Special impregnating compound for basalt fiber reinforced vinyl resin as well as preparation method and application of impregnating compound

Abstract

The invention discloses a special impregnating compound for basalt fiber reinforced vinyl resin as well as a preparation method and application of the special impregnating compound. The impregnating compound is prepared from the following raw materials in percentage by mass: 1 to 2 percent of silane coupling agent, 10 to 20 percent of film-forming agent, 0.3 to 0.7 percent of lubricating agent, 0.15 to 0.25 percent of pH (Potential of Hydrogen) regulator, 0.05 to 0.1 percent of antistatic agent and the balance of water, wherein the film-forming agent is an epoxy resin emulsion film-forming agent, the solid content of the epoxy resin emulsion film-forming agent is 20-40 wt%, and the epoxy equivalent is 100-350 g / equivalent. The impregnating compound is specially used for basalt fiber reinforced vinyl resin, the problem of poor bonding property of basalt fiber and vinyl resin is well solved, the mechanical property of a basalt fiber reinforced vinyl resin composite material can be improved, and the impregnating compound is environment-friendly, convenient to use and easy to scale.

Description

Technical Field

[0001] This invention relates to the field of basalt fiber impregnating agents. More specifically, it relates to a basalt fiber reinforced vinyl ester resin impregnating agent, its preparation method, and its application. Background Technology

[0002] Basalt fiber is a continuous fiber produced by melting basalt rock at a high temperature of approximately 1450-1500℃ and then drawing it at high speed through a platinum-rhodium alloy spinneret. It is one of the four key high-performance fibers being developed in my country. Among all high-tech fibers, it has the lowest energy consumption in production and generates no wastewater, waste gas, waste residue, or toxic substances. It is a typical resource-saving, environmentally friendly, and green high-tech fiber, meeting the requirements of energy conservation and emission reduction policies and a low-carbon economy. Currently, basalt fiber is developing rapidly in China, with numerous local governments and enterprises investing in its production and research. Basalt fiber not only has high mechanical strength but also excellent comprehensive properties such as high-temperature resistance, corrosion resistance, electrical insulation, and flame resistance. Therefore, it is commonly used as a reinforcement in composite materials. Among these applications, basalt fiber-reinforced polymer-based composites are the most widespread, attracting significant attention in aerospace, automotive parts, shipbuilding materials, construction, and electronic products.

[0003] Vinyl ester resin is a thermosetting resin containing carbon-carbon double bonds in its molecule, obtained by heating epoxy resin and methacrylic acid under conditions of additives and diluents. Because vinyl ester resins share some basic chain segments with epoxy resins while retaining the double bond portion of unsaturated polyester resins, they combine the advantages of both. They possess not only the excellent mechanical properties and chemical resistance of epoxy resins but also the easy curing and excellent molding properties of methacrylic acid esters. Therefore, vinyl ester resins have broad application prospects as the resin matrix for advanced polymer-based composite materials.

[0004] However, basalt fiber is an inorganic material with a relatively smooth surface and high chemical inertness. Especially during high-temperature melting, the silanol groups on the fiber surface dehydrate and condense into inactive bridging oxygen bonds, further reducing the active sites. Vinyl resin, on the other hand, is an organic material. The significant difference in polarity between the two makes it difficult to form a strong interfacial bond when they come into contact, and may even lead to voids and cracks. Under these circumstances, stress concentration occurs at the interface when the composite material is subjected to external forces, severely affecting the material's mechanical strength. Therefore, surface modification is necessary to enhance the strength of the two-phase interface. The most common modification method is sizing agent modification, which involves coating the fiber surface with a sizing agent coating composed of film-forming agents, coupling agents, lubricants, and antistatic agents. The sizing agent can fill surface defects, thereby improving the fiber's inherent strength, and also creates an irregular surface, enhancing the mechanical interlocking effect between the basalt fiber and the vinyl resin. Currently, sizing agent coating has become a step in the basalt fiber production process, and the development of various resin-specific sizing agents is key to the development of basalt fiber products.

[0005] Existing sizing agents all use vinyl resins as film-forming agents, which have achieved good modification effects. However, the preparation process of film-forming agents is complicated, the production cost is high and it is difficult to scale up. At the same time, they also use acetone, which is highly toxic and not conducive to environmental protection. Therefore, it is necessary to develop new sizing agents that are easy to formulate and are green and sustainable. Summary of the Invention

[0006] Based on the above facts, the purpose of this invention is to provide a special sizing agent for basalt fiber reinforced vinyl ester resin, its preparation method, and its application. This sizing agent is specifically designed for basalt fiber reinforced vinyl ester resin, effectively solving the problem of poor bonding between basalt fiber and vinyl ester resin. It can improve the mechanical properties of basalt fiber reinforced vinyl ester resin composites, and is environmentally friendly, easy to use, and readily scalable.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] On one hand, the present invention provides a special sizing agent for basalt fiber reinforced vinyl ester resin, wherein the raw materials forming the sizing agent contain the following components by weight percentage:

[0009] 1-2% silane coupling agent, 10-20% film-forming agent, 0.3-0.7% lubricant, 0.15-0.25% pH adjuster, 0.05-0.1% antistatic agent, and the balance being water;

[0010] The film-forming agent is an epoxy resin emulsion film-forming agent, and the solid content of the epoxy resin emulsion film-forming agent is 20-40 wt%, and the epoxy equivalent is 100-350 g / equivalent.

