A glass fiber sizing and its method of preparation, product and use

Abstract

The application provides a glass fiber sizing agent, which comprises effective components and water, and the solid content is 5.0%-8.0%; the effective components comprise silane coupling agent, film forming agent, lubricant, surfactant, interface reinforcing agent, crosslinking agent, wetting agent and pH value regulator; the percentage of the solid mass of each effective component in the total mass of the sizing agent is shown as follows: 7%-25% of silane coupling agent, 43%-80% of film forming agent, 5%-16% of lubricant, 1%-7% of surfactant, 1%-5% of interface reinforcing agent, 1%-5% of crosslinking agent, 2%-6% of wetting agent and 1%-7% of pH value regulator; the glass fiber yarn produced by using the sizing agent has good bunching property, the yarn is soft and easy to disperse after tension, has less hairiness, has very fast impregnation speed in dicyclopentadiene resin and good impregnation effect; meanwhile, the sizing agent is suitable for weaving and pultrusion process, the prepared composite material glass fiber has good interface compatibility with resin, and has very excellent static mechanical and fatigue properties.

Description

Technical Field

[0001] This application relates to the field of glass fiber sizing agents, and more particularly to a glass fiber sizing agent for reinforcing dicyclopentadiene resin, its preparation method, and its application. Background Technology

[0002] Dicyclopentadiene, a crosslinked thermosetting resin, can be used to prepare polydicyclopentadiene (PDCPD) through ring-opening polymerization. PDCPD possesses mechanical properties similar to thermoplastic engineering plastics. Compared to traditional thermosetting resins, dicyclopentadiene has a very low viscosity before polymerization, exhibiting excellent flowability and easily filling mold cavities of complex-shaped parts. This enables one-step monolithic polymerization to produce high-performance composite materials. Furthermore, the product shape can be freely designed, the reaction time is short and efficient, and the molding cycle is freely adjustable. The polymerized material exhibits excellent mechanical properties, high impact strength, and high flexural modulus. In addition, the material itself has a good surface finish and can be self-demolded without the need for release agents during polymerization, making it particularly suitable for surface decoration and structural components.

[0003] Dicyclopentadiene is a pure hydrocarbon, free of heteroatoms, thus exhibiting excellent corrosion resistance, especially against acids and alkalis. This makes it suitable for manufacturing parts requiring corrosion resistance. Its water resistance is also outstanding, making it suitable for lining containers for corrosive chemicals, pipes, buckets, basins, and sanitary ware. Compared to traditional thermosetting materials, polydicyclopentadiene has good low-temperature resistance; even at -70°C, its physical properties are not easily affected by temperature, making it suitable for manufacturing products used in low-temperature environments. Polydicyclopentadiene does not produce harmful substances, including PCDDs, when burned. This product also does not contain any of the six specific hazardous substances listed under RoHS standards, nor any chemicals that can cause endocrine disorders. It is recyclable, making it an excellent environmentally friendly material.

[0004] Dicyclopentadiene (DCPD) is mainly derived from petroleum cracking products and benzene-head fractions of coal tar. With the continuous development of my country's economy, the domestic market demand for chemical products and materials synthesized from DCPD is constantly expanding. Although polydicyclopentadiene (PCPD) has excellent mechanical properties, the performance of pure resin often fails to meet the requirements of many engineering components, thus requiring reinforcement materials. Glass fiber, as the most typical resin reinforcement material on the market, is considered the most promising material for reinforcing such resins. However, there is currently no dedicated sizing agent for PCPD on the market. Therefore, designing a glass fiber sizing agent suitable for reinforcing PCPD resin will significantly promote and enhance the development of the entire composite materials industry. Simultaneously, it has significant meaning and far-reaching impact on research in the cutting-edge field of novel composite materials. Summary of the Invention

[0005] This application aims to provide a glass fiber impregnating agent suitable for reinforcing dicyclopentadiene resin, its preparation method, and its application. Glass fiber yarns produced using this impregnating agent are soft, have few hairs, and impregnate in dicyclopentadiene resin very quickly with good impregnation effect. It is also suitable for both weaving and pultrusion processes. The resulting composite glass fiber exhibits excellent interfacial compatibility with the resin and possesses superior static mechanical and fatigue properties.

[0006] According to one aspect of this application, a glass fiber sizing agent suitable for reinforcing dicyclopentadiene resin is provided, the sizing agent containing an effective component and water; the solid content of the sizing agent is 5.0% to 8.0%; the effective component includes a silane coupling agent, a film-forming agent, a lubricant, a surfactant, an interface enhancer, a wetting agent, and a pH adjuster; the percentage of the solid mass of each effective component to the total solid mass of the sizing agent is expressed as follows:

[0007]

[0008] The interface enhancer is polystyrene nanoparticles.

