CN112521030B - High-mechanical-property glass fiber impregnating compound and preparation method and application thereof - Google Patents

High-mechanical-property glass fiber impregnating compound and preparation method and application thereof Download PDF

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CN112521030B
CN112521030B CN202011417761.9A CN202011417761A CN112521030B CN 112521030 B CN112521030 B CN 112521030B CN 202011417761 A CN202011417761 A CN 202011417761A CN 112521030 B CN112521030 B CN 112521030B
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silane coupling
coupling agent
emulsion
unsaturated polyester
agent
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CN112521030A (en
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章建忠
陆琦
刘阳
张鑫
张志坚
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Jushi Group Co Ltd
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Jushi Group Co Ltd
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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
    • C03C25/465—Coatings containing composite materials
    • C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • 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
    • C03C25/323—Polyesters, e.g. alkyd 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
    • C03C25/24—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
    • C03C25/24—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
    • C03C25/42—Coatings containing inorganic 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
    • C03C25/42—Coatings containing inorganic materials
    • C03C25/44—Carbon, e.g. graphite
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/06—Unsaturated polyesters

Abstract

The application provides a glass fiber impregnating compound with high mechanical property, which comprises an effective component and water; the mass of the effective component accounts for 2.5-10.5% of the total mass of the impregnating compound; the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows: 7.0-19% of a coupling agent, 3.0-8.0% of a lubricant, 59-87% of a film forming agent, 2.0-10% of a dispersing agent and 1.0-4.0% of a pH value regulator; wherein the film forming agent consists of nano material modified epoxy emulsion and unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1-1: 4. The glass fiber yarn produced by coating the impregnating compound has high breaking strength of glass fiber, good compatibility with target polyester resin and high mechanical property of SMC products.

Description

High-mechanical-property glass fiber impregnating compound and preparation method and application thereof
Technical Field
The application relates to the technical field of glass fiber reinforced resin, in particular to a glass fiber impregnating compound with high mechanical property, a preparation method of the impregnating compound and application of the impregnating compound.
Background
The glass fiber reinforced plastic material is prepared by compounding glass fiber serving as a reinforcing material and a thermosetting polymer. The high-strength light-weight high-strength corrosion-resistant steel has the advantages of light weight, high strength, corrosion resistance, low cost, high industrial design and the like, and is widely favored in the application fields of automobiles, rail transit and the like. In recent years, with the development of lightweight automobiles, some half-junction members and even structural members, which are originally made of steel or alloy, are gradually replaced by glass fiber reinforced plastic materials. Therefore, more severe requirements are also put on the mechanical strength of the glass fiber reinforced plastics.
The glass fiber is used as a main reinforcing material of the glass fiber reinforced plastic, and the glass fiber has strong surface polarity and cannot be compatible with a polymer matrix material (such as unsaturated polyester) with weak polarity, so that the problem of interface combination between the reinforcing material and matrix resin is easily caused. When the composite material is subjected to external load, the resin matrix cannot transfer the composite material to the glass fiber with relatively high mechanical property, so that the overall mechanical property of the composite material is influenced. Therefore, the surface of the finished glass fiber is usually coated with a layer of sizing agent (the main components include polymer emulsion film former, coupling agent, lubricant, antistatic agent, etc.) to play a role of transition connection between the glass fiber and the polymer material. The existing glass fiber impregnating compound is mainly used as a bridge through a silane coupling agent, and is connected with glass fibers and a resin matrix through a single chemical bond, and simultaneously, microcracks generated on the surface in the production process of the glass fibers are compensated to a certain extent. However, the silane coupling agent is subjected to bulk polycondensation, so that the bonding sites are limited, the problem of interfacial bonding between the glass fibers and the resin matrix still exists, and microcracks of the glass fibers also remain in large quantities. Therefore, how to develop the impregnating compound can enhance the surface integrity of the glass fiber and enhance the interface bonding of the glass fiber and the matrix resin, thereby enhancing the tensile breaking strength of the glass fiber and the mechanical property of the glass fiber reinforced resin composite material, and becoming a key problem for further expanding the application field of the glass fiber reinforced plastic material.