[0011] The main function of epoxy resin emulsion film-forming agents is to match the polarity of basalt fibers and vinyl ester resins, thereby improving their compatibility. In addition, epoxy resin emulsion film-forming agents also protect and reinforce basalt fibers. The epoxy emulsion can penetrate into defects or cracks on the fiber surface, preventing stress concentration under external forces. It also improves fiber bundle cohesion and prevents fiber breakage and fraying.

[0012] Furthermore, the film-forming agent is formed by emulsifying epoxy resin, and the epoxy equivalent of the epoxy resin is 150-300 g / equivalent. By controlling the epoxy equivalent of the epoxy resin, the mechanical properties of the composite material obtained by basalt fiber reinforced vinyl ester resin are improved.

[0013] Furthermore, the epoxy equivalent of the epoxy resin includes, but is not limited to, 150-250 g / equivalent, 200-300 g / equivalent, 250-300 g / equivalent, 250 g / equivalent, etc.

[0014] Furthermore, the film-forming agent is an epoxy acrylate film-forming agent.

[0015] Furthermore, the preparation of the film-forming agent includes the following steps:

[0016] Epoxy acrylate and deionized water are mixed in a mass ratio of 1:2 to 1:4 and stirred until homogeneous to fully disperse the epoxy acrylate and obtain a mixture.

[0017] Add the emulsifier (e.g., polyoxyethylene ether) to the mixture and continue stirring to ensure that the emulsifier is completely dissolved. The mass of the emulsifier should be 5-10% of the mass of the epoxy acrylate.

[0018] Emulsification is performed using a high-shear mixer at a speed of 2000-4000 rpm for 10-20 minutes until a stable emulsion is formed.

[0019] Furthermore, the pH of the emulsion is adjusted to 5-7 using acid or alkali to improve its stability.

[0020] Furthermore, the epoxy equivalent of the epoxy acrylate is 150-300 g / equivalent. Exemplary epoxy acrylates have epoxy equivalents including, but not limited to, 150-250 g / equivalent, 200-300 g / equivalent, 250-300 g / equivalent, 250 g / equivalent, etc.

[0021] Furthermore, the prepared emulsion is cooled to room temperature and then transferred to a sealed container for storage, avoiding direct sunlight and moisture.

[0022] Furthermore, the solid content of the epoxy resin emulsion film-forming agent is 25-35 wt%.

[0023] The film-forming agent prepared by the above method is used to improve the poor bonding between basalt fiber and vinyl resin.

[0024] Furthermore, the silane coupling agent is a vinyl silane coupling agent, or a mixture of a vinyl silane coupling agent and one or more selected from epoxy silane coupling agents and amino silane coupling agents.

[0025] The choice of silane coupling agent directly affects the effect of the impregnating agent on improving the mechanical properties of basalt fiber reinforced vinyl ester resin composites. Specifically, in the technical solution of this invention, the silane coupling agent includes a vinyl silane coupling agent. The alkoxy groups therein can undergo a hydrolysis reaction to generate silanol groups, which further dehydrate and condense with the silanol groups on the surface of the basalt fiber to form Si-O-Si bonds. Meanwhile, the organic groups in the vinyl silane coupling agent can undergo a crosslinking reaction with the vinyl ester resin, resulting in chemical bonding between the basalt fiber and the vinyl ester resin, greatly enhancing the interfacial adhesion.

[0026] Furthermore, the silane coupling agent is a mixture of vinyl silane coupling agent and epoxy silane coupling agent at a mass ratio of 6:(5-8), preferably 6:(5.6-7.2), and more preferably 6:(6-7). Under these conditions, the aforementioned effects of the wetting agent are even better.

[0027] Furthermore, the vinylsilane coupling agent is selected from one or more of A151, A171, A172 and A174.

[0028] Furthermore, the epoxy silane coupling agent is selected from A187 and / or A1871.

[0029] Furthermore, the aminosilane coupling agent is selected from one or more of A1100, A1110, A1120 and A1210.

[0030] Furthermore, the lubricant is a mixture of a nonionic lubricant and a cationic lubricant at a mass ratio of (2.5-4):1. In this case, the resulting wetting agent effectively improves the mechanical properties of the basalt fiber reinforced vinyl ester resin composite.

[0031] Furthermore, the lubricant is a mixture of a nonionic lubricant and a cationic lubricant in a mass ratio of (2.5-3.5):1.

[0032] Furthermore, the nonionic lubricant is selected from one or more of polyoxyethylene ether lubricants, amide lubricants, and ester lubricants.

[0033] Furthermore, the cationic lubricant is selected from one or more of polyoxyethylene amine salt lubricants, quaternary ammonium salt lubricants, and imidazoline lubricants.

[0034] Basalt fiber is made by melting basalt rock at high temperature and then drawing it at high speed through a platinum-rhodium alloy spinneret. Friction is inevitable during the production process. Adding nonionic lubricants can reduce the coefficient of friction and protect the fibers from damage. Cationic wetting agents can also reduce the coefficient of friction and improve the wear resistance of the fibers.

[0035] Furthermore, the pH adjuster is selected from acids. The hydrolysis reaction of silane coupling agents needs to be carried out within a suitable pH range, generally in an acidic environment with a pH of around 3-5. Therefore, acidic substances need to be added to adjust the pH to a suitable value.

[0036] Furthermore, the pH adjuster is selected from organic acids or inorganic acids.

[0037] Furthermore, the pH adjuster is selected from one or more of citric acid, glacial acetic acid, boric acid, and formic acid.