[0009] Furthermore, the percentage of the solid mass of each effective component to the total solid mass of the wetting agent is expressed as follows:

[0010]

[0011]

[0012] Furthermore, the percentage of the solid mass of each effective component to the total solid mass of the wetting agent is expressed as follows:

[0013]

[0014] The silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent, wherein the first silane coupling agent is a vinyl silane coupling agent and the second silane coupling agent is an amino silane coupling agent.

[0015] Furthermore, the mass ratio of the first silane coupling agent to the second silane coupling agent is (2-4):1.

[0016] Furthermore, the film-forming agent is a mixture of a first film-forming agent and a second film-forming agent; the first film-forming agent is an unsaturated polyester resin with a molecular weight of 200-450; the second film-forming agent is an acrylic resin with a molecular weight of 800-1200.

[0017] Furthermore, the mass ratio of the first film-forming agent to the second film-forming agent is (1-3):1.

[0018] Furthermore, the lubricant is a polyethylene glycol derivative lubricant; the surfactant is a polypyrrolidone surfactant; the crosslinking agent is a copolymer of ethylene and maleic anhydride; the wetting agent is an acetylenic diol wetting agent; and the pH adjuster is selected from citric acid and / or glacial acetic acid.

[0019] Furthermore, the percentage of the solid mass of each effective component to the total solid mass of the wetting agent is expressed as follows:

[0020]

[0021] The silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent, wherein the first silane coupling agent is a vinyl silane coupling agent and the second silane coupling agent is an amino silane coupling agent; the film-forming agent is a mixture of a first film-forming agent and a second film-forming agent; the first film-forming agent is an unsaturated polyester resin; the second film-forming agent is an acrylic resin; the surfactant is a polypyrrolidone surfactant; the interface reinforcing agent is polystyrene nanoparticles; the crosslinking agent is a copolymer of ethylene and maleic anhydride; the wetting agent is an acetylenic diol wetting agent; and the pH adjuster is citric acid and / or glacial acetic acid.

[0022] Furthermore, the water used as the wetting agent in this application is preferably deionized water.

[0023] The functions and contents of each effective component in the glass fiber impregnating agent of this application are explained as follows:

[0024] Silane coupling agents are the most reactive raw materials in the wetting agent system. The siloxy groups they contain can form highly reactive silanol groups after hydrolysis, which can react with the silanol groups on the surface of glass fibers to form relatively stable Si-O-Si bonds. In glass fiber production, coupling agents mainly play two roles: (1) Protecting the drawing process and ensuring the success rate of drawing; During the glass fiber drawing process, due to the high speed, the glass fiber will complete the liquid to solid transformation very quickly. In this process, a lot of microcracks will be formed on the surface. Silane coupling agents can compensate for these microcracks by reacting with the silanol groups on the surface of glass fibers through their own silanol groups, ensuring the normal drawing process of glass fibers. (2) The link between glass fibers and resin. The silanol groups of silane coupling agents can combine with the silanol groups on glass fibers, while the characteristic functional group R group can react with the functional groups on the matrix resin. Therefore, it is one of the key factors that determine the strength of glass fiber composite materials. Choosing a suitable coupling agent can not only improve the production uptime of glass fibers and the mechanical properties of subsequent products, but also reduce the production cost of glass fibers. In glass

[0025] When preparing glass fiber impregnation agents, the amount of silane coupling agent needs to be controlled. Insufficient silane coupling agent will affect the glass fiber drawing process and the performance of the composite material due to insufficient active groups; excessive silane coupling agent, exceeding the required "saturation" concentration, will result in wasted coupling agent and increased production costs. This application controls the percentage of the solid mass of the silane coupling agent to the total solid mass of the impregnation agent to be 7%–25%, preferably 8%–23%, more preferably 10%–21%, and even more preferably 11%–18%.

