WO2023201777A1 - 一种玻璃纤维浸润剂及其制备方法、玻璃纤维产品和应用 - Google Patents

一种玻璃纤维浸润剂及其制备方法、玻璃纤维产品和应用 Download PDF

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Publication number
WO2023201777A1
WO2023201777A1 PCT/CN2022/090352 CN2022090352W WO2023201777A1 WO 2023201777 A1 WO2023201777 A1 WO 2023201777A1 CN 2022090352 W CN2022090352 W CN 2022090352W WO 2023201777 A1 WO2023201777 A1 WO 2023201777A1
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Prior art keywords
agent
glass fiber
silane coupling
film
coupling agent
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PCT/CN2022/090352
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English (en)
French (fr)
Inventor
杨国明
徐胜杰
费其锋
姚尧平
朱钟鸣
范亮
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巨石集团有限公司
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Priority to BR112023021595A priority Critical patent/BR112023021595A2/pt
Priority to US18/288,462 priority patent/US20240140862A1/en
Publication of WO2023201777A1 publication Critical patent/WO2023201777A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/40—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/36—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/465—Coatings containing composite materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/12—General methods of coating; Devices therefor
    • C03C25/16—Dipping
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/326—Polyureas; Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/34—Condensation polymers of aldehydes, e.g. with phenols, ureas, melamines, amides or amines
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/465—Coatings containing composite materials
    • C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Definitions

  • the present application relates to the technical field of glass fiber sizing agents, and in particular to a glass fiber sizing agent and its preparation method, glass fiber products and applications.
  • the first is to reduce the cost of raw materials, including resin, fiberglass and core materials.
  • the second is to improve the overall production efficiency to dilute the unit production cost.
  • the purpose of this application is to provide a glass fiber sizing agent.
  • the glass fiber yarn produced by coating it has good clustering properties, is soft and has good dispersion after a certain tension; it has a fast penetration speed and a complete penetration effect in epoxy resin;
  • the interface compatibility between glass fiber and resin is good; it is suitable for weaving technology, especially for the production of heavy-weight wind blade fabrics.
  • the composite material made by vacuum infusion of this fabric and epoxy resin has good static mechanics and fatigue properties.
  • a glass fiber sizing agent contains effective components and water; the solid content of the sizing agent is 4.0 to 6.0%.
  • the effective components include silane coupling agents, film-forming agents, lubricants, surfactants, leveling agents, interface enhancers, wetting agents, defoaming agents and pH regulators; each effective component of the wetting agent.
  • the percentage of the solid mass of each effective component in the sizing agent to the total solid mass of the sizing agent is expressed as follows:
  • the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:
  • the silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent, the first silane coupling agent is an aminosilane coupling agent, and the second silane coupling agent
  • the coupling agent is an epoxy silane coupling agent.
  • the mass ratio C1 of the first silane coupling agent and the second silane coupling agent is 1:5 ⁇ 1:3.
  • the first silane coupling agent is aminopropyltriethoxysilane or/and ⁇ -aminopropyltrimethoxysilane.
  • the second silane coupling agent is ⁇ -glycidoxypropyltrimethoxysilane.
  • 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 bisphenol A-type epoxy resin, and the second film-forming agent is Polyurethane resin.
  • the mass ratio C2 of the first film-forming agent to the second film-forming agent is 1:1 ⁇ 2:1.
  • the first film-forming agent is bisphenol A-type epoxy resin with a molecular weight of 2000-3000.
  • the second film-forming agent is a polyurethane resin with a molecular weight of 200 to 400.
  • the first film-forming agent is bisphenol A-type epoxy resin with a molecular weight of 2300-2700.
  • the second film-forming agent is a polyurethane resin with a molecular weight of 250 to 350.
  • the lubricant is polyethyleneimine lubricant or/and fatty amide and its derivatives.
  • the surfactant is pyrrolidone and its derivatives or/and pyridinium salt and its derivatives.
  • the defoaming agent is an organic silicone compound or/and a polyether defoaming agent.
  • the leveling agent is modified polyacrylate or/and modified organosiloxane.
  • the interface enhancer is silica nanoparticles or/and alumina nanoparticles.
  • the wetting agent is an acetylene glycol wetting agent or/and a modified polyoxyethylene derivative.
  • the pH adjuster is glacial acetic acid or/and citric acid.
  • the solid mass of each effective component of the sizing agent accounts for the percentage of the total mass of the sizing agent solids and is expressed as follows:
  • the silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent
  • the first silane coupling agent is an aminosilane coupling agent
  • the second silane coupling agent is a cyclic 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 bisphenol A-type epoxy resin.
  • the second film-forming agent is Polyurethane resin is selected; the lubricant is polyethyleneimine lubricant or/and fatty amide and its derivatives; the surfactant is pyrrolidone and its derivatives or/and pyridine salt and its derivatives; the flow
  • the leveling agent is made of modified polyacrylate or/and modified organosiloxane; the interface enhancer is made of silica nanoparticles or/and alumina nanoparticles; the wetting agent is made of acetylenic diols. agent or/and modified polyoxyethylene derivatives; the defoaming agent is an organic silicone compound or/and a polyether defoaming agent; the pH adjuster is citric acid or/and glacial acetic acid.
  • the water in the sizing agent of the present application is deionized water.
  • the role of water in the sizing agent of this application is the dispersed phase of each component.
  • a preparation method for the aforementioned glass fiber sizing agent including the following steps:
  • Pre-disperse the silane coupling agent Add 30% to 45% of the total mass of the wetting agent to water in the container, then add the pH adjuster and silane coupling agent in sequence, pre-disperse the silane coupling agent, and stir until the solution is clear. Obtain silane coupling agent pre-dispersion;
  • Dilution of film-forming agents, lubricants, surfactants, leveling agents, interface enhancers, wetting agents and defoaming agents Dilute film-forming agents, lubricants, surfactants, leveling agents, interface enhancers, wetting agents Wetting agents and defoaming agents are diluted with water respectively;
  • the film-forming agent is diluted with 3 to 4 times its mass of water; the interface enhancer is dispersed with 5 to 8 times its mass of water; and the defoaming agent is dispersed with 3 to 5 times of its mass. Its mass of water is diluted.
  • the lubricant is diluted with warm water at a temperature of 45-60°C, 5-6 times its mass; the surfactant is diluted with warm water at a temperature of 45-60°C, 4-6 times its mass.
  • the interface enhancer is diluted with warm water at a temperature of 45 to 60°C, 4 to 6 times its mass; the wetting agent is diluted with warm water at a temperature of 45 to 60°C, 5 to 6 times its mass. quality warm water for dilution.
  • the pre-dispersion of the silane coupling agent and the dilution of the film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent and defoaming agent are not in order.
  • the silane coupling agent can be pre-dispersed first. , you can also dilute the film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent and defoaming agent first, or you can do it at the same time.
  • a glass fiber product produced by coating with the aforementioned glass fiber sizing agent is provided.
  • the application of glass fiber products produced by coating the aforementioned glass fiber sizing agent in epoxy-based composite materials is provided.
  • the glass fiber sizing agent provided in some embodiments of the present application includes effective components and water.
  • the effective components include silane coupling agents, film-forming agents, lubricants, surfactants, leveling agents, interface enhancers, and wetting agents. , defoaming agent and pH regulator; among them, the solid content of the sizing agent is 4.0% to 6.0%; the percentage of the solid mass of each effective component to the total solid mass of the sizing agent is expressed as follows: Silane coupling agent 6% to 26 %, film-forming agent 45% to 78%, lubricant 5% to 15%, surfactant 1% to 6%, leveling agent 1% to 5%, interface enhancer 1% to 6%, wetting agent 1 % ⁇ 5%, defoaming agent 1% ⁇ 5%, pH adjuster 1% ⁇ 7%.
  • Silane coupling agent is one of the most reactive raw materials in the sizing system.
  • the silane hydroxyl groups formed after hydrolysis are highly active and can react with the silane hydroxyl groups on the surface of the glass fiber to form Si-O-Si bonds.
  • the coupling agent mainly plays two roles: (1) During the glass fiber drawing and forming process, due to the high traction speed, surface micro-cracks will be formed during the rapid transformation of the glass fiber from liquid to solid.