[0038] Furthermore, the antistatic agent is selected from one or more of quaternary ammonium salts, sulfate esters, phosphate esters, and polyethylene glycol derivatives. The addition of the antistatic agent can increase the conductivity of the fiber, reduce static electricity accumulation, and prevent damage caused by charge buildup.

[0039] Furthermore, the raw materials forming the wetting agent, by weight percentage, contain the following components:

[0040] 1.3% silane coupling agent, 15.6% film-forming agent, 0.47% lubricant, 0.22% pH adjuster, 0.07% antistatic agent and the balance being water.

[0041] Furthermore, the raw materials forming the wetting agent, by weight percentage, contain the following components:

[0042] 0.6% vinyl silane coupling agent, 0.7% epoxy silane coupling agent, 15.6% film-forming agent, 0.36% nonionic lubricant, 0.11% cationic lubricant, 0.22% pH adjuster, 0.07% antistatic agent and the balance being water.

[0043] Under the given formulation conditions and the selection of each component, the resulting wetting agent exhibits the best effect in improving the mechanical properties of basalt fiber reinforced vinyl ester resin composites.

[0044] In another aspect, the present invention provides a method for preparing the wetting agent as described above, the method comprising the following steps:

[0045] The film-forming agent, lubricant, pH adjuster, and antistatic agent were diluted with water to obtain aqueous solutions of the film-forming agent, lubricant, pH adjuster, and antistatic agent, respectively.

[0046] The silane coupling agent is hydrolyzed in the presence of an aqueous solution of the pH adjuster and a portion of water to obtain a hydrolyzed solution.

[0047] The hydrolyzed solution, the aqueous solution of the film-forming agent, the aqueous solution of the lubricant, the aqueous solution of the antistatic agent, and the remaining water are mixed to obtain the wetting agent.

[0048] Furthermore, in the preparation method, the method of hydrolyzing the silane coupling agent includes: mixing the aqueous solution of the pH adjuster and a portion of water, then adding the silane coupling agent under stirring conditions, and dispersing until there are no oil droplets on the surface of the solution to obtain the hydrolyzed solution.

[0049] Furthermore, during the process of mixing the hydrolyzed solution, the aqueous solution of the film-forming agent, the aqueous solution of the lubricant, the aqueous solution of the antistatic agent, and the remaining water, each component is added sequentially, and after adding one component, it needs to be mixed thoroughly before adding another.

[0050] In another aspect, the present invention provides the use of the as-described wetting agent in basalt fiber reinforced vinyl resin.

[0051] Furthermore, the application includes the following steps:

[0052] A sizing agent is coated on the surface of basalt fiber to obtain basalt fiber with a sizing agent coating on the surface;

[0053] The basalt fibers with a wetting agent coating on their surface are mixed with a vinyl ester resin solution, heated and molded, and then cooled to room temperature to obtain a basalt fiber reinforced vinyl ester resin composite material.

[0054] Furthermore, the molding method is vacuum bag pressure assisted molding.

[0055] Furthermore, the method for applying the wetting agent includes the following steps:

[0056] Add sizing agent to the sizing tank and allow the unsized basalt fibers to pass through the sizing tank at a uniform speed, ensuring that the residence time in the sizing tank is about 10 seconds. The mass of the sizing agent is about 0.8-1.2% of the fiber mass. Then, cure in an oven at 100°C for 2 hours to obtain basalt fibers with a sizing agent coating on the surface.

[0057] Furthermore, the preparation of the composite material includes the following steps:

[0058] The basalt fiber with a wetting agent coating on its surface is mixed with vinyl ester resin liquid using a vacuum bag-assisted molding method, heated and molded, and then cooled to room temperature to obtain a basalt fiber reinforced vinyl ester resin composite material. The basalt fiber accounts for about 50-70% of the mass of the composite board, preferably 70%.

[0059] The beneficial effects of this invention are as follows:

[0060] The sizing agent provided in this invention is specifically designed for basalt fiber-reinforced vinyl ester resin, addressing the shortage of dedicated sizing agents for vinyl ester resin. This sizing agent is water-soluble, environmentally friendly, readily available, easy to formulate, and readily scalable. Furthermore, it exhibits good uniformity and stability. It not only increases the interfacial bonding force between basalt fiber and vinyl ester resin in composite materials reinforced with basalt fiber, but also protects the fibers and improves the mechanical properties of the composite material. Attached Figure Description

[0061] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0062] Figure 1 This illustrates an exemplary basalt fiber wetting agent coating process in an embodiment of the present invention.

[0063] Figure 2 SEM images of the fracture morphology of basalt fiber reinforced vinyl ester resin composites modified with a general sizing agent or the sizing agent of Example 1 at different magnifications are shown.

[0064] Figure 3 SEM images at different magnifications of the fracture morphology of short beam shear tests of basalt fiber reinforced vinyl ester resin composites modified with a general sizing agent or the sizing agent of Example 1 are shown. Detailed Implementation

[0065] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further explains the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0066] Example 1

[0067] A basalt fiber reinforced vinyl ester resin impregnating agent, with the following weights of each component based on a total weight of 100 kg:

[0068] 1.26 kg of silane coupling agent, including 0.6 kg of vinyl silane coupling agent (γ-methacryloyloxypropyltrimethoxysilane, brand name A174, solid content 80 wt%) and 0.66 kg of epoxy silane coupling agent (γ-glycidoxypropyltrimethoxysilane, brand name A187, solid content 80 wt%).