[0026] This application uses a mixture of a first silane coupling agent and a second silane coupling agent, wherein the first silane coupling agent is a vinyl silane coupling agent and the second silane coupling agent is an aminosilane coupling agent. The R group in the vinyl silane coupling agent is an olefin double bond, which ensures that the glass fiber is rapidly impregnated in dicyclopentadiene resin during subsequent composite material preparation and participates in the polymerization reaction, resulting in a very tight bond between the glass fiber and the resin. The aminosilane coupling agent contains an amine group, exhibiting very high reactivity. It reacts with the film-forming agent and crosslinking agent during the baking process, ensuring the overall bundled structure of the glass fiber and smooth application processes. This application strictly limits the ratio of the two silane coupling agents. Excessive use of aminosilane coupling agent leads to overly strong and rigid glass fiber bundles, hindering impregnation. While excessive use of vinyl silane coupling agent promotes the impregnation of dicyclopentadiene resin into the glass fiber and increases its participation in the reaction to ensure interfacial bonding, excessive use resulting in insufficient aminosilane coupling agent leads to inadequate yarn bundles and fraying, directly deteriorating the processability of the glass fiber. Therefore, this application controls the mass ratio of vinyl silane coupling agent to aminosilane coupling agent to be (2-4):1, preferably (2.7-3.6):1. Specifically, when the mass ratio of vinyl silane coupling agent to aminosilane coupling agent is 3.1:1, the glass fibers produced by the impregnating agent prepared in combination with other components achieve the required properties well.

[0027] The first silane coupling agent can be γ-methacryloxypropyltrimethoxysilane or vinyltrimethoxysilane; the second silane coupling agent can be γ-aminopropyltriethoxysilane or γ-aminopropyltrimethoxysilane.

[0028] Film-forming agents are the most abundant and important component of sizing agents. They not only affect the smoothness of the glass fiber drawing process but also determine the bundle structure, hardness, and abrasion resistance of the finished glass fiber. Furthermore, film-forming agents also affect the dispersion and process smoothness of glass fibers in subsequent processing. Generally, film-forming agents are also a key factor in the interfacial bonding between glass fibers and the matrix resin. In glass fiber production, the amount of film-forming agent used needs to be controlled within a suitable range. Insufficient film-forming agent content will lead to uneven coating of the sizing agent, and the sizing agent will not effectively protect the glass fibers, thus affecting the glass fiber drawing start-up rate, as well as its process performance and mechanical properties. Excessive film-forming agent content will result in excessively good yarn bundle structure, making it difficult to disperse, increasing fuzz, and hindering the penetration and bonding with the resin. Therefore, this application controls the percentage of the solid mass of the film-forming agent to the total solid mass of the sizing agent to be 43%–80%, preferably 45%–76%, more preferably 50%–72%, and even more preferably 53%–70%. Within the aforementioned range, the film-forming agent not only ensures good dispersibility and hardness of the glass fiber, but also ensures the smoothness of the subsequent process, compatibility with the matrix resin, and mechanical properties of the composite material.

[0029] Furthermore, the film-forming agent in this application is a mixture of a first film-forming agent and a second film-forming agent. The first film-forming agent is an unsaturated polyester with a low molecular weight, specifically 200-450, preferably 230-400, and more preferably 260-360. The low molecular weight unsaturated polyester has low viscosity and can be quickly impregnated by dicyclopentadiene. The second film-forming agent is an acrylic resin with a high molecular weight, 800-1200, preferably 850-1100, and more preferably 900-1050. Both film-forming agents contain unsaturated double bonds and can participate in the polymerization reaction of dicyclopentadiene. The low molecular weight unsaturated polyester resin ensures that the glass fibers can be easily dispersed after tensioning, thereby ensuring the impregnation performance and interfacial bonding between the glass fibers and the dicyclopentadiene resin. The high molecular weight acrylic resin ensures the uniformity of the film-forming agent and the bundled nature of the glass fibers. The dosage of the two film-forming agents needs to be strictly controlled. Excessive use of the first film-forming agent will result in overly soft yarn, prone to fraying, and affecting subsequent processing performance. Excessive use of the second film-forming agent will lead to excessively good bundle bonding, making it difficult for the yarn to be impregnated by resin and increasing hairiness. In this application, controlling the mass ratio of the first and second film-forming agents to (1-3):1 ensures that the prepared glass fibers exhibit excellent properties. Preferably, the mass ratio is (1.5-2.5):1.

[0030] Lubricants are also a common component of glass fiber impregnation agents, mainly used to improve the wear resistance of glass fibers and ensure smooth operation during glass fiber production and use. The lubricant used in this application is preferably a polyethylene glycol derivative lubricant, which is directly soluble in water and has excellent lubrication effects. It can effectively reduce friction between the glass fiber and the bundling wheel during the drawing process, reducing the probability of glass fiber damage, and also significantly reducing fuzz during subsequent processing and use. The amount of lubricant used needs to be strictly controlled. Using too much lubricant not only increases production costs, but also makes it easy for the lubricant to adhere to the surface of the tensioning equipment during glass fiber use. As the amount of lubricant adhering increases, it can lead to yarn adhesion and breakage. If the amount of lubricant is too small, it can easily cause yarn breakage during the drawing process and yarn interruption during subsequent use. Therefore, this application controls the solid mass of the lubricant to account for 5% to 16% of the total solid mass of the impregnation agent, preferably 7% to 15%, more preferably 7% to 14%, and even more preferably 8% to 13%.