Disclosure of Invention
The glass fiber produced by coating the glass fiber impregnating compound has the advantages of high tensile breaking strength of precursor, good interface bonding with target unsaturated polyester resin, good soaking effect, good cutting dispersibility, less hairiness generated in production and use and the like. Meanwhile, the glass fiber reinforced unsaturated polyester resin composite material produced by using the impregnating compound can obviously improve the mechanical property of the composite material.
In order to achieve the technical effects, the following technical scheme is adopted in the application:
according to one aspect of the application, a high-mechanical-property glass fiber impregnating compound is provided, and the impregnating compound comprises an effective component and water; wherein the effective components comprise a silane coupling agent, a lubricant, a film forming agent, a dispersing agent and a pH value regulator; the mass of the effective component accounts for 2.5-10.5% of the total mass of the impregnating compound;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
7.0-19% of a silane coupling agent;
3.0-8.0% of a lubricant;
59-87% of a film forming agent;
2.0-10% of a dispersant;
1.0-4.0% of a pH value regulator;
wherein the film forming agent consists of a nano material modified epoxy emulsion and an unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1-1: 4;
the nano material modified epoxy emulsion is self-emulsifying water-based epoxy emulsion grafted by one or a mixture of any more of nano silicon oxide, nano titanium oxide, graphene and carbon nano tubes;
the nano material modified epoxy emulsion is a nano material modified bisphenol F type epoxy emulsion and/or a nano material modified bisphenol S type epoxy emulsion;
the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent; the first silane coupling agent is an aminoethyl silane coupling agent; the second silane coupling agent is a silane coupling agent containing vinyl and ester groups;
the dispersing agent is polyethylene glycol and/or polypropylene glycol;
the lubricant is one or a mixture of any more of fatty acid lubricant, fatty amide lubricant and polyol ester lubricant.
Wherein the bisphenol F type epoxy emulsion is an emulsion prepared from bisphenol F type epoxy resin; the bisphenol S type epoxy emulsion is an emulsion prepared from bisphenol S type epoxy resin.
Preferably, the epoxy equivalent of the bisphenol F type epoxy resin is 600-4500 g/eq.
Preferably, the epoxy equivalent of the bisphenol S type epoxy resin is 600-4500 g/eq.
Preferably, the solid content of the nano material modified epoxy emulsion is 45-55%.
Preferably, the unsaturated polyester emulsion is a branched chain type unsaturated polyester emulsion with the unsaturation degree of 200-1500.
Wherein the unsaturated polyester emulsion is an emulsion prepared from unsaturated polyester resin.
Preferably, the solid content of the unsaturated polyester emulsion is 25-35%.
Preferably, the mass ratio of the first silane coupling agent to the second silane coupling agent is 1:1 to 1: 5.
Preferably, the first silane coupling agent is one or a mixture of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane; more preferably, the first silane coupling agent is N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane.
Preferably, the second silane coupling agent is one or a mixture of more of vinyltrimethoxysilane, vinyltriethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propylmethyldimethoxysilane and gamma- (methacryloyloxy) propyltriethoxysilane; more preferably, the second silane coupling agent is γ - (methacryloyloxy) propyl methyldimethoxysilane.
Preferably, the molecular weight of the polyethylene glycol is 500-3000.
Preferably, the molecular weight of the polypropylene glycol is 500-3000.
Preferably, the lubricant is a fatty amide lubricant.
Preferably, the pH value regulator is organic polybasic acid.
Preferably, the pH regulator is citric acid and/or maleic acid.