[0069] 15.6 kg of film-forming agent;

[0070] 0.47 kg of lubricant, including 0.36 kg of nonionic lubricant (PEG400MONO (Emerest 2640), solid content 100 wt%) and 0.11 kg of cationic lubricant (polyoxyethylene amine salt, brand name Emery 6760L, solid content 65 wt%).

[0071] 0.22 kg of pH adjuster (glacial acetic acid, 90 wt%);

[0072] 0.07 kg of antistatic agent (quaternary ammonium salt, brand name Katax 6660, solid content 100 wt%); and

[0073] The remaining water;

[0074] The film-forming agent is an epoxy resin emulsion film-forming agent, specifically an epoxy acrylate film-forming agent formed by emulsifying epoxy resin, with an epoxy equivalent of 250 g / equivalent and a solid content of 30 wt%. The specific preparation method of this film-forming agent is as follows:

[0075] Mix 10 kg of epoxy acrylate (epoxy equivalent of 250 g / equivalent) with 20 kg of deionized water and stir gently for 5 minutes to ensure uniformity.

[0076] Add 1 kg of polyoxyethylene ether (TWEEN 20) and continue stirring for 5 minutes to ensure the emulsifier is fully dissolved. Use a high-shear stirrer at 2500 rpm and stir for 10 minutes until a stable emulsion is formed.

[0077] Adjust the pH of the emulsion to 6.0-6.5 with diluted sodium hydroxide or acetic acid. Cool the emulsion to room temperature and transfer it to a dry, airtight container for storage, away from direct sunlight.

[0078] The preparation method of this wetting agent includes the following steps:

[0079] (1) Mix 0.198 kg of glacial acetic acid and 0.022 kg of purified water, seal and set aside for later use;

[0080] (2) Add 0.1 kg of the above diluted glacial acetic acid to 12 kg of pure water, mix well, and slowly add 0.6 kg of γ-methacryloxypropyltrimethoxysilane while stirring. Stir for 30 min until the solution is clear.

[0081] (3) Add 0.12 kg of the above diluted glacial acetic acid to 13.2 kg of pure water, mix well, and slowly add 0.66 kg of γ-glycidoxypropyltrimethoxysilane while stirring. Stir for 20 min until the solution is clear.

[0082] (4) Measure 15.6 kg of epoxy resin emulsion film-forming agent, add 31.2 kg of purified water, stir thoroughly and mix evenly;

[0083] (5) Measure 0.36 kg of PEG400MONO, add 3.6 kg of purified water at 45°C, stir thoroughly and mix evenly;

[0084] (6) Measure 0.11 kg of polyoxyethylene amine salt, add 1.1 kg of purified water at 45°C, stir thoroughly and mix evenly;

[0085] (7) Measure 0.07 kg of quaternary ammonium salt, add 1.3 kg of pure water at 85°C, stir thoroughly and mix evenly;

[0086] (8) Add 10 kg of purified water, hydrolyzed γ-methacryloxypropyltrimethoxysilane, hydrolyzed γ-glycidyl etheroxypropyltrimethoxysilane, diluted PEG400MONO, diluted polyoxyethylene amine salt, diluted epoxy resin emulsion film-forming agent, and diluted quaternary ammonium salt to the container in sequence, and finally add the remaining water to make the total weight reach 100 kg.

[0087] Example 2

[0088] A basalt fiber reinforced vinyl ester resin impregnating agent, with the following weights of each component based on a total weight of 100 kg:

[0089] 1.31 kg of silane coupling agent, including 0.65 kg of vinyl silane coupling agent (γ-methacryloyloxypropyltrimethoxysilane, brand name A174, solid content 80 wt%) and 0.66 kg of epoxy silane coupling agent (γ-glycidoxypropyltrimethoxysilane, brand name A187, solid content 80 wt%).

[0090] 15.6 kg of film-forming agent;

[0091] 0.47 kg of lubricant, including 0.36 kg of nonionic lubricant (PEG400MONO (Emerest 2640), solid content 100 wt%) and 0.11 kg of cationic lubricant (polyoxyethylene amine salt, brand name Emery 6760L, solid content 65 wt%).

[0092] 0.25 kg of pH adjuster (glacial acetic acid, 90 wt%);

[0093] 0.07 kg of antistatic agent (quaternary ammonium salt, brand name Katax 6660, solid content 100 wt%); and

[0094] The remaining water;

[0095] The film-forming agent is an epoxy resin emulsion film-forming agent, specifically an epoxy acrylate film-forming agent formed by emulsifying epoxy resin, with an epoxy equivalent of 250 g / equivalent and a solid content of 30 wt%.

[0096] The preparation method of this wetting agent includes the following steps:

[0097] (1) Mix 0.225 kg of glacial acetic acid and 0.025 kg of purified water, seal and set aside for later use;

[0098] (2) Add 0.13 kg of diluted glacial acetic acid to 13 kg of purified water, mix well, and then slowly add 0.65 kg of γ-methacryloxypropyltrimethoxysilane while stirring. Stir for 30 min until the solution is clear.

[0099] (3) Add 0.12 kg of diluted glacial acetic acid to 13.2 kg of purified water, mix well, and slowly add 0.66 kg of γ-glycidoxypropyltrimethoxysilane while stirring. Stir for 20 min until the solution is clear.