  • the silane hydroxyl group of the silane coupling agent can well compensate for these micro-cracks by reacting with the silanol hydroxyl group on the surface of the glass fiber and ensure the normal drawing process of the glass fiber; (2)
  • the R group of the coupling agent can react with the functional groups on the matrix resin, and the silicone hydroxyl group can combine with the silicone hydroxyl group on the glass fiber, so it is one of the key factors that determines the strength of FRP products. Choosing the appropriate silane coupling agent can not only improve the performance of the glass fiber itself and the mechanical properties of the subsequently prepared FRP products, but also reduce the production cost of the glass fiber.
  • the dosage of silane coupling agent needs to be controlled within a certain range. If the dosage of silane coupling agent is too small, it will affect the glass fiber drawing process and the performance of the composite material due to insufficient active groups; if the dosage is too much, If too much, part of the silane coupling agent will be wasted, increasing costs.
  • the percentage of the solid mass of the silane coupling agent to the total solid mass of the sizing agent can be 6% to 26%, or 7% to 25%, or 9% to 21%, or 9% to 21%. 10% ⁇ 16%.
  • the silane coupling agent may be a mixture of a first silane coupling agent and a second silane coupling agent
  • the first silane coupling agent may be an aminosilane coupling agent
  • the second silane coupling agent may be Epoxy silane coupling agent.
  • the aminosilane coupling agent contains amine groups and has very high reactivity. It can not only react with the film-forming agent during the baking process to ensure the overall bundling of the glass fiber, but also react quickly with the epoxy resin during subsequent processing to form Very stable chemical bonds, thereby enhancing the interface bonding between glass fiber and epoxy resin and improving the mechanical properties of composite materials.
  • the R group in the epoxy silane coupling agent is an epoxy group, which can ensure that the glass fiber can quickly penetrate into the epoxy resin due to the principle of "similar compatibility" during the subsequent preparation of composite materials.
  • the difference between the aminosilane coupling agent and the epoxy silane coupling agent is The proportional relationship will also affect the performance of the glass fiber; too much aminosilane coupling agent will make the glass fiber too tightly packed and hard, which is not conducive to penetration; too much epoxy silane coupling agent will be beneficial to the epoxy resin on the glass fiber.
  • the mass ratio C1 of the aminosilane coupling agent and the epoxy silane coupling agent can be controlled to be 1:5-1:3, or 1:4.3-1:3.7.
  • the mass ratio C1 of aminosilane coupling agent and epoxy silane coupling agent is 1:4, all properties of the glass fiber produced by the sizing prepared by combining with other components can be well achieved. Require.
  • the first silane coupling agent may be aminopropyltriethoxysilane or/and ⁇ -aminopropyltrimethoxysilane.
  • the second silane coupling agent can be gamma-glycidoxypropyltrimethoxysilane.
  • Film-forming agent is the most important and largest component of the sizing agent. It not only determines the molding process, bundling, softness and wear resistance of glass fiber, but also affects the dispersion and process smoothness of subsequent processing. In addition, film-forming agents are also one of the key factors in the interface bonding between glass fiber and matrix resin. In the actual production of glass fiber, the dosage of film-forming agent needs to be controlled within an appropriate range.
  • the solid mass of the film-forming agent can be controlled to account for 45% to 78% of the total solid mass of the sizing agent, or it can be 50% to 75%, or it can be 52% to 73%, or it can be 55% ⁇ 72%.
  • the film-forming agent can not only ensure better dispersion and softness of the glass fiber, but also ensure the smoothness of the glass fiber process, compatibility with the matrix resin and the mechanical properties of the composite material.
  • the film-forming agent may be a mixture of a first film-forming agent and a second film-forming agent.
  • the first film-forming agent may be bisphenol A-type epoxy resin
  • the second film-forming agent may be polyurethane resin.
  • the first film-forming agent can be a bisphenol A-type epoxy resin with a relatively large molecular weight. Specifically, it can be a bisphenol A-type epoxy resin with a molecular weight of 2,000 to 3,000, or a bisphenol A-type epoxy resin with a molecular weight of 2,300. ⁇ 2700 bisphenol A type epoxy resin. Epoxy resins with larger molecular weights can ensure the film-forming properties of the sizing agent.
  • the second film-forming agent can be a polyurethane resin with a smaller molecular weight. Specifically, it can be a polyurethane resin with a molecular weight of 200 to 400, or a polyurethane resin with a molecular weight of 250 to 400. It can also be a polyurethane resin with a molecular weight of 250 to 400. It is a polyurethane resin with a ratio of 250 to 350.
  • the small molecular weight polyurethane resin can ensure that the glass fiber can be easily dispersed after tension, ensuring the penetration performance and interface bonding effect. At the same time, the dosage of the two film-forming agents needs to be strictly controlled.
  • the mass ratio C2 of the first film-forming agent and the second film-forming agent can be controlled to be 1:1 ⁇ 2:1.
  • the mass ratio C2 of the first film-forming agent and the second film-forming agent in this application is 1:1 to 2:1, all properties of the prepared glass fiber can reach excellent levels.
  • the mass ratio of the silane coupling agent to the film-forming agent is 1:3 to 1:6, which not only ensures the film formation and coating uniformity of the sizing agent, but also ensures the interaction between the sizing agent and the glass.
  • the skeleton and matrix resin are fully reactive.
  • Lubricant is one of the main components of glass fiber sizing agent. Its main purpose is to increase the wear resistance of glass fiber and ensure the smoothness of the drawing process and use.
  • the lubricant in this application may be polyethyleneimine lubricant or/and fatty amide and its derivatives. This type of lubricant has very good dispersibility in water, has a significant lubrication effect, and can effectively reduce the generation of hairiness.
  • the fatty amide and its derivatives may include one or both of alkoxy-modified fatty amide and quaternized fatty amide. The amount of lubricant used in glass fiber production must also be strictly controlled.
  • the solid mass of the lubricant can be controlled to account for 5% to 15% of the total solid mass of the sizing agent, or it can be 7% to 14%, or it can be 7% to 13%, or it can be 7% to 7%. 12%.
  • Surfactants mainly play a role in stabilizing the components of the sizing agent due to their amphiphilic nature.
  • the composition of the sizing agent is complex, and different components are prone to agglomeration or even precipitation after mixing, which affects the normal drawing process and the uniformity of the sizing agent coating. Adding an appropriate amount of surfactant can effectively solve related problems.
  • the surfactant in this application can be pyrrolidone and its derivatives or/and pyridinium salt and its derivatives. It has very good amphiphilicity and is the most common surfactant in the industry. It can well ensure that the wetting agent system stability.
  • the solid mass of the surfactant can be controlled to account for 1% to 6% of the total solid mass of the sizing agent, or 1% to 5%, or 2% to 5%, or 2%. ⁇ 4%.
  • the leveling agent can effectively reduce the surface tension and improve the overall permeability of the sizing agent, thus increasing the rate at which the epoxy resin penetrates the glass fiber.
  • the leveling agent can increase the coverage of the sizing agent, so that a flat, smooth and uniform coating film can be formed during the film-forming process of the sizing agent, thereby indirectly enhancing the interface bonding between glass fiber and epoxy resin.
  • the leveling agent selected in this application can be polyacrylate or/and organosiloxane leveling agent. These two leveling agents can not only promote the flow and leveling of the coating film, but also will not affect the interlayer adhesion of the coating film. Strong, and has partial defoaming effect.
  • the polyacrylate can include one or both of epoxy-modified polyacrylate and amine-modified polyacrylate;
  • the organosiloxane leveling agent can include epoxy- and polyether-modified copolymers.
  • the amount of leveling agent needs to be strictly controlled. Too much or too little leveling agent will have adverse effects: too much leveling agent will exceed the saturation concentration, which will increase the cost of the sizing agent; too little leveling agent will not Effectively reducing surface tension, the coverage uniformity of the sizing agent cannot be guaranteed, which fundamentally affects the permeability of the glass fiber.
  • the solid mass of the leveling agent can be controlled to account for 1% to 5% of the total solid mass of the sizing agent, or 1% to 4%, or 2% to 4%.
  • interface reinforcing agents are also one of the key technical points. Due to the high glass fiber content of heavy fabrics after infusion, the fatigue resistance of composite materials often decreases significantly. Therefore, it is necessary to introduce additives that can improve the interface bonding. To improve fatigue performance, interface enhancers can play a similar role.
  • the interface enhancer in this application can be silica nanoparticles or/and alumina nanoparticles. Specifically, the interface enhancer in this application is nanoscale silica particles, and the surface of silica has a lot of silicone hydroxyl groups. , on the one hand, it can react with the silicone hydroxyl groups in glass fiber and silane coupling agents.