Preferably, the impregnating compound comprises an effective component and water; wherein the effective components comprise a silane coupling agent, a lubricant, a film forming agent, a dispersing agent and a pH value regulator; the mass of the effective component accounts for 3-10% of the total mass of the impregnating compound;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
8.0-18% of a silane coupling agent;
3.5-7.8% of a lubricant;
63-83% of a film forming agent;
3.0-9.0% of a dispersant;
1.2-3.8% of a pH value regulator;
wherein the film forming agent consists of a nano material modified epoxy emulsion and an unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1.2-1: 3.5; the dispersing agent is polyethylene glycol and/or polypropylene glycol; the nano material modified epoxy emulsion is self-emulsifying water-based epoxy emulsion grafted by one or a mixture of any more of nano silicon oxide, titanium oxide, graphene and carbon nano tubes; the unsaturated polyester emulsion is a branched chain type unsaturated polyester emulsion with the unsaturation degree of 400-1200.
In the high-mechanical-property glass fiber impregnating compound, the film-forming agent consists of a nano-material modified epoxy emulsion and an unsaturated polyester emulsion. The nano material modified epoxy emulsion comprises a nano material and an epoxy emulsion, wherein the nano material modified epoxy emulsion can effectively fill microcracks generated in the production process of glass fibers and enhance the strength of the glass fibers, and the epoxy emulsion serving as a glass fiber binder improves the bundling property and the stiffness of yarns; the unsaturated polyester emulsion in the formula has good compatibility with unsaturated polyester resin, contains a large amount of unsaturated double bonds, can be crosslinked with the unsaturated polyester resin, and further enhances the interface combination of the glass fiber and the resin matrix. Therefore, the glass fiber produced by coating the impregnating compound has the advantages of high tensile breaking strength of the precursor, strong bonding property with polyester resin, high mechanical strength of the prepared composite material and the like. In addition, the sizing agent also comprises a silane coupling agent, a lubricating agent, a dispersing agent and a pH regulator, so that the glass fiber coated with the sizing agent has a good soaking effect, good yarn bundling property and less hairiness in production.
The function and the content of each component in the high-mechanical-property glass impregnating compound are explained as follows:
the high-mechanical-property glass fiber impregnating compound comprises an effective component and water; wherein, the effective components comprise a silane coupling agent, a lubricant, a film forming agent, a dispersant and a pH value regulator; the mass of the effective components accounts for 2.5-10.5% of the total mass of the impregnating compound; the mass of the optimized effective component accounts for 3-10% of the total mass of the impregnating compound; further preferably, the mass of the effective components accounts for 4-9% of the total mass of the impregnating compound.
The film forming agent is the main component of the glass fiber sizing agent, has the functions of protecting glass fibers, improving the cuttability and bundling property of the glass fibers and the compatibility with matrix resin, and has decisive influence on the continuous production and subsequent application of the glass fibers. In the high-mechanical-property glass fiber impregnating compound, the film-forming agent is limited to occupy 59-87% of the total mass of effective components; preferably, the film forming agent accounts for 63-83% of the total mass of the effective components; further preferably, the film forming agent accounts for 66-80% of the total mass of the effective components.
Compared with the traditional film forming agent, the first film forming agent adopts nano material modified epoxy emulsion, and is prepared by dissolving self-emulsifying aqueous epoxy resin into water to prepare self-emulsifying aqueous epoxy resin emulsion, then adding nano material, and grafting the nano material onto epoxy resin molecules through chemical bonds. The nano material can effectively fill micro cracks generated in the production process of the glass fiber due to the unique nano small-size effect, so that the mechanical strength of the glass fiber is greatly enhanced; different from the method for adding the nano particles into the impregnating compound, the method combines the nano particles and epoxy resin molecules into a whole through chemical bonds in advance, so that the nano particles are not easy to agglomerate when the impregnating compound coats the glass fibers, and the small-size effect of the nano particles can be fully exerted. Preferably, the nano material is one or a mixture of any more of nano silicon oxide, nano titanium oxide, graphene and carbon nano tubes; further preferably, the nano material is selected from nano silicon oxide. In addition, the self-emulsifying water-based epoxy resin emulsion is used as the glass fiber binder, and can improve the bundling property and the stiffness of the glass fiber. Meanwhile, after being combined with other film forming agent components, the glass fiber/polyester composite material can be well compatible with polyester resin to form a transition layer between the glass fiber and the polyester resin. Preferably, the nanomaterial-modified epoxy emulsion is a nanomaterial-modified bisphenol F-type epoxy emulsion and/or a nanomaterial-modified bisphenol S-type epoxy emulsion. Wherein the bisphenol F type epoxy emulsion is an emulsion prepared from bisphenol F type epoxy resin; the bisphenol S type epoxy emulsion is emulsion prepared from bisphenol S type epoxy resin. Preferably, the epoxy equivalent of the bisphenol F type epoxy resin is 600-4500 g/eq. Preferably, the epoxy equivalent of the bisphenol S type epoxy resin is 600-4500 g/eq.