[0031] Surfactants are also an important component of wetting agents. Wetting agents have complex compositions, and many raw materials lack hydrophilicity. Different components are prone to aggregation or even precipitation after mixing. Surfactants, being amphiphilic, can stabilize the components of the wetting agent, thus ensuring the uniformity of the coating. The surfactant used in this application is a polypyrrolidone surfactant, which has excellent amphiphilicity and can effectively ensure the stability of the wetting agent system. Experiments have shown that too little surfactant leads to instability in the wetting agent, resulting in uneven coating of the glass fiber surface and ultimately affecting performance; too much surfactant, exceeding the "saturation concentration," indirectly increases production costs; furthermore, most surfactants carry a charge, while the matrix resin is essentially uncharged, and excessive charge concentration can affect the resin's penetration into the glass fiber. This application controls the solid mass of the surfactant to account for 1% to 7% of the total solid mass of the wetting agent, preferably 1% to 5%, more preferably 2% to 5%, and even more preferably 2% to 4%.

[0032] One of the key aspects of this application is the introduction of an interface reinforcing agent into the impregnating agent. The interface reinforcing agent effectively improves the interfacial bonding between glass fiber and resin, thereby enhancing the overall static mechanical properties and fatigue resistance of the composite material. The interface reinforcing agent in this application is polystyrene nanoparticles. These nanoparticles have a very large surface area, effectively increasing the contact area between the glass fiber and resin. Simultaneously, the nanoparticles on the glass fiber surface act as "protrusions," allowing them to "embed" into the resin during bonding, thus improving the interfacial bonding and making it less prone to peeling from the resin. The use of polystyrene nanoparticles allows for rapid impregnation with dicyclopentadiene resin through non-covalent interactions. The amount of polystyrene nanoparticles needs to be controlled within a certain range. Too little amount results in only a slight increase in specific surface area and "protrusion" points, failing to significantly improve the interfacial bonding between the glass fiber and resin. Too much amount leads to excessive "protrusions" on the glass fiber surface, affecting the wear resistance of the glass fiber and causing breakage during drawing and a significant increase in fuzz during subsequent use. Therefore, the theoretical solid mass of the interface reinforcing agent in this application accounts for 1% to 5% of the total solid mass of the wetting agent, preferably 1% to 4%, more preferably 1% to 3%, and even more preferably 2% to 3%.

[0033] The second key point of this application is the introduction of a crosslinking agent. The crosslinking agent plays two main roles: First, during the film-forming process of the sizing agent, the crosslinking agent can partially react with the film-forming agent, increasing the molecular weight and thus increasing the bundled nature of the glass fibers, preventing them from becoming too scattered and affecting smoothness of use. Second, some of the crosslinking agent reacts with dicyclopentadiene, increasing the interfacial bonding between the glass fibers and the resin, and improving the static mechanical properties of the composite material. Preferably, the crosslinking agent in this application is a wetting agent containing polyfunctional unsaturated double bonds, such as a copolymer of ethylene and maleic anhydride. In this application, the theoretical solid mass of the crosslinking agent after dehydration accounts for 1% to 5% of the total solid component mass of the sizing agent. This content selection can simultaneously consider the bundled nature of the glass fibers and the interfacial bonding performance between the glass fibers and the resin. Preferably, it is 1% to 4%, more preferably 2% to 4%, and most preferably 2% to 3%.

[0034] Another key aspect of this application is the wetting agent. The wetting agent significantly reduces the surface tension of the impregnating agent after film formation, improves the resin's penetration speed and effect on the glass fiber, and enhances the interfacial bonding between the glass fiber and the resin, ultimately improving the static mechanical properties of the composite material. Preferably, the wetting agent in this application is an acetylenic diol-based wetting agent, which can rapidly wet and penetrate dicyclopentadiene. In this application, the theoretical solid mass of the wetting agent after dehydration accounts for 2% to 6% of the total solid component mass of the impregnating agent, preferably 2% to 5%, more preferably 2% to 4%, and most preferably 2% to 3%.

[0035] pH adjusters are mainly used in the glass fiber industry for the hydrolysis of coupling agents and for adjusting the pH value of wetting agents. In this application, the pH adjuster can be glacial acetic acid and / or citric acid, more preferably glacial acetic acid. The solid mass of the pH adjuster accounts for 1% to 7% of the total solid mass of the wetting agent, preferably 1% to 6%, more preferably 2% to 6%, and most preferably 2% to 5%.