  • nano-level silica attachment can increase the specific surface area of glass fiber and increase the bonding sites between glass fiber and epoxy resin, thereby improving the interface bonding effect and the mechanical and fatigue properties of the final composite material. Due to its small size, nanoscale silica has very good dispersion in water and does not require additional treatment. The dosage of silica interface reinforcing agent needs to be controlled within a certain range.
  • the solid mass of the interface enhancer can be controlled to account for 1% to 6% of the total mass of the solid components of the sizing agent, or it can be 1% to 5%, or it can be 2% to 5%, or it can be 2% ⁇ 4%.
  • wetting agents can significantly reduce the surface tension of the sizing agent, accelerate the penetration speed and effect of epoxy resin into glass fiber, and enhance the interface bonding between glass fiber and matrix resin. , improve the mechanical properties of composite materials.
  • the wetting agent in this application can be an acetylenic glycol wetting agent or/and a modified polyoxyethylene derivative.
  • the wetting agent in this application is an acetylenic glycol wetting agent.
  • Acetylene glycol wetting agents have very good dispersion, can reduce surface tension, increase the adhesion of glass fiber and epoxy resin, and have low foaming/defoaming functions, which can effectively ensure the stability of glass fiber in epoxy resin. Soaked state.
  • the amount of wetting agent needs to be controlled. If too much wetting agent is used, the wetting effect will be saturated and the cost will be high, which will cause the cost of the wetting agent to be too high. If the amount is too small, the wetting effect will be affected, thereby affecting the glass. Soaking speed and soaking effect of fibers in epoxy resin.
  • the solid mass of the wetting agent can be controlled to account for 1% to 5% of the total mass of the solid components of the wetting agent, or it can be 1% to 4%, or it can be 2% to 4%, or it can be 2% ⁇ 3%.
  • Defoaming agents are mainly used to eliminate bubbles generated during the preparation and circulation of glass fiber sizing agents. During the preparation and circulation process of glass fiber sizing agent, due to the presence of emulsifiers and surfactants, a large number of bubbles will be generated. These bubbles will affect the distribution of sizing agent on the oiling roller, thereby affecting the uniformity of coating and the normal production process. Defoaming agents can effectively avoid the generation of bubbles and ensure normal production of glass fiber.
  • the defoaming agent in this application can be an organic silicone compound or/and a polyether defoaming agent. In a special example, the defoaming agent is an organic silicone compound.
  • the amount of defoaming agent needs to be controlled within a certain range. If the amount of defoaming agent is too large, the defoaming effect will be saturated, and the excess will increase the cost; if the amount is too small, the defoaming effect will not be obvious, affecting the glass fiber and environmental protection. Penetrating effect of oxygen resin.
  • the solid mass of the defoaming agent can be controlled to be 1% to 5% of the total solid mass of the sizing agent, or 2% to 4%, or 2% to 3%.
  • the glass fiber yarn products produced have good clustering properties, are soft and have good dispersion after being stretched under a certain tension; they soak into epoxy resin quickly and have a complete soaking effect; the interface compatibility between glass fiber and resin is good; applicable In the weaving process, it is especially suitable for the production of heavy-weight wind blade fabrics.
  • the composite material made of this fabric and epoxy resin vacuum infusion has good static mechanics and fatigue properties.
  • the pH regulator in this application is mainly used for hydrolysis of silane coupling agent and adjusting the pH value of the sizing agent, so that the pH value of the sizing agent is controlled within the range of 6 to 7.
  • the pH adjuster can be glacial acetic acid or/and citric acid, specifically glacial acetic acid.
  • the solid mass of the pH adjuster can be controlled to account for 1% to 7% of the total mass of the solid components of the infiltration agent, or it can be 2% to 6%, or it can be 2% to 5%.
  • the percentage of the solid mass of each effective component in the sizing to the total solid mass of the sizing is expressed as follows: silane coupling agent 7% to 25%, film-forming agent 50% to 75%, lubricant 7% ⁇ 14%, surfactant 1% ⁇ 5%, leveling agent 1% ⁇ 4%, interface enhancer 1% ⁇ 5%, wetting agent 1% ⁇ 4%, defoaming agent 2% ⁇ 4%, pH Value regulator 2% to 6%.
  • the percentage of the solid mass of each effective component in the sizing to the total solid mass of the sizing is expressed as follows: silane coupling agent 9% to 21%, film-forming agent 52% to 73%, lubricant 7% ⁇ 13%, surfactant 2% ⁇ 5%, leveling agent 2% ⁇ 4%, interface enhancer 2% ⁇ 5%, wetting agent 2% ⁇ 4%, defoaming agent 2% ⁇ 3%, pH Value regulator 2% to 6%.
  • the percentage of the solid mass of each effective component in the sizing to the total solid mass of the sizing is expressed as follows: silane coupling agent 10% to 16%, film-forming agent 55% to 72%, lubricant 7% ⁇ 12%, surfactant 2% ⁇ 4%, leveling agent 2% ⁇ 4%, interface enhancer 2% ⁇ 4%, wetting agent 2% ⁇ 3%, defoaming agent 2% ⁇ 3%, pH Value regulator 2% to 5%.
  • a glass fiber sizing agent characterized in that the sizing agent contains effective components and water, the solid content of the sizing agent is 4.0% to 6.0%; the effective components include silane coupling agent, film-forming agent, lubricant, surface activity agent, leveling agent, interface enhancer, wetting agent, defoaming agent and pH adjuster; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:
  • the silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent
  • the first silane coupling agent is an aminosilane coupling agent
  • the second silane coupling agent is an epoxy silane coupling agent.
  • a glass fiber sizing agent characterized in that the sizing agent contains effective components and water, the solid content of the sizing agent is 4.0% to 6.0%; the effective components include silane coupling agent, film-forming agent, lubricant, surface activity agent, leveling agent, interface enhancer, wetting agent, defoaming agent and pH adjuster; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:
  • 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 bisphenol A epoxy resin
  • the second film-forming agent is polyurethane resin
  • a glass fiber sizing agent characterized in that the sizing agent contains effective components and water, the solid content of the sizing agent is 4.0% to 6.0%; the effective components include silane coupling agent, film-forming agent, lubricant, surface activity agent, leveling agent, interface enhancer, wetting agent, defoaming agent and pH adjuster; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:
  • the silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent
  • the first silane coupling agent is an aminosilane coupling agent
  • the second silane coupling agent is an epoxy 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 bisphenol A-type epoxy resin
  • the second film-forming agent is polyurethane resin.
  • a glass fiber sizing agent characterized in that the sizing agent contains effective components and water, the solid content of the sizing agent is 4.0% to 6.0%; the effective components include silane coupling agent, film-forming agent, lubricant, surface activity agent, leveling agent, interface enhancer, wetting agent, defoaming agent and pH adjuster; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:
  • the lubricant is polyethyleneimine lubricant;
  • the surfactant is polypyrrolidone surfactant;
  • the leveling agent is modified polyacrylate;
  • the interface enhancer is silica nanoparticles;
  • the wetting agent is alkyne Diol wetting agent; defoaming agent is organic silicone complex; pH adjuster is acetic acid or/and citric acid.
  • a glass fiber sizing agent characterized in that the sizing agent contains effective components and water, the solid content of the sizing agent is 4.0% to 6.0%; the effective components include silane coupling agent, film-forming agent, lubricant, surface activity agent, leveling agent, interface enhancer, wetting agent, defoaming agent and pH adjuster; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:
  • the silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent, the first silane coupling agent is an aminosilane coupling agent, and the second silane coupling agent is an epoxy silane coupling agent.
  • the film-forming agent is a mixture of the first film-forming agent and the second film-forming agent.
  • the first film-forming agent is bisphenol A-type epoxy resin, and the second film-forming agent is polyurethane resin; the lubricant is polyethylene imine.
  • Lubricant or/and fatty amide and its derivatives is Lubricant or/and fatty amide and its derivatives; surfactant is pyrrolidone and its derivatives or/and pyridine salt and its derivatives; leveling agent is modified polyacrylate or/and modified organosiloxane ;
  • the interface enhancer is silica nanoparticles or/and alumina nanoparticles;
  • the wetting agent is an acetylene glycol wetting agent or/and modified polyoxyethylene derivative;
  • the defoaming agent is an organic silicone compound or / and polyether defoaming agent;
  • the pH adjuster is citric acid or/and glacial acetic acid.
  • a glass fiber sizing agent characterized in that the sizing agent contains effective components and water, the solid content of the sizing agent is 4.0% to 6.0%; the effective components include silane coupling agent, film-forming agent, lubricant, surface activity agent, leveling agent, interface enhancer, wetting agent, defoaming agent and pH adjuster; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:
  • the silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent, the first silane coupling agent is an aminosilane coupling agent, and the second silane coupling agent is an epoxy silane coupling agent.