The second film forming agent is unsaturated polyester emulsion, and the polyester emulsion has higher stiffness after film forming, so that the stiffness of the coated glass fiber can be effectively improved; because the polyester emulsion and the polyester resin matrix have similar polarities and are dissolved mutually, the resin permeability of the coated glass fiber can be effectively improved. In addition, the unsaturated polyester emulsion is prepared from unsaturated polyester resin, and the unsaturated polyester emulsion refers to that polyester molecules contain a large number of unsaturated double bonds, and can greatly enhance the interface bonding performance between the coated glass fiber and the polyester resin matrix through chemical bonding when being bonded with the unsaturated resin, so that the mechanical property of the composite material can be improved. Preferably, the unsaturated polyester emulsion is a branched chain type unsaturated polyester emulsion with the unsaturation degree of 200-1500; more preferably, the unsaturated polyester emulsion is a branched unsaturated polyester emulsion with the unsaturation degree of 400-1200.
In the research process, when the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1-1: 4, the yarn has good mechanical property, good bundling property, moderate stiffness and resin permeation speed. When the proportion of the nano material modified epoxy emulsion is too high, the polyester resin of the glass fiber product is easy to have poor soaking effect, and white yarns are easy to generate; when the proportion of the unsaturated polyester emulsion is too high, the bundling property of a glass fiber product is easily deteriorated, the product is brittle and easy to break, and hairiness is increased during production and use. Preferably, the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1.2-1: 3.5; further preferably, the mass ratio of the nanomaterial-modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1.5-1: 3.2.
The lubricant used in the application mainly aims to ensure the lubricating effect of the glass fiber in the processes of wire drawing, post-treatment and use, and if the content of the lubricant is too low, the lubricating effect cannot be achieved, and if the content of the lubricant is too low, the film formation of the sizing agent on the surface of the glass fiber is influenced, and the permeation and the compatibility of the glass fiber in the reinforced matrix resin are finally influenced. Wherein the lubricant accounts for 3.0-8.0% of the total mass of the effective components; preferably, the lubricant accounts for 3.5-7.8% of the total mass of the effective components; more preferably, the lubricant accounts for 4-7.5% of the total mass of the effective components.