[0036] According to a second aspect of this application, a method for preparing the aforementioned glass fiber impregnating agent is provided, comprising the following steps:

[0037] 1S: Add water equal to 25%–40% of the total mass of the wetting agent to the container, then add the pH adjuster and silane coupling agent in sequence, and stir until the solution is clear;

[0038] 2S: Dilute the film-forming agent with water and add it to the container described in 1S;

[0039] 3S: Dilute the lubricant with warm water and add it to the container described in 2S;

[0040] 4S: Dilute the surfactant with warm water and add it to the container described in 3S;

[0041] 5S: Dilute the interface enhancer with warm water and add it to the container described in 4S;

[0042] 6S: Add the crosslinking agent to the container described in 5S after stirring and diluting it with warm water;

[0043] 7S: Dilute the wetting agent with warm water and add it to the container described in 6S, then add the remaining water and stir well.

[0044] In step 2S, the film-forming agent is diluted with 2 to 3 times its mass of water.

[0045] In step 3S, the lubricant is diluted with 5-6 times its mass of water at a temperature of 40-50°C; in step 4S, the surfactant is diluted with 3-5 times its mass of water at a temperature of 40-50°C; in step 5S, the interface enhancer is diluted with 3-5 times its mass of water at a temperature of 40-50°C; in step 5S, the crosslinking agent is diluted with 6-8 times its mass of water at a temperature of 40-50°C; and in step 7S, the wetting agent is diluted with 6-8 times its mass of water at a temperature of 40-50°C.

[0046] According to a third aspect of this application, a glass fiber product produced by coating with the aforementioned glass fiber sizing agent is provided.

[0047] According to the fourth aspect of this application, the aforementioned glass fiber sizing agent is provided for use in the preparation of yarn for dicyclopentadiene resin-based composite materials.

[0048] Glass fiber yarns produced using the impregnating agent of this application exhibit good bundle properties, and after being subjected to a certain tension, they are soft and have good dispersibility. During use, they have less fuzz and good smoothness. They penetrate quickly and completely into dicyclopentadiene resin, and the interfacial compatibility between glass fiber and resin is good. They are also suitable for weaving and pultrusion processes. The resulting composite materials have excellent static mechanical and fatigue properties. Detailed Implementation

[0049] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be arbitrarily combined with each other.

[0050] The glass fiber impregnating agent for reinforcing dicyclopentadiene resin provided in some embodiments of this application comprises an effective component and water, with a solid content of 5.0% to 8.0%. The effective component comprises a silane coupling agent, a film-forming agent, a lubricant, a surfactant, an interface reinforcing agent, a crosslinking agent, a wetting agent, and a pH adjuster. The percentage of the solid mass of each effective component to the total solid mass of the impregnating agent is expressed as follows: silane coupling agent 7% to 25%, film-forming agent 43% to 80%, lubricant 5% to 16%, surfactant 1% to 7%, interface reinforcing agent 1% to 5%, crosslinking agent 1% to 5%, wetting agent 2% to 6%, and pH adjuster 1% to 7%. The interface reinforcing agent is polystyrene nanoparticles.

[0051] In some embodiments, the percentage of the solid mass of each effective component in the wetting agent relative to the total solid mass of the wetting agent is expressed as follows: silane coupling agent 8%–23%, film-forming agent 45%–76%, lubricant 7%–15%, surfactant 1%–5%, interface enhancer 1%–4%, crosslinking agent 1%–4%, wetting agent 2%–5%, and pH adjuster 1%–6%.

[0052] In some embodiments, the percentage of the solid mass of each effective component in the wetting agent relative to the total solid mass of the wetting agent is expressed as follows: silane coupling agent 10%–21%, film-forming agent 50%–72%, lubricant 7%–14%, surfactant 2%–5%, interface enhancer 1%–3%, crosslinking agent 2%–4%, wetting agent 2%–4%, and pH adjuster 2%–6%.

[0053] In some embodiments, the percentage of the solid mass of each effective component in the wetting agent relative to the total solid mass of the wetting agent is expressed as follows: silane coupling agent 11%–18%, film-forming agent 53%–70%, lubricant 8%–13%, surfactant 2%–4%, interface enhancer 2%–3%, crosslinking agent 2%–3%, wetting agent 2%–3%, and pH adjuster 2%–5%.