  • the film-forming agent is a mixture of the first film-forming agent and the second film-forming agent, the first film-forming agent is bisphenol A type epoxy resin, the second film-forming agent is polyurethane resin; the first silane coupling agent and the second film-forming agent
  • the mass ratio C1 of the disilane coupling agent is 1:5-1:3; the mass ratio C2 of the first film-forming agent and the second film-forming agent is 1:1-2:1.
  • a glass fiber sizing agent characterized in that the sizing agent contains effective components and water, the solid content of the sizing agent is 4.0% to 6.0%; the effective components include silane coupling agent, film-forming agent, lubricant, surface activity agent, leveling agent, interface enhancer, wetting agent, defoaming agent and pH adjuster; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:
  • the silane coupling agent is a mixture of a first silane coupling agent and a second silane coupling agent
  • the first silane coupling agent is an aminosilane coupling agent
  • the second silane coupling agent is an epoxy silane coupling agent
  • the film-forming agent is a mixture of the first film-forming agent and the second film-forming agent, the first film-forming agent is bisphenol A type epoxy resin, the second film-forming agent is polyurethane resin; the first silane coupling agent and the second film-forming agent
  • the mass ratio C1 of the disilane coupling agent is 1:5 ⁇ 1:3; the mass ratio C2 of the first film-forming agent and the second film-forming agent is 1:1 ⁇ 2:1;
  • the lubricant is polyethyleneimine Lubricant or/and fatty amide and its derivatives; surfactant is pyrrolidone and its derivatives or/and pyridine salt and its derivatives; leveling agent is modified polyacrylate or/and modified organosiloxane ;
  • the interface enhancer is silica nanoparticles or/and alumina nanoparticles;
  • the wetting agent is an acetylene glycol wetting agent or/and modified polyoxyethylene derivative;
  • the defoaming agent is an organic silicone
  • the preparation method of the glass fiber sizing agent of Preferred Example 1 to Preferred Example 7 includes the following steps:
  • 3S Mix the silane coupling agent pre-dispersion, diluted film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent and defoaming agent, and add the remaining amount to the container of water, stir evenly.
  • the specific formulas of some examples of the glass fiber sizing agent of the present application are shown in Table 1.
  • the solid content of Examples 1 to 4 is 5.0%, the solid content of Examples 5 to 8 is 4.0%, and the solid content of Examples 9 to 12 is The solid content is 6.0%, the solid content of Example 13 is 4.5%, and the solid content of Example 14 is 5.5%.
  • the values in Table 1 are the percentage of the solid mass of each effective component in the total solid mass of the sizing agent, the C1 value and The C2 value is the ratio of the solid mass percentage of the corresponding effective components.
  • the solid content of the sizing agent is 5.5%.
  • the mass of each component of the solid component as a percentage of the total mass of the solid component is expressed as follows:
  • the preparation method of Comparative Example 1 includes the following steps:
  • Table 2 records the performance test results of the glass fiber sizing agents in Examples 1-18 of the present application and Comparative Example 1.
  • the glass fiber yarn produced by coating with this sizing agent is soft, disperses very well after a certain tension, soaks into the epoxy resin quickly and completely, and has very good interface compatibility; it is suitable for the weaving process, especially for the production of large-scale yarns.
  • the heavy weight wind blade base material can effectively solve the problems of slow resin penetration and reduced fatigue performance of heavy weight fabrics.
  • the composite material made of fabrics prepared using this sizing agent and vacuum infused with epoxy resin has very good mechanics and Anti-fatigue properties.
  • the solid mass of each effective component refers to the mass of non-aqueous substances in each effective component, and is not limited to the solid component.