The dispersing agent has the function of preventing the aggregation and precipitation of the nano material end in the nano material modified epoxy emulsion, so that the nano material can fully exert the small-size effect. Meanwhile, the dispersant also has the lubricating effect of the lubricant to a certain extent. Preferably, the dispersant selected by the application is polyethylene glycol and/or polypropylene glycol; more preferably, the molecular weight of polyethylene glycol is 500-3000, the molecular weight of polypropylene glycol is 500-3000; further preferably, the dispersant is polyethylene glycol with a molecular weight of 800-. Wherein the dispersant accounts for 2.0-10% of the total mass of the effective components; preferably, the dispersing agent accounts for 3.0-9.0% of the total mass of the effective components; more preferably, the dispersing agent accounts for 4.5-7.5% of the total mass of the effective components
The silane coupling agent (with the structural general formula of YSiX) is selected and used in the application 3 ) Is a coupling agent. In the general structural formula, Y is an organic terminal, and is generally an alkene or a hydrocarbon group with a functional group such as an amino group, a mercapto group, an epoxy group, an azido group, an isocyanate group and the like at the terminal; x is a hydrolyzable group such as chlorine, methoxy, ethoxy, and the like. Due to the special chemical structure, the silane coupling agent can be used as a bridge for combining the inorganic glass fiber and the organic polymer film forming agent, so that the whole impregnating compound film can be fixed on the surface of the glass fiber through chemical bonds, and better bundling property, toughness and stiffness of the glass fiber in the processing or cutting process can be maintained. Wherein the silane coupling agent accounts for 7.0-19% of the total mass of the effective components; preferably, the silane coupling agent accounts for 8.0-18% of the total mass of the effective components; more preferably, the silane coupling agent accounts for 9.0-16% of the total mass of the effective components.
The application further defines the silane coupling agent as a blend of a first silane coupling agent that is an aminoethyl-type silane coupling agent and a second silane coupling agent that is a vinyl and ester group containing silane coupling agent. The organic end of the two silane coupling agents selected for use in the present application can be effectively combined with the film-forming agent of the present application. In the research process, when the mass ratio of the first silane coupling agent to the second silane coupling agent is 1: 1-1: 5, the produced glass fiber product has moderate stiffness and bundling property; when the proportion of the first silane coupling agent is too high, the mechanical property of the coated glass fiber reinforced polyester resin composite material is insufficient; when the proportion of the second silane coupling agent is too high, the yarn bundling performance is obviously reduced, and the yarn stiffness is not enough. Preferably, the mass ratio of the first silane coupling agent to the second silane coupling agent is 1: 1.2-1: 4.8; more preferably, the mass ratio of the first silane coupling agent to the second silane coupling agent is 1:1.5 to 1: 4.5.
The first silane coupling agent can provide abundant amino groups and can form firm chemical bond combination with epoxy groups in the film forming agent. The second silane coupling agent and the unsaturated polyester emulsion film-forming agent have good physical compatibility, and both contain rich unsaturated double bonds, so that a whole can be formed through chemical bonds after film forming; on the other hand, the resin can react with the reinforced unsaturated polyester resin, so that the resin and the glass fiber interface are better combined.
The impregnating compound system is suitable for an acid environment, so that the pH value of the impregnating compound is adjusted by adopting the pH value adjusting agent. Preferably, the pH value regulator adopts organic polybasic acid, and the organic polybasic acid can increase the concentration of hydrogen ions, thereby improving the product effect. Further preferably, citric acid and/or maleic acid is used as the pH regulator. Wherein the pH value regulator accounts for 1.0-4.0% of the total mass of the effective components; preferably, the pH value regulator accounts for 1.2-3.8% of the total mass of the effective components; more preferably, the pH value regulator accounts for 1.5-3.5% of the total mass of the effective components.
The water in the present application is the dispersed phase of the components in the sizing. Among them, deionized water is preferred.
According to a second aspect of the present application, a method for preparing the high-mechanical-property glass fiber impregnating compound is provided, which comprises the following steps:
s1: adding a pH value regulator into water for pre-dispersion to prepare a solution;
s2: dispersing a silane coupling agent in the solution obtained in the step S1;
s3: respectively carrying out pre-dissolving treatment on the lubricant and the dispersant, and adding the pre-dissolved lubricant and the dispersant into the solution obtained in the step S2;
s4: diluting the nano material modified epoxy emulsion with water of which the volume is 5-10 times that of the nano material modified epoxy emulsion; diluting the unsaturated polyester emulsion with water with the volume 7-12 times that of the unsaturated polyester emulsion; and (4) sequentially adding the diluted nano material modified epoxy emulsion and the unsaturated polyester emulsion into the solution obtained in the step S3, and uniformly mixing.