[0054] In some embodiments, the silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent, wherein the first silane coupling agent is a vinyl silane coupling agent and the second silane coupling agent is an amino silane coupling agent. The mass ratio of the first silane coupling agent to the second silane coupling agent is (2-4):1, preferably (2.7-3.6):1; exceptionally, it is 3.1:1. The film-forming agent is a mixture of a first film-forming agent and a second film-forming agent, wherein the first film-forming agent is an unsaturated polyester resin with a molecular weight of 200-450; the second film-forming agent is an acrylic resin with a molecular weight of 800-1200, and the mass ratio of the first film-forming agent to the second film-forming agent is (1-3):1, preferably (1.5-2.5):1. The lubricant is a polyethylene glycol derivative lubricant; the surfactant is a polypyrrolidone surfactant; the crosslinking agent is a copolymer of ethylene and maleic anhydride; the wetting agent is an acetylenic glycol wetting agent; and the pH adjuster is citric acid and / or glacial acetic acid.

[0055] The preparation method of glass fiber impregnating agent provided in some embodiments of this application includes the following steps:

[0056] 1S: Add water equal to 25%–40% of the total mass of the wetting agent to the container, then add the pH adjuster and silane coupling agent in sequence, and stir until the solution is clear;

[0057] 2S: Dilute the film-forming agent with 2 to 3 times its mass of water and add it to the container described in 1S;

[0058] 3S: Dilute the lubricant with 5 to 6 times its mass of water at a temperature of 40 to 50°C and add it to the container described in 2S;

[0059] 4S: Dilute the surfactant with 3 to 5 times its mass of water at a temperature of 40 to 50°C and add it to the container described in 3S;

[0060] 5S: Dilute the interface enhancer with 3 to 5 times its mass of water at a temperature of 40 to 50°C and add it to the container described in 4S;

[0061] 6S: Add the crosslinking agent to the container described in 5S after stirring and diluting it with 6-8 times its mass of water at a temperature of 40-50°C;

[0062] 7S: Dilute the wetting agent with 6 to 8 times its mass of water at a temperature of 40 to 50°C, add it to the container described in 6S, then add the remaining water and stir well.

[0063] Specific formulations of some embodiments of the glass fiber impregnating agent applicable to reinforced dicyclopentadiene resin of this application are shown in Table 1.

[0064] In Examples 1-4, the solid content was 6.5%, and the vinyl silane coupling agent was γ-methacryloxypropyltrimethoxysilane, and the amino silane coupling agent was γ-aminopropyltrimethoxysilane; in Examples 5-8, the solid content was 5.0%, and the vinyl silane coupling agent was vinyltrimethoxysilane, and the amino silane coupling agent was aminopropyltriethoxysilane; in Examples 9-12, the solid content was 7.0%, and the vinyl silane coupling agent was γ-methacryloxypropyltrimethoxysilane, and the amino silane coupling agent was γ-aminopropyltrimethoxysilane.

[0065] In Examples 1-12, the first film-forming agent is an unsaturated polyester resin with a molecular weight of 200-450; the second film-forming agent is an acrylic resin with a molecular weight of 800-1200; the lubricant is a polyethylene glycol derivative lubricant; the surfactant is a polypyrrolidone surfactant; the interface reinforcing agent is polystyrene nanoparticles; the crosslinking agent is a copolymer of ethylene and maleic anhydride; the wetting agent is an acetylenic diol wetting agent; and the pH adjuster is acetic acid and / or citric acid.

[0066] The values ​​in Table 1 represent the percentage of the solid mass of each effective component to the total solid mass of the wetting agent.

[0067] Table 1 shows the proportions of each effective component of the wetting agent in the embodiments.

[0068]

[0069] Table 1 (continued) Proportions of each solid component of the wetting agent in the examples

[0070]

[0071] To better illustrate this application, the following embodiments A1 and A2 are further provided. It should be noted that the following description is for the purpose of explaining this application and not for limiting the scope of this application in any way.

[0072] Example A1

[0073] The solid content of the wetting agent is 5.5%, and the percentage of each component's mass to the total mass of the solid components is expressed as follows:

[0074]

[0075]

[0076] Among them, the vinyl silane coupling agent is vinyltrimethoxysilane, the aminosilane coupling agent is aminopropyltriethoxysilane, the first film-forming agent is an unsaturated polyester resin with a molecular weight of 200-450, the second film-forming agent is an acrylic resin with a molecular weight of 800-1200, the lubricant is a polyethylene glycol derivative lubricant, the surfactant is a polypyrrolidone surfactant, the interface reinforcing agent is polystyrene nanoparticles, the crosslinking agent is a copolymer of ethylene and maleic anhydride, the wetting agent is an acetylenic diol wetting agent, and the pH adjuster is acetic acid.