  • This application provides a glass fiber sizing agent.
  • the glass fiber yarn produced by using the sizing agent of this application has good clustering properties, is soft and has good dispersion after being stretched under a certain tension. It can soak into epoxy resin very quickly and has a complete soaking effect. , the interface compatibility between glass fiber and resin is good; it is suitable for weaving process, especially for the production of heavy-weight wind blade fabrics.
  • the composite material made by vacuum infusion of this fabric and epoxy resin has good static mechanics and fatigue properties.

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Abstract

一种玻璃纤维浸润剂，包含有效组分和水，浸润剂的固含量为4.0％～6.0％；有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；各有效组分的固体质量占浸润剂固体总质量的百分比表示为：硅烷偶联剂6％～26％、成膜剂45％～78％、润滑剂5％～15％、表面活性剂1％～6％、流平剂1％～5％、界面增强剂1％～6％、润湿剂1％～5％、消泡剂1％～5％、pH值调节剂1％～7％；由该浸润剂生产的玻纤纱线集束性好、经一定张力后柔软且分散性好；在环氧树脂中浸透速度快、浸透效果完全；玻纤与树脂的界面相容性好，适用于编织工艺，尤其适用于生产大克重风力叶片织物，该织物与环氧树脂真空灌注而成的复合材料静态力学以及疲劳性能好。

Description

一种玻璃纤维浸润剂及其制备方法、玻璃纤维产品和应用
本申请要求在2022年4月20日提交中国国家知识产权局、申请号为202210415238.5、发明名称为“一种玻璃纤维浸润剂及其制备方法、玻璃纤维产品和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及玻璃纤维浸润剂技术领域，尤其涉及一种玻璃纤维浸润剂及其制备方法、玻璃纤维产品和应用。
背景技术
风电进入平价阶段后，市场竞争越发激烈，各整机商以及叶片生产商都在通过各方面降低成本、提升效率以维持行业健康稳定的发展。风力叶片主流的降本措施主要有两种途径，第一就是降低原材料成本，包括树脂、玻纤以及芯材等，第二就是提高整体的生产效率以摊薄单位生产成本。
在这种背景下，一些处于行业研究前沿的整机商提出了一个综合的解决方案——大克重织物，使用大克重织物有两点优势：(1)提升铺设效率，相同厚度主梁可以少1/3-1/2，极大地缩短了铺设时间，减少了人工和模具占用成本；(2)玻纤含量显著提升，有效降低树脂用量，大克重织物纤维之间排布更加密实，灌注后的树脂使用量可以降低2-3％。
大克重织物虽然有非常明显的成本和效率优势，但是也有着非常高的技术要求，这些要求主要是针对玻璃纤维浸润剂的。首先，大克重织物的纤维排布更加密实，铺设完成后，树脂的灌注速度就会受到影响，灌注流道变少，就会出现灌注时间更久甚至灌不透等问题，这就要求玻璃纤维浸润剂与环氧树脂有更好的相容性，提升整体的灌注速度，不影响整体的灌注时间，并确保主梁能够完全浸透；第二，大克重织物灌注后的玻纤含量提升，会直接影响主梁的疲劳性能，一般而言，在一定范围内，玻纤含量越高，疲劳性能越差，这就要求玻璃纤维浸润剂重新设计，以保证叶片的疲劳性能。
目前市场上还没有针对于玻璃纤维大克重织物的专用浸润剂，下游客户都迫切希望能够推出大克重风电织物的专门解决方案以满足行业发展的需求。因而，设计一款能够适合 于大克重风电织物用的玻璃纤维对于整个风电行业的发展具有明显的提升和促进作用，同时，对于新型复合材料前沿领域的研究有着深远的影响和明显的意义。
发明内容
本申请的目的是提供一种玻璃纤维浸润剂，由其涂覆生产的玻璃纤维纱线集束性好，经一定张力后柔软且分散性好；在环氧树脂中浸透速度快、浸透效果完全；玻纤与树脂的界面相容性好；适用编织工艺，尤其适用于生产大克重风力叶片织物，由该织物与环氧树脂真空灌注而成的复合材料静态力学及疲劳性能好。
根据本申请的一个方面，提供了一种玻璃纤维浸润剂，所述浸润剂含有有效组分和水；所述浸润剂的固含量为4.0～6.0％。所述有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；所述浸润剂各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000001
在一些实施例中，所述浸润剂中各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000002
Figure PCTCN2022090352-appb-000003
在一些实施例中，所述浸润剂各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000004
在一些实施例中，所述硅烷偶联剂为第一硅烷偶联剂和第二硅烷偶联剂的混合物，所述第一硅烷偶联剂为氨基硅烷偶联剂，所述第二硅烷偶联剂为环氧基硅烷偶联剂。
在一些实施例中，所述第一硅烷偶联剂和所述第二硅烷偶联剂的质量比C1为1:5～1:3。
在一些实施例中，所述第一硅烷偶联剂为氨丙基三乙氧基硅烷或/和γ-氨丙基三甲氧基硅烷。
在一些实施例中，所述第二硅烷偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷。
在一些实施例中，所述成膜剂为第一成膜剂和第二成膜剂的混合物，所述第一成膜剂 为双酚A型环氧树脂，所述第二成膜剂为聚氨酯树脂。
在一些实施例中，所述第一成膜剂与所述第二成膜剂的质量比C2为1:1～2:1。
在一些实施例中，所述第一成膜剂为分子量2000～3000的双酚A型环氧树脂。
在一些实施例中，所述第二成膜剂为分子量200～400的聚氨酯树脂。
在一些实施例中，所述第一成膜剂为分子量2300～2700的双酚A型环氧树脂。
在一些实施例中，所述第二成膜剂为分子量250～350的聚氨酯树脂。
在一些实施例中，所述润滑剂为聚乙烯亚胺类润滑剂或/和脂肪酰胺及其衍生物。
在一些实施例中，所述表面活性剂为吡咯烷酮及其衍生物或/和吡啶盐及其衍生物。
在一些实施例中，所述消泡剂为有机硅酮复合物或/和聚醚类消泡剂。
在一些实施例中，所述流平剂为改性的聚丙烯酸酯或/和改性有机硅氧烷。
在一些实施例中，所述界面增强剂为二氧化硅纳米粒子或/和氧化铝纳米粒子。
在一些实施例中，所述润湿剂为炔二醇类润湿剂或/和改性聚氧乙烯衍生物。
在一些实施例中，所述pH值调节剂为冰醋酸或/和柠檬酸。
在一些实施例中，所述浸润剂各有效组分的固体质量占浸润剂固体，总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000005
其中，所述硅烷偶联剂为第一硅烷偶联剂和第二硅烷偶联剂的混合物，所述第一硅烷偶联剂选用氨基硅烷偶联剂，所述第二硅烷偶联剂选用环氧基硅烷偶联剂；所述成膜剂为第一成膜剂和第二成膜剂的混合物，所述第一成膜剂选用双酚A型环氧树脂，所述第二成膜剂选用聚氨酯树脂；所述润滑剂选用聚乙烯亚胺类润滑剂或/和脂肪酰胺及其衍生物；所述表面活性剂选用吡咯烷酮及其衍生物或/和吡啶盐及其衍生物；所述流平剂选用改性的聚丙烯酸酯或/和改性有机硅氧烷；所述界面增强剂选用二氧化硅纳米粒子或/和氧化铝纳米粒子；所述润湿剂选用炔二醇类润湿剂或/和改性聚氧乙烯衍生物；所述消泡剂选用有机硅酮复合物或/和聚醚类消泡剂；所述pH值调节剂选用柠檬酸或/和冰醋酸。
在一些实施例中，本申请浸润剂中水为去离子水。本申请浸润剂中水的作用是各组分的分散相。
根据本申请的第二个方面，提供前述玻璃纤维浸润剂的制备方法，包括如下步骤：
预分散硅烷偶联剂：在容器中加入浸润剂总质量30％～45％的水，随后依次加入pH值调节剂和硅烷偶联剂，对硅烷偶联剂进行预分散，搅拌至溶液澄清，得到硅烷偶联剂预分散液；
成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂和消泡剂的稀释：将成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂和消泡剂分别用水进行稀释；
将稀释后的成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂和消泡剂溶液加入到硅烷偶联剂预分散液中，然后补足余量的水，搅拌均匀即可。
在一些实施例中，所述成膜剂采用3～4倍其质量的水进行稀释；所述界面增强剂采用5～8倍其质量的水进行分散；所述消泡剂采用3～5倍其质量的水进行稀释。
在一些实施例中，所述润滑剂采用温度为45～60℃的，5～6倍其质量的温水进行稀释；所述表面活性剂采用温度为45～60℃的，4～6倍其质量的温水进行稀释；所述界面增强剂采用温度为45～60℃的，4～6倍其质量的温水进行稀释；所述润湿剂剂采用温度为45～60℃的，5～6倍其质量的温水进行稀释。
