dispersing for 20 minutes, the compound mineral filler and biomass-based elastic toughening agent were added in turn, and shearing and stirring were continued for 20 minutes to form a uniform slurry; Reinforcement component mixing: The treated aramid short fibers and self-repairing microcapsules were slowly added to the resulting slurry, and stirred under reduced pressure conditions of -0.08MPa for 10 minutes to form a uniform slurry. Avoid shear damage to the microcapsule structure; Preparation of curing system: Premix the polyimide end-capping modified curing agent and tertiary amine accelerator in proportion, add them dropwise to the main system, stir for 10 minutes, and finally use vacuum degassing treatment at 0.1MPa, 60℃, for 10 minutes; Molding and curing: Inject the prepared mixture into a metal mold coated with a release agent, pre-curing conditions are 80℃ for 2h, then heat to 120℃ and keep warm for 4h to complete curing. After demolding, let it stand at room temperature for 24 hours to complete stress release; Post-processing and testing: The cured samples are cut to size, polished, and subjected to mechanical properties, wear testing and aging test quality control procedures.

[0074] The performance test results of the embodiment are shown in the following table:

[0075]

[0076] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention. Therefore, the embodiments should be regarded as illustrative and non-restrictive in all respects. The scope of the present invention is defined by the appended claims rather than the foregoing description, and it is intended that all changes that come within the meaning and range of equivalents of the claims be included therein.

[0077] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A high-molecular-weight, high-strength composite resin anti-wear and environmentally friendly material, characterized by: It consists of the following raw materials in parts by weight: Bio-based epoxy resin: 40-60 parts; Surface modified aramid chopped fibers: 10-20 parts; Nano silicon dioxide: 2-5 parts; Polyimide end-blocking modified phenol-free curing agent: 8-12 parts; Biomass-based elastic toughening agent: 5-15 parts; Natural functional mineral filler: 3-10 parts; Microcapsule self-repairing agent: 2-6 parts; Bio-based catalyst promoter: 0.5-1.5 parts.

2. The high-molecular-weight, high-strength composite resin anti-wear and environmentally friendly material according to claim 1, characterized in that: The following raw materials are also included, among which, Bio-based epoxy resin: 60 parts; Surface modified aramid chopped fibers: 20 parts; Nano silicon dioxide: 5 parts; Polyimide end-blocking modified phenol-free curing agent: 12 parts; Biomass-based elastic toughening agent: 15 parts; Natural functional mineral filler: 10 parts; Microcapsule self-repairing agent: 6 parts; Bio-based catalyst promoter: 1.5 parts.

3. The high-molecular-weight, high-strength composite resin anti-wear and environmentally friendly material according to claim 1, characterized in that: The following raw materials are also included, among which, Bio-based epoxy resin: 40 parts; Surface modified aramid chopped fibers: 10 parts; Nano silicon dioxide: 2 parts; Polyimide end-blocking modified phenol-free curing agent: 8 parts; Biomass-based elastic toughening agent: 5 parts; Natural functional mineral filler: 3 parts; Microcapsule self-repairing agent: 2 parts; Bio-based catalyst promoter: 0.5 parts.

4. The high-molecular-weight, high-strength composite resin anti-wear and environmentally friendly material according to claim 1, characterized in that: The microcapsule self-repairing agent has a core material of polyurea-epoxy block copolymer and a shell material of urea-formaldehyde copolymer, with the ratio being 4:

1.

5. The high-molecular-weight, high-strength composite resin anti-wear and environmentally friendly material according to claim 1, characterized in that: The natural functional mineral filler is a mixture of kaolin and sodium montmorillonite in a mass ratio of 1:1, and both are ultrafine powders with a particle size of less than 2 μm.

6. The high-molecular-weight, high-strength composite resin anti-wear and environmentally friendly material according to claim 1, characterized in that: The bio-based catalyst promoter is one of triisobutylamine and 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30).

7. The high-molecular-weight, high-strength composite resin anti-wear and environmentally friendly material according to claim 1, characterized in that: The biomass-based elastic toughening agent is a polylactic acid grafted ethylene-methacrylate copolymer, with a grafting rate of about 1.5% and a particle size of 0.5 μm.

8. The method for preparing a high molecular weight, high strength composite resin anti-wear and environmentally friendly material according to claim 1, characterized in that: The following steps are included: S1, aramid fiber pretreatment: Aramid chopped fibers were dried at 80°C for 2 hours, then soaked in a 1 wt% silane coupling agent solution (ethanol / water = 95 / 5, pH adjusted to 4.5) for 30 minutes, and then vacuum dried for later use; S2, resin matrix dispersion: at a constant temperature of 80 ° C, nano-SiO2 was slowly added to the bio-based epoxy resin using a high shear disperser. After dispersion for 20 minutes, the compound mineral filler and biomass-based elastic toughening agent were added in sequence. The shear stirring was continued for 20 minutes to form a uniform slurry. S3, reinforcing component mixing: slowly add the aramid staple fibers and self-repairing microcapsules treated in step 1 to the slurry obtained in step 2, and stir under reduced pressure (-0.08 MPa) for 10 minutes to avoid shear damage to the microcapsule structure; S4, preparation of curing system: premix the polyimide end-capping modified curing agent and the tertiary amine accelerator in proportion, add dropwise to the main system, stir for 10 minutes, and finally perform vacuum degassing treatment at 0.1 MPa, 60°C, for 10-15 minutes; S5, Molding and Curing: The prepared mixture is injected into a metal mold coated with a release agent, pre-cured at 80°C for 2 hours, then heated to 120°C and kept for 4 hours to complete the curing. After demolding, it is left to stand at room temperature for 24 hours to complete the stress release. S6, post-processing and testing: The cured samples are cut to size, polished, and subjected to mechanical properties, wear tests and aging test quality control procedures.

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