[0077] Example A2

[0078] The solid content of the wetting agent is 6.5%, and the percentage of each component's mass to the total mass of the solid components is expressed as follows:

[0079]

[0080] Among them, the vinyl silane coupling agent is γ-methacryloxypropyltrimethoxysilane, the amino silane coupling agent is γ-aminopropyltrimethoxysilane, the first film-forming agent is an unsaturated polyester resin with a molecular weight of 200-450, the second film-forming agent is an acrylic resin with a molecular weight of 800-1200, the lubricant is a polyethylene glycol derivative lubricant, the surfactant is a polypyrrolidone surfactant, the interface reinforcing agent is polystyrene nanoparticles, the crosslinking agent is a copolymer of ethylene and maleic anhydride, the wetting agent is an acetylenic glycol wetting agent, and the pH adjuster is acetic acid.

[0081] In addition, comparative examples 1-3 are provided to facilitate the explanation of the technical solutions of this application.

[0082] Comparative Example 1

[0083] The wetting agent has a solid content of 5.0%. The percentage of each solid component by mass relative to the total mass of the solid component is expressed as follows:

[0084]

[0085] The preparation method of Comparative Example 1 includes the following steps:

[0086] (1) Add 25% to 40% of the total amount of water to a container equipped with a variable speed stirrer, and add pH adjuster and silane coupling agent in sequence, stirring until the solution is clear;

[0087] (2) Dilute the film-forming agent with 3 to 5 times its weight of water and add it to the container;

[0088] (3) Dilute the lubricant with 4 to 5 times its weight of water at 55°C and add it to the container;

[0089] (4) Dilute the surfactant with 4 to 5 times its weight of water and add it to the container;

[0090] (5) Dilute the wetting agent with 5 to 6 times its weight of water at 55°C and add it to the container;

[0091] (6) Finally, add the remaining water to the container, stir well, and you will get the finished product.

[0092] Comparative Example 2

[0093] The solid content of the wetting agent is 6.0%, and the percentage of each component's mass to the total mass of the solid components is expressed as follows:

[0094]

[0095]

[0096] The preparation method of Comparative Example 2 includes the following steps:

[0097] (1) Add water of 25% to 40% of the total mass of the wetting agent to a container equipped with a variable speed stirrer, and then slowly add the pH adjuster and silane coupling agent in sequence, stirring until the solution is clear;

[0098] (2) Dilute the film-forming agent with 3 to 5 times its weight of water and add it to the container;

[0099] (3) Dilute the lubricant with 4 to 5 times its weight of water and add it to the container;

[0100] (4) Dilute the surfactant with 4 to 5 times its weight of water and add it to the container;

[0101] (5) Disperse the interface enhancer with 5 to 6 times its mass of water and add it to the container;

[0102] (6) Dilute the crosslinking agent with 5 to 6 times its weight of water and add it to the container;

[0103] (7) Finally, add the remaining water to the container and stir well to obtain the product.

[0104] Comparative Example 3

[0105] The solid content of the wetting agent is 7.0%. The percentage of each solid component by mass relative to the total mass of the solid component is expressed as follows:

[0106]

[0107] The preparation method of Comparative Example 3 includes the following steps:

[0108] (1) Add 25% to 40% of the total amount of water to a container equipped with a variable speed stirrer, and add pH adjuster and silane coupling agent in sequence, stirring until the solution is clear;

[0109] (2) Dilute the film-forming agent with 3 to 5 times its weight of water and add it to the container;

[0110] (3) Dilute the lubricant with 4 to 5 times its weight of water and add it to the container;

[0111] (4) Dilute the surfactant with 4 to 5 times its mass of water at 55°C and add it to the container;

[0112] (5) Dilute the crosslinking agent with 5 to 6 times its weight of water at 55°C and add it to the container;

[0113] (6) Finally, add the remaining water to the container, stir well, and you will get the finished product.

[0114] Table 2 records the performance test results of the glass fiber impregnating agents of Examples 1-12, Examples A1, A2 and Comparative Examples 1-3 of this application.

[0115] Table 2 Performance test results of the examples and comparative examples

[0116]

[0117] Table 2 (continued) Performance test results of examples and comparative examples

[0118]

[0119]

[0120] Table 2 (continued) Performance test results of examples and comparative examples

[0121]

[0122]

[0123] Note: (1) All data are based on 2400tex direct yarn and its unidirectional fabric; (2) The bending strength of 6mm pultruded bar is tested according to ISO 3597 test standard; (3) The shear strength of 6mm pultruded bar is tested according to ASTM D4475 test standard; (4) The tensile strength of unidirectional plate at 0 degrees and 90 degrees is tested according to ISO 527-5 test standard; (5) The fatigue performance of unidirectional plate is tested according to ISO 13003 test standard.