[0100] (4) Measure 15.6 kg of epoxy resin emulsion film-forming agent, add 31.2 kg of purified water, stir thoroughly and mix evenly;

[0101] (5) Measure 0.36 kg of PEG400MONO, add 3.6 kg of purified water at 45°C, stir thoroughly and mix evenly;

[0102] (6) Measure 0.11 kg of polyoxyethylene amine salt, add 1.1 kg of purified water at 45°C, stir thoroughly and mix evenly;

[0103] (7) Measure 0.07 kg of quaternary ammonium salt, add 1.3 kg of pure water at 85°C, stir thoroughly and mix evenly;

[0104] (8) Add 10 kg of purified water, hydrolyzed γ-methacryloxypropyltrimethoxysilane, hydrolyzed γ-glycidyl etheroxypropyltrimethoxysilane, diluted PEG400MONO, diluted polyoxyethylene amine salt, diluted epoxy resin emulsion film-forming agent, and diluted quaternary ammonium salt to the container in sequence, and finally add the remaining water to make the total weight reach 100 kg.

[0105] Example 3

[0106] A basalt fiber reinforced vinyl ester resin impregnating agent, with the following weights of each component based on a total weight of 100 kg:

[0107] 1.21 kg of silane coupling agent, including 0.6 kg of vinyl silane coupling agent (γ-methacryloyloxypropyltrimethoxysilane, brand name A174, solid content 80 wt%) and 0.61 kg of epoxy silane coupling agent (γ-glycidoxypropyltrimethoxysilane, brand name A187, solid content 80 wt%).

[0108] 15.6 kg of film-forming agent;

[0109] 0.47 kg of lubricant, including 0.36 kg of nonionic lubricant (PEG400MONO (Emerest 2640), solid content 100 wt%) and 0.11 kg of cationic lubricant (polyoxyethylene amine salt, brand name Emery 6760L, solid content 65 wt%).

[0110] 0.2 kg of pH adjuster (glacial acetic acid, 90 wt%);

[0111] 0.07 kg of antistatic agent (quaternary ammonium salt, brand name Katax 6660, solid content 100 wt%); and

[0112] The remaining water;

[0113] The film-forming agent is an epoxy resin emulsion film-forming agent, specifically an epoxy acrylate film-forming agent formed by emulsifying epoxy resin, with an epoxy equivalent of 250 g / equivalent and a solid content of 30 wt%.

[0114] The preparation method of this wetting agent includes the following steps:

[0115] (1) Mix 0.18 kg of glacial acetic acid and 0.02 kg of purified water, seal and set aside for later use;

[0116] (2) Add 0.1 kg of diluted glacial acetic acid to 12 kg of purified water, mix well, and then slowly add 0.6 kg of γ-methacryloxypropyltrimethoxysilane while stirring. Stir for 30 min until the solution is clear.

[0117] (3) Add 0.1 kg of diluted glacial acetic acid to 12.2 kg of purified water, mix well, and slowly add 0.61 kg of γ-glycidoxypropyltrimethoxysilane while stirring. Stir for 20 min until the solution is clear.

[0118] (4) Measure 15.6 kg of epoxy emulsion, add 31.2 kg of purified water, stir thoroughly and mix evenly;

[0119] (5) Measure 0.36 kg of PEG400MONO, add 3.6 kg of purified water at 45°C, stir thoroughly and mix evenly;

[0120] (6) Measure 0.11 kg of polyoxyethylene amine salt, add 1.1 kg of purified water at 45°C, stir thoroughly and mix evenly;

[0121] (7) Measure 0.07 kg of quaternary ammonium salt, add 1.3 kg of pure water at 85°C, stir thoroughly and mix evenly;

[0122] (8) Add 10 kg of purified water, hydrolyzed γ-methacryloxypropyltrimethoxysilane, hydrolyzed γ-glycidyl etheroxypropyltrimethoxysilane, diluted PEG400MONO, diluted polyoxyethylene amine salt, diluted epoxy emulsion, and diluted quaternary ammonium salt to the container in sequence, and finally add the remaining water to make the total weight reach 100 kg.

[0123] Example 4

[0124] A basalt fiber reinforced vinyl ester resin impregnating agent, with the following weights of each component based on a total weight of 100 kg:

[0125] 1.26 kg of silane coupling agent, including 0.6 kg of vinyl silane coupling agent (γ-methacryloyloxypropyltrimethoxysilane, brand name A174, solid content 80 wt%) and 0.66 kg of epoxy silane coupling agent (γ-glycidoxypropyltrimethoxysilane, brand name A187, solid content 80 wt%).

[0126] 14.6 kg of film-forming agent;

[0127] 0.47 kg of lubricant, including 0.36 kg of nonionic lubricant (PEG400MONO (Emerest 2640), solid content 100 wt%) and 0.11 kg of cationic lubricant (polyoxyethylene amine salt, brand name Emery 6760L, solid content 65 wt%).

[0128] 0.22 kg of pH adjuster (glacial acetic acid, 90 wt%);

[0129] 0.07 kg of antistatic agent (quaternary ammonium salt, brand name Katax 6660, solid content 100 wt%); and

[0130] The remaining water;

[0131] The film-forming agent is an epoxy resin emulsion film-forming agent, specifically an epoxy acrylate film-forming agent formed by emulsifying epoxy resin, with an epoxy equivalent of 250 g / equivalent and a solid content of 30 wt%.

[0132] The preparation method of this wetting agent includes the following steps:

[0133] (1) Mix 0.198 kg of glacial acetic acid and 0.022 kg of purified water, seal and set aside for later use;

[0134] (2) Add 0.1 kg of diluted glacial acetic acid to 12 kg of purified water, mix well, and then slowly add 0.6 kg of γ-methacryloxypropyltrimethoxysilane while stirring. Stir for 30 min until the solution is clear.