Preferably, the specific operation of step S4 is: diluting the nano material modified epoxy emulsion with water of which the volume is 5-10 times that of the nano material modified epoxy emulsion to prepare emulsion with the average particle size of a dispersed phase being 0.4-3.0 mu m; diluting the unsaturated polyester emulsion with water with the volume 7-12 times that of the unsaturated polyester emulsion to prepare emulsion with the average particle size of a dispersed phase of 0.5-3.5 mu m; and (4) sequentially adding the diluted nano material modified epoxy emulsion and the unsaturated polyester emulsion into the solution obtained in the step S3, and uniformly mixing.
According to a third aspect of the present application, a glass fiber product produced by coating the high-mechanical-property glass fiber sizing agent is provided.
According to a fourth aspect of the present application, there is provided the use of said glass fiber product in the field of automotive manufacturing.
The glass fiber reinforced resin matrix produced by coating the high-mechanical-property glass fiber impregnating compound is unsaturated polyester resin and/or vinyl resin.
In the high-mechanical-property glass fiber sizing agent, the beneficial effects of selecting the above ranges of the contents of the components will be illustrated by giving specific experimental data through examples.
The following are examples of preferred ranges for each component included in the glass fiber composition according to the present application.
Preferred example 1
The high-mechanical-property glass fiber impregnating compound comprises effective components and water, wherein the mass of the effective components accounts for 2.5-10.5% of the total mass of the impregnating compound;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
7.0-19% of a silane coupling agent;
3.0-8.0% of a lubricant;
59-87% of a film forming agent;
2.0-10% of a dispersant;
1.0-4.0% of a pH value regulator;
wherein the film forming agent consists of a nano material modified epoxy emulsion and an unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1-1: 4.
Preferred example two
The high-mechanical-property glass fiber impregnating compound comprises an effective component and water, wherein the mass of the effective component accounts for 3% -10% of the total mass of the impregnating compound;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
8.0-18% of a silane coupling agent;
3.5-7.8% of a lubricant;
63-83% of a film forming agent;
3.0-9.0% of a dispersant;
1.2-3.8% of a pH value regulator;
wherein the film forming agent consists of nano material modified epoxy emulsion and unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1.2-1: 3.5.
Preferred example three
The high-mechanical-property glass fiber impregnating compound comprises an effective component and water, wherein the mass of the effective component accounts for 2.5% -10.5% of the total mass of the impregnating compound;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
7.0-19% of a silane coupling agent;
3.0-8.0% of a lubricant;
59-87% of a film forming agent;
2.0-10% of a dispersant;
1.0-4.0% of a pH value regulator;
wherein the film forming agent consists of nano material modified epoxy emulsion and unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1-1: 4;
the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent; the first silane coupling agent is an aminoethyl silane coupling agent; the second silane coupling agent is a silane coupling agent containing vinyl and ester groups; the mass ratio of the first silane coupling agent to the second silane coupling agent is 1: 1-1: 5.
Preferred example four
The high-mechanical-property glass fiber impregnating compound comprises an effective component and water, wherein the mass of the effective component accounts for 3% -10% of the total mass of the impregnating compound;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
8.0-18% of a silane coupling agent;
3.5-7.8% of a lubricant;
63-83% of a film forming agent;
3.0-9.0% of a dispersant;
1.2-3.8% of a pH value regulator;
wherein the film forming agent consists of a nano material modified epoxy emulsion and an unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1-1: 4;
the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent; the first silane coupling agent is an aminoethyl silane coupling agent; the second silane coupling agent is a silane coupling agent containing vinyl and ester groups; the mass ratio of the first silane coupling agent to the second silane coupling agent is 1: 1-1: 5.