其中，硅烷偶联剂的预分散以及成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂和消泡剂的稀释没有先后顺序，可以先预分散硅烷偶联剂，也可以先稀释成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂和消泡剂，也可以同时进行。
根据本申请的第三个方面，提供由前述玻璃纤维浸润剂涂覆生产的玻璃纤维产品。
根据本申请的第四个方面，提供前述玻璃纤维浸润剂涂覆生产的玻璃纤维产品在环氧基复合材料中的应用。
根据本申请的第五个方面，提供前述环氧基复合材料在风电领域的应用。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚，下面将结合本申请的实施例，对本申请的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互任意组合。
本申请一些实施例提供的玻璃纤维浸润剂，包含有效组分和水，有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；其中，浸润剂的固含量为4.0％～6.0％；各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：硅烷偶联剂6％～26％、成膜剂45％～78％、润滑剂5％～15％、表面活性剂1％～6％、流平剂1％～5％、界面增强剂1％～6％、润湿剂1％～5％、消泡剂1％～5％、pH值调节剂1％～7％。
硅烷偶联剂是浸润剂体系中反应活性最强的原料之一，其水解后形成的硅羟基活性高，可与玻璃纤维表面的硅羟基反应，形成Si-O-Si键。在玻璃纤维浸润剂体系中，偶联剂主要起两方面作用：(1)在玻璃纤维拉丝成型过程中，由于牵引速度很快，玻璃纤维从液态快速转变成固态过程中会形成表面微裂纹，硅烷偶联剂的硅羟基能通过与玻璃纤维表面的硅羟基反应，很好地弥补这些微裂纹，保证玻璃纤维的正常拉丝过程；(2)玻璃纤维与树脂之间的“桥梁”作用，硅烷偶联剂的R基团能够与基体树脂上的官能团反应，而硅羟基能与玻璃纤维上的硅羟基结合，因而它是决定玻璃钢制品强度的关键因素之一。选择合适的硅烷偶联剂，不仅能提高玻璃纤维本身性能以及后续所制备的玻璃钢产品的力学性能，还可以降低玻璃纤维的生产成本。在玻璃纤维浸润剂调配时，硅烷偶联剂的用量需控制在一定的范围内，硅烷偶联剂用量过少，会因为活性基团不够而影响玻璃纤维拉丝过程以及复合材料的性能；用量过多，部分硅烷偶联剂会浪费，增加成本。在一些实施例 中，硅烷偶联剂的固体质量占浸润剂固体总质量的百分比可以为6％～26％，也可以为7％～25％，也可以为9％～21％，还可以为10％～16％。
在一些实施例中，硅烷偶联剂可以为第一硅烷偶联剂和第二硅烷偶联剂的混合物，第一硅烷偶联剂可以为氨基硅烷偶联剂，第二硅烷偶联剂可以为环氧基硅烷偶联剂。氨基硅烷偶联剂中含有胺基，反应活性非常高，不仅能在烘制过程中与成膜剂反应保证玻璃纤维整体集束性，而且还能在后续加工中与环氧树脂快速发生反应，形成非常稳定的化学键，从而增强玻璃纤维与环氧树脂的界面结合，提高复合材料的力学性能。环氧基硅烷偶联剂中的R基团为环氧基团，它能够保证玻璃纤维在后续的复合材料制备过程中，因“相似相容”的原理在环氧树脂中快速浸透。本申请中，当第一硅烷偶联剂为氨基硅烷偶联剂，第二硅烷偶联剂为环氧基硅烷偶联剂时，氨基硅烷偶联剂和环氧基硅烷偶联剂两者的比例关系也会影响玻璃纤维的性能；氨基硅烷偶联剂过多会使得玻璃纤维集束性太好而且硬，不利于浸透；环氧基硅烷偶联剂过多虽然有利于环氧树脂对玻璃纤维的浸透，但是氨基硅烷偶联剂过少不仅会引起纱线集束性能不够而容易出现散丝问题，而且也会影响复合材料的力学性能。在一些实施例中，可以控制氨基硅烷偶联剂和环氧基硅烷偶联剂的质量比C1为1:5～1:3，也可以为1:4.3～1:3.7。特例性的，当氨基硅烷偶联剂和环氧基硅烷偶联剂的质量比C1为1:4时，与其他组分配合制备的浸润剂生产的玻璃纤维各项性能都能很好的达到要求。
在一些实施例中，第一硅烷偶联剂可以为氨丙基三乙氧基硅烷或/和γ-氨丙基三甲氧基硅烷。在一些实施例中，第二硅烷偶联剂可以为γ-缩水甘油醚氧丙基三甲氧基硅烷。
成膜剂是浸润剂中最重要也是占比最多的成分，它不仅能决定玻璃纤维的成型过程、集束性、柔软度和耐磨性，而且还能影响后续加工的分散性和工艺顺畅性，此外，成膜剂也是玻璃纤维与基体树脂界面结合的关键因素之一。在玻璃纤维实际生产中，成膜剂的用量需控制在合适的范围内。研究表明，成膜剂含量不足，会导致浸润剂涂覆出现问题，不能确保浸润剂有效保护玻璃纤维，从而影响玻璃纤维地使用工艺性能和力学性能；成膜剂含量过多，则会使得纱线集束性过好，不容易散开，毛羽增多，也不利于树脂的浸透。在一些实施例中，可以控制成膜剂的固体质量占浸润剂固体总质量的百分比为45％～78％，也可以为50％～75％，也可以为52％～73％，还可以为55％～72％。在上述范围内，成膜剂不仅能确保玻璃纤维有较好的分散性和柔软度，而且还能保证玻璃纤维工艺顺畅性、与基体树脂的相容性以及复合材料的力学性能。
在一些实施例中，成膜剂可以为第一成膜剂和第二成膜剂的混合物。其中，第一成膜剂可以为双酚A型环氧树脂，第二成膜剂可以为聚氨酯树脂。在一些实施例中，第一成膜剂可以为分子量较大的双酚A型环氧树脂，具体的，可以为分子量为2000～3000的双酚A型环氧树脂，也可以为分子量为2300～2700的双酚A型环氧树脂。分子量较大的环氧树脂能够确保浸润剂的成膜性。在一些实施例中，第二成膜剂可以为分子量较小的聚氨酯树脂，具体的，可以为分子量为200～400的聚氨酯树脂，也可以为分子量为250～400的聚氨酯树脂，还可以为分子量为250～350的聚氨酯树脂。小分子量的聚氨酯树脂，能保证玻璃纤维在经过张力以后能够非常容易地分散，保证浸透性能以及界面结合作用。同时，两种成膜剂的用量需严格控制，第一成膜剂用量过多，会导致集束性过好，纱线不容易被树脂浸透；第二成膜剂用量过多，则会导致纱线过于柔软，容易出现散丝现象，影响后续的使用工艺性能。在一些实施例中，可以控制第一成膜剂和第二成膜剂的质量比C2为1:1～2:1。当本申请中第一成膜剂和第二成膜剂的质量比C2为1:1～2:1时，制备的玻璃纤维各项性能均能达到优良的程度。
在一些实施例中，硅烷偶联剂和成膜剂的质量比为1:3～1:6，其作用为既保证了浸润剂的成膜以及涂覆均匀性，又可以给予浸润剂与玻璃骨架以及基体树脂充分的反应活性。
润滑剂是玻璃纤维浸润剂的主要成分之一，其主要是为了增加玻璃纤维的耐磨性，保证拉丝过程以及使用过程中的顺畅性。本申请的润滑剂可以为聚乙烯亚胺类润滑剂或/和脂肪酰胺及其衍生物。此类润滑剂在水中具有非常好的分散性，润滑效果显著，能够有效减少毛羽的产生。其中，脂肪酰胺及其衍生物可以包括烷氧基改性的脂肪酰胺、季铵化的脂肪酰胺中的一种或两种。在玻璃纤维生产中润滑剂的用量也要严格控制，润滑剂用量太少，会影响拉丝以及使用过程的顺畅性，容易引起拉丝过程中的断丝以及后续使用中断纱等问题；但是过多的润滑剂不仅会增加成本，而且也会影响玻璃纤维的使用工艺性，因为多余的润滑剂在玻璃纤维使用中很容易粘附在张力设备的表面，随着粘结的润滑剂增多，粘附力增加，也会导致纱线粘结以及断纱等情况。在一些实施例中，可以控制润滑剂的固体质量占浸润剂固体总质量为5％～15％，也可以为7％～14％，也可以为7％～13％，还可以为7％～12％。
表面活性剂由于其具有两亲性，因而主要起着稳定浸润剂各组分的作用。浸润剂成分复杂，不同的组分在混合后容易出现团聚甚至沉淀问题，从而影响正常拉丝过程以及浸润剂涂覆的均匀性，加入适量的表面活性剂就能有效地解决相关问题。本申请的表面活性剂 可以为吡咯烷酮及其衍生物或/和吡啶盐及其衍生物，其具有非常好的两亲性，是工业中最常见的表面活性剂，它能够很好地保证浸润剂体系的稳定性。同时，浸润剂中表面活性剂用量太少，浸润剂会发生沉降，出现表面涂覆不均匀问题，并最终影响玻璃纤维的性能；用量过大，达到“饱和浓度”后，多余部分不起到作用间接增加生产成本，并且大多数表面活性剂都带有电荷，而基体树脂是不带电的，过多的电荷集中会影响树脂对玻璃纤维的浸透，因而表面活性剂的用量有一定的要求。在一些实施例中，可以控制表面活性剂的固体质量占浸润剂固体总质量的1％～6％，也可以为1％～5％，也可以为2％～5％，还可以为2％～4％。
流平剂能有效降低表面张力，改善浸润剂整体的渗透性，从而提高环氧树脂浸透玻璃纤维的速率。此外，流平剂可以增加浸润剂的覆盖性，使浸润剂成膜过程中形成一个平整、光滑、均匀的涂膜，从而间接增强玻璃纤维与环氧树脂的界面结合作用。本申请选用的流平剂可以为聚丙烯酸酯或/和有机硅氧烷流平剂，这两种流平剂不仅可以促进涂膜的流动和流平，还不会影响涂膜的层间附着力，并且带有部分消泡作用。其中，聚丙烯酸酯可以包括环氧改性的聚丙烯酸酯、胺基改性的聚丙烯酸酯中的一种或两种；有机硅氧烷流平剂可以包括环氧和聚醚改性的共聚物、环氧和聚酯改性的共聚物中的一种或两种。同时，需严格控制流平剂的用量，流平剂用量过多或过少都会产生不利影响：流平剂用量过多，超过饱和浓度，会增加浸润剂成本；流平剂用量过少，不能有效降低表面张力，浸润剂的覆盖均匀性不能保证，从根本上影响玻璃纤维的浸透性。在一些实施例中，可以控制流平剂的固体质量占浸润剂固体总质量为1％～5％，也可以为1％～4％，还可以为2％～4％。