[0135] (3) Add 0.12 kg of diluted glacial acetic acid to 13.2 kg of purified water, mix well, and slowly add 0.66 kg of γ-glycidoxypropyltrimethoxysilane while stirring. Stir for 20 min until the solution is clear.

[0136] (4) Measure 14.6 kg of epoxy resin emulsion film-forming agent, add 29.2 kg of purified water, stir thoroughly and mix evenly;

[0137] (5) Measure 0.36 kg of PEG400MONO, add 3.6 kg of purified water at 45°C, stir thoroughly and mix evenly;

[0138] (6) Measure 0.11 kg of polyoxyethylene amine salt, add 1.1 kg of purified water at 45°C, stir thoroughly and mix evenly;

[0139] (7) Measure 0.07 kg of quaternary ammonium salt, add 1.3 kg of pure water at 85°C, stir thoroughly and mix evenly;

[0140] (8) Add 10 kg of purified water, hydrolyzed γ-methacryloxypropyltrimethoxysilane, hydrolyzed γ-glycidyl etheroxypropyltrimethoxysilane, diluted PEG400MONO, diluted polyoxyethylene amine salt, diluted epoxy resin emulsion film-forming agent, and diluted quaternary ammonium salt to the container in sequence, and finally add the remaining water to make the total weight reach 100 kg.

[0141] Example 5

[0142] A basalt fiber reinforced vinyl ester resin impregnating agent, with the following weights of each component based on a total weight of 100 kg:

[0143] 1.26 kg of silane coupling agent, including 0.6 kg of vinyl silane coupling agent (γ-methacryloyloxypropyltrimethoxysilane, brand name A174, solid content 80 wt%) and 0.66 kg of epoxy silane coupling agent (γ-glycidoxypropyltrimethoxysilane, brand name A187, solid content 80 wt%).

[0144] 15.6 kg of film-forming agent;

[0145] 0.55 kg of lubricant, including 0.4 kg of nonionic lubricant (PEG400MONO (Emerest 2640), solid content 100 wt%) and 0.15 kg of cationic lubricant (polyoxyethylene amine salt, brand name Emery 6760L, solid content 65 wt%).

[0146] 0.22 kg of pH adjuster (glacial acetic acid, 90 wt%);

[0147] 0.07 kg of antistatic agent (quaternary ammonium salt, brand name Katax 6660, solid content 100 wt%); and

[0148] The remaining water;

[0149] The film-forming agent is an epoxy resin emulsion film-forming agent, specifically an epoxy acrylate film-forming agent formed by emulsifying epoxy resin, with an epoxy equivalent of 250 g / equivalent and a solid content of 30 wt%.

[0150] The preparation method of this wetting agent includes the following steps:

[0151] (1) Mix 0.198 kg of glacial acetic acid and 0.022 kg of purified water, seal and set aside for later use;

[0152] (2) Add 0.1 kg of diluted glacial acetic acid to 12 kg of purified water, mix well, and then slowly add 0.6 kg of γ-methacryloxypropyltrimethoxysilane while stirring. Stir for 30 min until the solution is clear.

[0153] (3) Add 0.12 kg of diluted glacial acetic acid to 13.2 kg of purified water, mix well, and slowly add 0.66 kg of γ-glycidoxypropyltrimethoxysilane while stirring. Stir for 20 min until the solution is clear.

[0154] (4) Measure 15.6 kg of epoxy resin emulsion film-forming agent, add 31.2 kg of purified water, stir thoroughly and mix evenly;

[0155] (5) Measure 0.4 kg of PEG400MONO, add 4.0 kg of purified water at 45℃, stir thoroughly and mix evenly;

[0156] (6) Measure 0.15 kg of polyoxyethylene amine salt, add 1.5 kg of purified water at 45°C, stir thoroughly and mix evenly;

[0157] (7) Measure 0.07 kg of quaternary ammonium salt, add 1.3 kg of pure water at 85°C, stir thoroughly and mix evenly;

[0158] (8) Add 10 kg of purified water, hydrolyzed γ-methacryloxypropyltrimethoxysilane, hydrolyzed γ-glycidyl etheroxypropyltrimethoxysilane, diluted PEG400MONO, diluted polyoxyethylene amine salt, diluted epoxy resin emulsion film-forming agent, and diluted quaternary ammonium salt to the container in sequence, and finally add the remaining water to make the total weight reach 100 kg.

[0159] Comparative Example 1

[0160] Example 1 was repeated, except that the silane coupling agent was replaced with 1.26 kg of epoxy silane coupling agent (γ-glycidoxypropyltrimethoxysilane, brand name A187, solid content 80 wt%), while the other conditions remained unchanged, and the wetting agent was prepared.

[0161] Comparative Example 2

[0162] Repeat Example 1, except that the amount of film-forming agent was changed to 9 kg, while the other conditions remained the same, to prepare the wetting agent.

[0163] Comparative Example 3

[0164] Example 1 was repeated, except that the film-forming agent was replaced with an epoxy acrylate film-forming agent with an epoxy equivalent of 400 g / equivalent, while the other conditions remained unchanged, and the wetting agent was prepared.