Preferred example five
The high-mechanical-property glass fiber impregnating compound comprises an effective component and water, wherein the mass of the effective component accounts for 4% -9% of the total mass of the impregnating compound;
the mass of each component of the effective component accounts for the following percentage of the total mass of the effective component:
9.0-17% of a silane coupling agent;
4.0-7.5% of a lubricant;
66-80% of a film forming agent;
4.5-7.5% of a dispersant;
1.5-3.5% of a pH value regulator;
wherein the film forming agent consists of a nano material modified epoxy emulsion and an unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1.5-1: 3.2;
the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent; the first silane coupling agent is an aminoethyl silane coupling agent; the second silane coupling agent is a silane coupling agent containing vinyl and ester groups; the mass ratio of the first silane coupling agent to the second silane coupling agent is 1: 1.5-1: 4.5.
Preferred example six
The high-mechanical-property glass fiber impregnating compound comprises effective components and water, wherein the mass of the effective components accounts for 5% -8% of the total mass of the impregnating compound;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
10-15% of silane coupling agent
6.0 to 7.0 percent of lubricant
65-72% of film-forming agent
4.8 to 7.0 percent of dispersant
1.0 to 3.2 percent of pH value regulator
Wherein the film forming agent consists of a nano material modified epoxy emulsion and an unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1.6-1: 3.0;
the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent; the first silane coupling agent is an aminoethyl silane coupling agent; the second silane coupling agent is a silane coupling agent containing vinyl and ester groups; the mass ratio of the first silane coupling agent to the second silane coupling agent is 1: 1.6-1: 4.2.
Preferred example seven
The high-mechanical-property glass fiber impregnating compound comprises an effective component and water, wherein the mass of the effective component accounts for 2.5% -10.5% of the total mass of the impregnating compound;
the mass of each component of the effective component accounts for the following percentage of the total mass of the effective component:
7.0-19% of a silane coupling agent;
3.0-8.0% of a lubricant;
59-87% of a film forming agent;
2.0-10% of a dispersant;
1.0-4.0% of a pH value regulator;
wherein the film forming agent consists of nano material modified epoxy emulsion and unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1-1: 4;
the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent; the first silane coupling agent is an aminoethyl silane coupling agent; the second silane coupling agent is a silane coupling agent containing vinyl and ester groups; the mass ratio of the first silane coupling agent to the second silane coupling agent is 1: 1-1: 5;
the nano material modified epoxy emulsion is self-emulsifying water-based epoxy emulsion grafted by one or a mixture of any more of nano silicon oxide, nano titanium oxide, graphene and carbon nano tubes;
the unsaturated polyester emulsion is a branched chain type unsaturated polyester emulsion with the unsaturation degree of 200-1500.
Preferred example eight
The high-mechanical-property glass fiber impregnating compound comprises an effective component and water, wherein the mass of the effective component accounts for 3% -10% of the total mass of the impregnating compound;
the mass of each component of the effective component accounts for the following percentage of the total mass of the effective component:
8.0-18% of a silane coupling agent;
3.5-7.8% of a lubricant;
63-83% of a film forming agent;
3.0-9.0% of a dispersant;
1.2-3.8% of a pH value regulator;
wherein the film forming agent consists of a nano material modified epoxy emulsion and an unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1.5-1: 3.2;
the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent; the first silane coupling agent is an aminoethyl silane coupling agent; the second silane coupling agent is a silane coupling agent containing vinyl and ester groups; the mass ratio of the first silane coupling agent to the second silane coupling agent is 1: 1.5-1: 4.5;
the nano material modified epoxy emulsion is self-emulsifying water-based epoxy emulsion grafted by one or a mixture of any more of nano silicon oxide, nano titanium oxide, graphene and carbon nano tubes;
the unsaturated polyester emulsion is a branched chain type unsaturated polyester emulsion with the unsaturation degree of 200-1500;
the dispersing agent is polyethylene glycol and/or polypropylene glycol, the molecular weight of the polyethylene glycol is 500-3000, and the molecular weight of the polypropylene glycol is 500-3000.