本申请中，界面增强剂的使用也是关键技术点之一，大克重织物由于灌注后玻璃纤维含量较高，复合材料的耐疲劳性能往往会明显下降，因而需要引入能够提升界面结合的助剂来提升疲劳性能，界面增强剂就能起到类似作用。本申请中界面增强剂可以选用二氧化硅纳米粒子或/和氧化铝纳米粒子，特例性地，本申请中的界面增强剂为纳米级二氧化硅颗粒，二氧化硅表面具有非常多的硅羟基，一方面，它能与玻璃纤维以及硅烷偶联剂中的硅羟基发生反应，另一方面，它也能参与到环氧树脂与胺固化剂的反应中，起到非常好的连接作用。此外，纳米级别的二氧化硅附着能够增加玻璃纤维的比表面积，增加玻璃纤维与环氧树脂的结合位点，进而提升界面结合作用以及最终复合材料的力学和疲劳性能。纳米级的二氧化硅由于其尺寸很小，在水中具有非常好的分散性，不用进行额外处理。二氧化硅界面增强剂的用量需要控制在一定的范围内，用量太少，比表面积以及结合位点增加 不多，增强玻璃纤维与树脂的界面结合不明显；用量过多，玻璃纤维表面的“突起”过多，则会影响玻璃纤维的耐磨性，导致拉丝过程不顺畅以及毛羽增多等问题。在一些实施例中，可以控制界面增强剂的固体质量占浸润剂固体组分总质量为1％～6％，也可以为1％～5％，也可以为2％～5％，还可以为2％～4％。
本申请的另一关键点则是润湿剂的使用，润湿剂能够显著降低浸润剂的表面张力，加快环氧树脂对玻璃纤维的浸透速度和效果，并增强玻璃纤维与基体树脂的界面结合，提升复合材料的力学性能。本申请的润湿剂可以为炔二醇类润湿剂或/和改性聚氧乙烯衍生物，特例性的，本申请润湿剂为炔二醇类润湿剂。炔二醇类润湿剂具有非常好的分散性，能够降低表面张力，增加玻璃纤维和环氧树脂的附着，同时自带低泡/消泡功能，可以有效保证玻璃纤维在环氧树脂中的浸透状态。同时，润湿剂的用量需进行控制，若润湿剂使用过多，润湿效果饱和，成本又高，会导致浸润剂成本过高；用量过少，则会影响润湿效果，从而影响玻璃纤维在环氧树脂中的浸透速度和浸透效果。在一些实施例中，可以控制润湿剂的固体质量占浸润剂固体组分总质量为1％～5％，也可以为1％～4％，也可以为2％～4％，还可以为2％～3％。
消泡剂主要用于消除玻璃纤维浸润剂在配制以及循环过程中产生的气泡。玻璃纤维浸润剂配制和循环过程中由于乳化剂及表面活性剂的存在，会产生大量的气泡，这些气泡会影响涂油辊上的浸润剂分布，进而影响涂覆均匀性以及正常的生产过程，而消泡剂可以有效避免气泡的产生，保证玻璃纤维正常生产。本申请消泡剂可以为有机硅酮复合物或/和聚醚类消泡剂，特例性的，消泡剂为有机硅酮复合物。并且，消泡剂的用量需控制在一定的范围内，消泡剂用量过大，消泡效果饱和，多余部分会增加成本；用量过少，则会消泡效果不明显，影响玻璃纤维与环氧树脂的浸透效果。在一些实施例中，可以控制消泡剂的固体质量占浸润剂固体组分总质量为1％～5％，也可以为2％～4％，还可以为2％～3％。
发明人通过实验发现，使用本申请的成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂与硅烷偶联剂配伍，并且在合适的含量配比下，所生产的玻璃纤维纱线产品的集束性好，经一定张力后柔软且分散性好；在环氧树脂中浸透速度快、浸透效果完全；玻璃纤维与树脂的界面相容性好；适用于编织工艺，尤其适用于生产大克重风力叶片织物，由该织物与环氧树脂真空灌注而成的复合材料静态力学及疲劳性能好。
本申请的pH值调节剂主要用于硅烷偶联剂的水解以及调节浸润剂的pH值，使浸润剂的pH值控制在6～7的范围内。本申请中pH值调节剂可以为冰醋酸或/和柠檬酸，特例 性地为冰醋酸。在一些实施例中，可以控制pH值调节剂的固体质量占浸润剂固体组分总质量百分比为1％～7％，也可以为2％～6％，还可以为2％～5％。
在一些实施例中，浸润剂中各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：硅烷偶联剂7％～25％、成膜剂50％～75％、润滑剂7％～14％、表面活性剂1％～5％、流平剂1％～4％、界面增强剂1％～5％、润湿剂1％～4％、消泡剂2％～4％、pH值调节剂2％～6％。
在一些实施例中，浸润剂中各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：硅烷偶联剂9％～21％、成膜剂52％～73％、润滑剂7％～13％、表面活性剂2％～5％、流平剂2％～4％、界面增强剂2％～5％、润湿剂2％～4％、消泡剂2％～3％、pH值调节剂2％～6％。
在一些实施例中，浸润剂中各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：硅烷偶联剂10％～16％、成膜剂55％～72％、润滑剂7％～12％、表面活性剂2％～4％、流平剂2％～4％、界面增强剂2％～4％、润湿剂2％～3％、消泡剂2％～3％、pH值调节剂2％～5％。
本申请提供的玻璃纤维浸润剂中，选择各组分含量的上述范围的有益效果将通过实施例给出具体实验数据进行说明。
下面是根据本申请的玻璃纤维浸润剂中所包括的各组分的优选取值范围示例。
优选示例一
一种玻璃纤维浸润剂，其特征在于，浸润剂包含有效组分和水，浸润剂的固含量为4.0％～6.0％；有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；浸润剂各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000006
Figure PCTCN2022090352-appb-000007
其中，硅烷偶联剂为第一硅烷偶联剂和第二硅烷偶联剂的混合物，第一硅烷偶联剂为氨基硅烷偶联剂，第二硅烷偶联剂为环氧基硅烷偶联剂。
优选示例二
一种玻璃纤维浸润剂，其特征在于，浸润剂包含有效组分和水，浸润剂的固含量为4.0％～6.0％；有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；浸润剂各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000008
其中，成膜剂为第一成膜剂和第二成膜剂的混合物，第一成膜剂为双酚A型环氧树脂，第二成膜剂为聚氨酯树脂。
优选示例三
一种玻璃纤维浸润剂，其特征在于，浸润剂包含有效组分和水，浸润剂的固含量为4.0％～6.0％；有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；浸润剂各有效组分的固体质量占浸润剂固体总质 量的百分比表示如下：
Figure PCTCN2022090352-appb-000009
其中，硅烷偶联剂为第一硅烷偶联剂和第二硅烷偶联剂的混合物，第一硅烷偶联剂为氨基硅烷偶联剂，第二硅烷偶联剂为环氧基硅烷偶联剂；成膜剂为第一成膜剂和第二成膜剂的混合物，第一成膜剂为双酚A型环氧树脂，第二成膜剂为聚氨酯树脂。
优选示例四
一种玻璃纤维浸润剂，其特征在于，浸润剂包含有效组分和水，浸润剂的固含量为4.0％～6.0％；有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；浸润剂各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000010
Figure PCTCN2022090352-appb-000011
其中，润滑剂为聚乙烯亚胺类润滑剂；表面活性剂为聚吡咯烷酮类表面活性剂；流平剂为改性的聚丙烯酸酯；界面增强剂为二氧化硅纳米粒子；润湿剂为炔二醇类润湿剂；消泡剂为有机硅酮复合物；pH值调节剂为醋酸或/和柠檬酸。
优选示例五
一种玻璃纤维浸润剂，其特征在于，浸润剂包含有效组分和水，浸润剂的固含量为4.0％～6.0％；有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；浸润剂各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000012
其中，硅烷偶联剂为第一硅烷偶联剂和第二硅烷偶联剂的混合物，第一硅烷偶联剂为氨基硅烷偶联剂，第二硅烷偶联剂为环氧基硅烷偶联剂；成膜剂为第一成膜剂和第二成膜剂的混合物，第一成膜剂为双酚A型环氧树脂，第二成膜剂为聚氨酯树脂；润滑剂为聚乙烯亚胺类润滑剂或/和脂肪酰胺及其衍生物；表面活性剂为吡咯烷酮及其衍生物或/和吡啶盐及其衍生物；流平剂为改性的聚丙烯酸酯或/和改性有机硅氧烷；界面增强剂为二氧化硅纳米粒子或/和氧化铝纳米粒子；润湿剂为炔二醇类润湿剂或/和改性聚氧乙烯衍生物；消泡剂为有机硅酮复合物或/和聚醚类消泡剂；pH值调节剂为柠檬酸或/和冰醋酸。
优选示例六
一种玻璃纤维浸润剂，其特征在于，浸润剂包含有效组分和水，浸润剂的固含量为 4.0％～6.0％；有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；浸润剂各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000013
其中，硅烷偶联剂为第一硅烷偶联剂和第二硅烷偶联剂的混合物，第一硅烷偶联剂为氨基硅烷偶联剂，第二硅烷偶联剂为环氧基硅烷偶联剂；成膜剂为第一成膜剂和第二成膜剂的混合物，第一成膜剂为双酚A型环氧树脂，第二成膜剂为聚氨酯树脂；第一硅烷偶联剂与第二硅烷偶联剂的质量比C1为1:5～1:3；第一成膜剂与第二成膜剂的质量比C2为1:1～2:1。
优选示例七
一种玻璃纤维浸润剂，其特征在于，浸润剂包含有效组分和水，浸润剂的固含量为4.0％～6.0％；有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；浸润剂各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000014
Figure PCTCN2022090352-appb-000015