[0165] Applications of the wetting agents prepared in the above embodiments and comparative examples in basalt fiber reinforced vinyl ester resins:

[0166] 1. Coat the surface of the basalt fiber with a sizing agent:

[0167] The sizing agent is placed in a sizing tank, and then the basalt fiber bundles or basalt fiber unidirectional fabric wound on the guide rollers are passed sequentially through the sizing tank and the oven to achieve coating and curing of the sizing agent. Finally, it is wound and wound on another guide roller to obtain basalt fibers or basalt fiber unidirectional fabrics with the sizing agent coated on the surface. The residence time of the basalt fiber bundles or basalt fiber fabrics in the sizing tank is about 10 seconds, the oven temperature is 100℃, and the curing time is 2 hours. The specific process is as follows: Figure 1As shown.

[0168] 2. Preparation and mechanical property testing of composite materials:

[0169] The reinforcing effect of the sizing agent was verified by measuring the mechanical strength of the basalt fiber reinforced vinyl ester resin composite. The composite was prepared using a vacuum bag compression molding method. The specific method is as follows:

[0170] 2.1 Preparation of adhesive solution

[0171] After mixing and stirring the vinyl resin, curing agent (methyl ethyl ketone peroxide), and accelerator (cobalt isooctanoate) in a mass ratio of 100:1.2:0.8, the total mass of the resin system is calculated according to the fiber cloth:resin = 1:1 to obtain the vinyl resin adhesive. At the same time, 500g of resin is weighed out for each square meter of composite material to prevent insufficient resin and for touch-up application.

[0172] 2.2 Material Laying

[0173] First, apply a layer of release agent to the aluminum alloy heating platform to facilitate subsequent demolding. Then, lay down the following layers in sequence: a lower layer of release cloth, a basalt fiber unidirectional cloth coated with a wetting agent (5 layers for tensile and dynamic thermomechanical samples, 30cm × 16cm in size; 18 layers for bending and shearing samples, 25cm × 10cm in size), an upper layer of release cloth, a flow guide net, and a vacuum bag. Install injection tubes and vacuum tubes at both ends, securing them with vacuum tape. The two rubber tubes should be placed between the two layers of release cloth. Furthermore, the vacuum tube opening should be wrapped with a breathable mesh to prevent blockage.

[0174] 2.3 Resin Introduction

[0175] Secure the vacuum bag with vacuum tape to form a sealed system between the vacuum bag and the aluminum alloy heating stage. Turn on the vacuum pump, ensuring the system is leak-proof, and then introduce the vinyl ester resin solution. Once the resin has completely impregnated the fiber cloth and flowed into the vacuum tube, clamp the injection tube and the vacuum tube. Heat to 50°C and maintain for 90 minutes. Turn off the heating stage and allow the sample to cool naturally to room temperature before demolding to obtain a basalt fiber unidirectional cloth reinforced vinyl ester resin composite board. The mass fraction of the basalt fiber cloth is approximately 70%.

[0176] 2.4 Mechanical property testing

[0177] The prepared basalt fiber reinforced vinyl ester resin composite board was mechanically processed into test strips of different sizes using a universal sample preparation machine.

[0178] (1) Tensile strength test

[0179] The tensile properties of the composite material were tested on a universal testing machine according to ISO 527. The specimen size was 250 mm × 15 mm × 1 mm. Reinforcing sheets were attached to both ends of the specimen using epoxy resin structural adhesive, and the specimen was cured in an oven at 50 °C for 1 hour. The tensile speed during the test was 5 mm·min. -1 .

[0180] (2) Bending strength test

[0181] The flexural properties of the composite material were tested on a universal testing machine according to ISO 178. The specimen size was 80 mm × 10 mm × 4 mm, the span was 64 mm, and the loading rate during the test was 10 mm·min. -1 .

[0182] (3) Interlaminar shear strength test

[0183] The shear properties of the composite material were tested on a universal testing machine according to ISO 14130. The specimen size was 40mm × 20mm × 4mm, the span was 20mm, and the loading rate was 10mm·min during the test. -1 .

[0184] (4) Characterization of fracture morphology

[0185] The fracture morphology of the specimens after bending or interlaminar shear tests was observed using a scanning electron microscope. The sample surface needs to be sputtered with gold before the test.

[0186] (5) Interfacial shear strength test

[0187] The interfacial shear strength of the basalt fiber-vinyl resin microcomposite was tested using a micro-debonding test. First, test samples were prepared by fixing basalt fiber monofilaments straight onto a paper frame with a central perforation using 502 glue. Resin was prepared, and a needle tip was dipped into the resin and quickly slid it across the fiber monofilament. The resin contracted into small spheres under surface tension. The samples were then cured in an oven at 100°C for 4 hours.

[0188] After preparing the sample, clamp the paper frame in the fixture, adjust the cutter so that it just clamps the resin droplet, and then pull the fiber at a speed of 0.005 mm / s. -1 The fiber can pass through the clamp while the resin cannot, until the droplet slips. The maximum tensile force is recorded, and the interfacial shear strength is calculated.

[0189] Test results:

[0190] The mechanical properties of the sizing agents described in the above embodiments for modifying basalt fiber reinforced vinyl ester resins are shown in Table 1 below. Specifically, the general-purpose sizing agent refers to the commercially available sizing agent BF826M.

[0191] Table 1

[0192]

[0193] The results of using the above-mentioned sizing agents to modify the mechanical properties of basalt fiber reinforced vinyl ester resin are shown in Table 2 below.

[0194] Table 2

[0195]

[0196] Figure 2 (a) i ), (a ii The following are SEM images of the fracture morphology of the basalt fiber reinforced vinyl ester resin composite material modified with the above-mentioned general impregnating agent at different magnifications during bending tests. Figure 2 (b) i (b) ii The images show SEM images of the fracture morphology of the sizing agent modified basalt fiber reinforced vinyl ester resin composite material in Example 1 above at different magnifications.