[0124] As can be seen from the above examples, by selecting the types and designing the content of each component of the sizing agent, we can obtain a sizing agent formulation that meets the requirements. Compared with comparative examples 1 to 3, the glass fibers prepared using the sizing agent formulation of this application in Examples 1 to 12 and Examples A1 to A2 have good performance, good yarn bundle properties, but looseness after over-tension, soft yarn, fast impregnation speed in polydicyclopentadiene resin, good interfacial bonding effect, and the pultruded rods prepared from the yarn have excellent bending and shear strength. The composite materials prepared from the fabric woven from the yarn have very good tensile strength and fatigue performance. In particular, the glass fibers prepared in Examples 2 and 5 have less hairiness, better dispersion uniformity after over-tension, and very good interfacial bonding. The impregnation speed in polydicyclopentadiene resin and the static mechanical and fatigue properties of the prepared composite materials are significantly better than those of commercially available products.

[0125] In summary, the glass fiber yarn produced using this sizing agent is soft, disperses very well under certain tension, penetrates rapidly and completely with polydicyclopentadiene resin, and exhibits excellent interfacial compatibility. It is also suitable for both pultrusion and braiding processes, and the resulting composite glass fiber exhibits excellent interfacial compatibility with the resin, demonstrating superior static mechanical and fatigue properties.

[0126] It should be noted that, in this application, the solid mass of each effective component refers to the mass of non-aqueous substances in each effective component, and is not limited to solid components.

[0127] Finally, it should be noted that in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0128] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit it. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. A glass fiber impregnating agent, characterized in that, The wetting agent comprises an effective component and water, and the solid content of the wetting agent is 5.0%~8.0%; the effective component comprises a silane coupling agent, a film-forming agent, a lubricant, a surfactant, an interface enhancer, a crosslinking agent, a wetting agent, and a pH adjuster; The percentage of the solid mass of each effective component to the total solid mass of the wetting agent is expressed as follows: Silane coupling agent 7%~25%; Film-forming agent 43%~80%; Lubricant 5%~16%; Surfactant 1%~7%; Interface enhancer 1%~5%; Crosslinking agent 1%~5% Wetting agent 2%~6%; pH adjuster 1%~7%; The interface enhancer is polystyrene nanoparticles; The silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent, wherein the first silane coupling agent is a vinyl silane coupling agent and the second silane coupling agent is an amino silane coupling agent. The film-forming agent is a mixture of a first film-forming agent and a second film-forming agent; the first film-forming agent is an unsaturated polyester resin with a molecular weight of 200-450; the second film-forming agent is an acrylic resin with a molecular weight of 800-1200. The crosslinking agent is a copolymer of ethylene and maleic anhydride.

2. The glass fiber impregnating agent as described in claim 1, characterized in that, The percentage of the solid mass of each effective component to the total solid mass of the wetting agent is expressed as follows: Silane coupling agents 8%~23%; Film-forming agent 45%~76%; Lubricant 7%~15%; Surfactant 1%~5%; Interface enhancer 1%~4%; Crosslinking agent 1%~4% Wetting agent 2%~5%; pH adjuster 1%~6%.

3. The glass fiber impregnating agent as described in claim 1 or 2, characterized in that, The mass ratio of the first silane coupling agent to the second silane coupling agent is (2~4):

1.

4. The glass fiber impregnating agent as described in claim 1, characterized in that, The mass ratio of the first film-forming agent to the second film-forming agent is (1~3):

1.

5. The glass fiber impregnating agent as described in claim 1 or 2, characterized in that, The lubricant is a polyethylene glycol derivative lubricant.

6. The glass fiber impregnating agent as described in claim 1 or 2, characterized in that, The wetting agent is an acetylenic diol wetting agent; the surfactant is a polypyrrolidone surfactant; and the pH adjuster is citric acid and / or glacial acetic acid.

7. A method for preparing a glass fiber impregnating agent as described in any one of claims 1 to 6, characterized in that, Includes the following steps: 1S: Add water equal to 25%~40% of the total mass of the wetting agent to the container, then add the pH adjuster and silane coupling agent in sequence, and stir until the solution is clear; 2S: Dilute the film-forming agent with water and add it to the container described in 1S; 3S: Dilute the lubricant with warm water and add it to the container described in 2S; 4S: Dilute the surfactant with warm water and add it to the container described in 3S; 5S: Dilute the interface enhancer with warm water and add it to the container described in 4S; 6S: Add the crosslinking agent to the container described in 5S after stirring and diluting it with warm water; 7S: Dilute the wetting agent with warm water and add it to the container described in 6S, then add the remaining water and stir well.

8. A glass fiber product produced by coating with the glass fiber sizing agent as described in any one of claims 1 to 7.

9. The application of the glass fiber sizing agent as described in any one of claims 1 to 7 in the preparation of yarn for dicyclopentadiene resin-based composite materials.

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