其中，硅烷偶联剂为第一硅烷偶联剂和第二硅烷偶联剂的混合物，第一硅烷偶联剂为氨基硅烷偶联剂，第二硅烷偶联剂为环氧基硅烷偶联剂；成膜剂为第一成膜剂和第二成膜剂的混合物，第一成膜剂为双酚A型环氧树脂，第二成膜剂为聚氨酯树脂；第一硅烷偶联剂与第二硅烷偶联剂的质量比C1为1:5～1:3；第一成膜剂与第二成膜剂的质量比C2为1:1～2:1；润滑剂为聚乙烯亚胺类润滑剂或/和脂肪酰胺及其衍生物；表面活性剂为吡咯烷酮及其衍生物或/和吡啶盐及其衍生物；流平剂为改性的聚丙烯酸酯或/和改性有机硅氧烷；界面增强剂为二氧化硅纳米粒子或/和氧化铝纳米粒子；润湿剂为炔二醇类润湿剂或/和改性聚氧乙烯衍生物；消泡剂为有机硅酮复合物或/和聚醚类消泡剂；pH值调节剂为柠檬酸或/和冰醋酸。
优选示例一至优选示例七的玻璃纤维浸润剂的制备方法，包括以下步骤：
1S：在容器中加入浸润剂总质量30％～45％的水，随后依次加入pH值调节剂和硅烷偶联剂，对硅烷偶联剂进行预分散，搅拌至溶液澄清，得到硅烷偶联剂预分散液；
2S：将成膜剂用3～4倍其质量的水稀释，将润滑剂用55℃、5～6倍其质量的水稀释，将表面活性剂用55℃、4～6倍其质量的温水稀释，将流平剂用55℃、4～6倍其质量的温水搅拌和稀释，将界面增强剂剂用5～8倍其质量的水稀释，将润湿剂用55℃、5～6倍其质量的水稀释，将消泡剂用3～5倍其质量的水稀释；
3S：将硅烷偶联剂预分散液、经稀释的成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂和消泡剂进行混合，并向容器中补足余量的水，搅拌均匀。
本申请的玻璃纤维浸润剂的部分实施例的具体配方如表1所示，实施例1～4的固含量为5.0％，实施例5～8的固含量为4.0％，实施例9～12的固含量为6.0％，实施例13的固含量为4.5％，实施例14的固含量为5.5％，表1中的数值为各有效组分固体质量占浸润剂固体总质量的百分比，C1值和C2值为相应有效组分固体质量百分比的比值。
表1 实施例的浸润剂各有效组分的配比
Figure PCTCN2022090352-appb-000016
表1(续) 实施例的浸润剂各有效组分的配比
Figure PCTCN2022090352-appb-000017
Figure PCTCN2022090352-appb-000018
表1(续) 实施例的浸润剂各有效组分的配比
Figure PCTCN2022090352-appb-000019
Figure PCTCN2022090352-appb-000020
此外，本文还列举了1个对比例，便于解释本申请的技术方案。
对比例1
浸润剂固含量5.5％。固体组分各成分的质量占所述固体组分总质量的百分比表示如下：
Figure PCTCN2022090352-appb-000021
对比例1的制备方法，包括以下步骤：
(1)在装有变速搅拌器的容器中加入总量30％～45％的水，分别依次加入pH值调节剂和酰胺基硅烷偶联剂，搅拌直至溶液澄清；
(2)将成膜剂用其质量3～5倍的水稀释后，加入容器中；
(3)将润滑剂用其质量4～6倍的55℃水稀释后，加入容器中；
(4)将表面活性剂用其质量4～5倍的水稀释后，加入容器中；
(5)将消泡剂用其质量3～5倍的水稀释后，加入容器中；
(6)最后，向容器中补足余量的水，搅拌均匀，即得成品。
表2中记录了本申请实施例1-18以及对比例1的玻璃纤维浸润剂的性能检测结果。
表2 实施例及对比例的性能测试结果
Figure PCTCN2022090352-appb-000022
表2(续) 实施例及对比例的性能测试结果
Figure PCTCN2022090352-appb-000023
表2(续) 实施例及对比例的性能测试结果
Figure PCTCN2022090352-appb-000024
注：(1)所有数据均基于2400tex纱线及其单向织物测试；(2)90度拉伸强度基于 ISO527-5测试标准测试；(3)疲劳性基于ISO13003测试标准测试。
从上述的实施例中可以看出，通过对浸润剂各组分的种类选择以及含量的设计，我们可以得到满足要求的浸润剂配方，与对比例1相比，本申请实施例1-18制备的玻璃纤维具有良好的性能，玻璃纤维毛羽少，纱线过张力后松散，纱质柔软，在环氧树脂中浸透速度快，界面结合效果好，制备的复合材料的力学性能和疲劳性能优异。
综上，采用该浸润剂涂覆生产的玻璃纤维纱线柔软，经过一定张力后分散非常好，与环氧树脂浸透快速而且完全，界面相容性非常好；适用编织工艺，尤其适用于生产大克重风力叶片基材，能够有效解决大克重织物的树脂浸透慢以及疲劳性能下降的问题，使用该该浸润剂制备的织物与环氧树脂真空灌注而成的复合材料具有非常好的力学以及抗疲劳性能。
需要说明的是，本申请中，各有效组分的固体质量是指各有效组分中非水物质的质量，并不限于是固体成分。
最后应说明的是：在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包含一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个…”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
以上实施例仅用以说明本申请的技术方案，而非对其限制。尽管参照前述实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的精神和范围。
工业实用性
本申请提供了一种玻璃纤维浸润剂，采用本申请的浸润剂生产的玻璃纤维纱线集束性好，经一定张力后柔软且分散性好，在环氧树脂中浸透速度非常快，浸透效果完全，玻璃纤维与树脂的界面相容性好；适用编织工艺，尤其适用于生产大克重风力叶片织物，该织物与环氧树脂真空灌注而成的复合材料静态力学及疲劳性能好。

Claims (15)

  1. 一种玻璃纤维浸润剂，其特征在于，所述浸润剂包含有效组分和水，所述浸润剂的固含量为4.0％～6.0％；所述有效组分包含硅烷偶联剂、成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂、消泡剂和pH值调节剂；所述浸润剂各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
    Figure PCTCN2022090352-appb-100001
  2. 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，所述浸润剂中各有效组分的固体质量占浸润剂固体总质量的百分比表示如下：
    Figure PCTCN2022090352-appb-100002
  3. 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，所述硅烷偶联剂为第一硅烷偶联剂和第二硅烷偶联剂的混合物，所述第一硅烷偶联剂为氨基硅烷偶联剂，所述第二硅烷偶联剂为环氧基硅烷偶联剂。
  4. 根据权利要求3所述的玻璃纤维浸润剂，其特征在于，所述第一硅烷偶联剂与所述第二硅烷偶联剂的质量比C1为1:5～1:3。
  5. 根据权利要求3所述的玻璃纤维浸润剂，其特征在于，所述第一硅烷偶联剂为氨丙基三乙氧基硅烷或/和γ-氨丙基三甲氧基硅烷；所述第二硅烷偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷。
  6. 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，所述成膜剂为第一成膜剂和第二成膜剂的混合物；所述第一成膜剂为双酚A型环氧树脂；所述第二成膜剂为聚氨酯树脂。
  7. 根据权利要求6所述的玻璃纤维浸润剂，其特征在于，所述第一成膜剂与所述第二成膜剂的质量比C2为1:1～2:1。
  8. 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，所述润滑剂为聚乙烯亚胺类润滑剂或/和脂肪酰胺及其衍生物；所述表面活性剂为吡咯烷酮及其衍生物或/和吡啶盐及其衍生物。
  9. 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，所述消泡剂为有机硅酮复合物或/和聚醚类消泡剂；所述流平剂为改性的聚丙烯酸酯或/和改性有机硅氧烷。
  10. 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，所述界面增强剂为二氧化硅纳米粒子或/和氧化铝纳米粒子。
  11. 根据权利要求1所述的玻璃纤维浸润剂，其特征在于，所述润湿剂为炔二醇类润湿剂或/和改性聚氧乙烯衍生物。
  12. 一种如权利要求1～11任一项所述的玻璃纤维浸润剂的制备方法，其特征在于，包括如下步骤：
    预分散硅烷偶联剂：在容器中加入浸润剂总质量30％～45％的水，随后依次加入pH值调节剂和硅烷偶联剂，对硅烷偶联剂进行预分散，搅拌至溶液澄清，得到硅烷偶联剂预分散液；
    成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂和消泡剂的稀释：对成 膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂和消泡剂分别用水进行稀释；
    将稀释后的成膜剂、润滑剂、表面活性剂、流平剂、界面增强剂、润湿剂和消泡剂加入硅烷偶联剂预分散液中，补足余量的水，搅拌均匀即得玻璃纤维浸润剂。
  13. 一种由如权利要求1～11任一项所述的玻璃纤维浸润剂涂覆生产的玻璃纤维产品。
  14. 一种根据权利要求13所述的玻璃纤维产品在环氧基复合材料中的应用。
  15. 一种根据权利要求14所述的环氧基复合材料在风电领域的应用。
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