[0197] Figure 3 (a) i ), (a ii The following are SEM images of the fracture morphology of the short beam shear test of the above-mentioned general-purpose sizing agent modified basalt fiber reinforced vinyl ester resin composite material at different magnifications: Figure 3 (b) i (b) ii The images show SEM images of the fracture morphology of the short beam shear test of the sizing agent modified basalt fiber reinforced vinyl ester resin composite material in Example 1 above, at different magnifications.

[0198] The SEM results above show that the surface of basalt fibers modified with the general-purpose sizing agent is relatively smooth, and there is a phenomenon of fibers being pulled out of the resin, indicating that the interfacial bonding strength is not ideal. However, the basalt fibers modified with the sizing agent in the examples have more resin matrix adhering to their surface, indicating that the fracture and damage occur more in the fiber phase and the numerical phase, rather than the interfacial phase. This shows that the special-purpose sizing agent in this invention has a better interfacial reinforcement effect than the general-purpose sizing agent.

[0199] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A special impregnating agent for basalt fiber reinforced vinyl ester resin, characterized in that, The raw materials forming the wetting agent, by weight percentage, contain the following components: 1-2% silane coupling agent, 10-20% film-forming agent, 0.3-0.7% lubricant, 0.15-0.25% pH adjuster, 0.05-0.1% antistatic agent, and the balance being water; The film-forming agent is an epoxy resin emulsion film-forming agent, and the solid content of the epoxy resin emulsion film-forming agent is 20-40 wt%, and the epoxy equivalent is 100-350 g / equivalent.

2. The wetting agent according to claim 1, characterized in that, The film-forming agent is an epoxy acrylate film-forming agent, and the preparation of the film-forming agent includes the following steps: Epoxy acrylate and deionized water are mixed in a mass ratio of 1:2 to 1:4 and stirred until homogeneous to fully disperse the epoxy acrylate and obtain a mixture. Add the emulsifier to the mixture and continue stirring to ensure that the emulsifier is completely dissolved. The mass of the emulsifier should be 5-10% of the mass of the epoxy acrylate. Emulsification is performed using a high-shear mixer at a speed of 2000-4000 rpm for 10-20 minutes until a stable emulsion is formed.

3. The wetting agent according to claim 1, characterized in that, The silane coupling agent is a vinyl silane coupling agent, or a mixture of a vinyl silane coupling agent and one or more selected from epoxy silane coupling agents and amino silane coupling agents; More preferably, the silane coupling agent is a mixture of vinyl silane coupling agent and epoxy silane coupling agent in a mass ratio of 6:(5-8); Preferably, the vinyl silane coupling agent is selected from one or more of A151, A171, A172 and A174; Preferably, the epoxy silane coupling agent is selected from A187 and / or A1871; Preferably, the aminosilane coupling agent is selected from one or more of A1100, A1110, A1120 and A1210.

4. The wetting agent according to claim 1, characterized in that, The lubricant is a mixture of nonionic lubricant and cationic lubricant in a mass ratio of (2.5-4):1; Preferably, the lubricant is a mixture of a nonionic lubricant and a cationic lubricant in a mass ratio of (2.5-3.5):1; Preferably, the nonionic lubricant is selected from one or more of polyoxyethylene ether lubricants, amide lubricants, and ester lubricants; Preferably, the cationic lubricant is selected from one or more of polyoxyethylene amine salt lubricants, quaternary ammonium salt lubricants, and imidazoline lubricants.

5. The wetting agent according to claim 1, characterized in that, The pH adjuster is selected from acids; Preferably, the pH adjuster is selected from organic acids or inorganic acids; Preferably, the pH adjuster is selected from one or more of citric acid, glacial acetic acid, boric acid, and formic acid.

6. The wetting agent according to claim 1, characterized in that, The antistatic agent is selected from one or more of quaternary ammonium salts, sulfate esters, phosphate esters, and polyethylene glycol derivatives.

7. The wetting agent according to claim 1, characterized in that, The raw materials forming the wetting agent, by weight percentage, contain the following components: 1.3% silane coupling agent, 15.6% film-forming agent, 0.47% lubricant, 0.22% pH adjuster, 0.07% antistatic agent and the balance being water.

8. The method for preparing the wetting agent according to any one of claims 1-7, characterized in that, Includes the following steps: The film-forming agent, lubricant, pH adjuster, and antistatic agent were diluted with water to obtain aqueous solutions of the film-forming agent, lubricant, pH adjuster, and antistatic agent, respectively. The silane coupling agent is hydrolyzed in the presence of an aqueous solution of the pH adjuster and a portion of water to obtain a hydrolyzed solution. The hydrolyzed solution, the aqueous solution of the film-forming agent, the aqueous solution of the lubricant, the aqueous solution of the antistatic agent, and the remaining water are mixed to obtain the wetting agent.

9. The use of the wetting agent as described in any one of claims 1-7 in basalt fiber reinforced vinyl ester resin.

10. The application according to claim 9, characterized in that, The application includes the following steps: The sizing agent is coated onto the surface of the basalt fiber to form a sizing agent coating. Basalt fibers coated with the sizing agent are mixed with vinyl ester resin, heated to form, and cooled to room temperature to obtain basalt fiber reinforced vinyl ester resin composite material. Preferably, the mass of the impregnating agent is 0.8-1.2% of the mass of the basalt fiber; Preferably, in the composite material, the mass percentage of basalt fiber to which the sizing agent coating is formed is 50-70%.

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