Detailed Description
In order to make the purpose, technical solutions and advantages of the present application clearer, the technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application, and it should be apparent that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The impregnating compound used in the embodiments 1-6 of the application has the following formula raw materials:
first silane coupling agent: examples 1 to 3 use N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, examples 4 to 6 use N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane;
second silane coupling agent: examples 1 to 3 use gamma- (methacryloyloxy) propyl trimethoxysilane, examples 4 to 6 use gamma- (methacryloyloxy) propyl methyldimethoxysilane;
lubricant: the lubricant is selected from fatty acid lubricants in examples 1 to 2, fatty amide lubricants in examples 3 to 4, and polyol ester lubricants in examples 5 to 6;
nano-material modified epoxy emulsion: in the examples 1-2, the bisphenol S type epoxy emulsion grafted by nano silicon oxide is selected, and in the examples 3-4, the bisphenol S type epoxy emulsion grafted by nano titanium oxide is selected; example 5 a bisphenol F type epoxy emulsion grafted with graphene was selected; example 6 carbon nanotube grafted bisphenol F type epoxy emulsion was selected.
Unsaturated polyester emulsion: examples 1 to 3 are branched unsaturated polyester emulsions having an unsaturation degree of 200 to 900, and examples 4 to 6 are branched unsaturated polyester emulsions having an unsaturation degree of 900 to 1500;
dispersing agent: polyethylene glycol is selected in examples 1 to 3, and polypropylene glycol is selected in examples 4 to 6;
pH value regulator: maleic acid is selected in examples 1 to 3, and citric acid is selected in examples 4 to 6;
the content of effective components is as follows: example 1 was 2.5%, example 2 was 4%, example 3 was 6%, example 4 was 8%, example 5 was 9%, and example 6 was 10.5%.
The total mass percentage of each effective component in the embodiment of the high-mechanical-property glass fiber sizing agent is shown in table 1.
TABLE 1 formulation of high mechanical Property glass fiber sizing for examples 1-6
Figure DEST_PATH_IMAGE001
The preparation method of examples 1 to 6 is as follows:
s1: adding deionized water with the mass 50-60 times that of the silane coupling agent into a clean container, slowly adding a pH value regulator, and stirring to completely dissolve the pH value regulator;
s2: slowly adding a first silane coupling agent and a second silane coupling agent into the solution obtained in the step S1, adding each silane coupling agent, and then respectively stirring for 20-30 minutes until the first silane coupling agent and the second silane coupling agent are uniformly dispersed to form a clear aqueous solution without oily flowers on the surface;
s3: respectively dissolving a lubricant and a dispersant into hot water with the temperature of 50-60 ℃ and the mass of each of the hot water and the dispersant being 5-10 times that of the lubricant and the dispersant, stirring and diluting the mixture, and then adding the diluted mixture into the aqueous solution obtained in the step S2;
s4: diluting the nano material modified epoxy emulsion with water with the volume of 5-10 times of the emulsion to prepare emulsion with the average particle size of dispersed phase of 0.4-3.0 mu m; diluting the unsaturated polyester emulsion with water with the volume of 7-12 times of the emulsion to prepare emulsion with the average particle size of a dispersed phase of 0.5-3.5 mu m; and (4) sequentially adding the two emulsions into the solution obtained in the step S3, and uniformly mixing to obtain the impregnating compound.
The nano material modified epoxy emulsion can be selected from products on the market at present, and can also be prepared by a preparation method in a modified epoxy resin grafted nano silicon dioxide mechanism published by Hokkaido (refer to the Beijing university of Industrial science, the 2015, the 41 (8)) period. The preparation principle is as follows: the p-aminobenzoic acid is used as an intermediate, the amino end of the p-aminobenzoic acid can react with an epoxy group to open the ring and extend the chain of the epoxy resin emulsion molecule, and the carboxyl end of the p-aminobenzoic acid chemically reacts with the hydroxyl of the nano material, so that the chemical bonding between the nano material and the epoxy resin emulsion molecule is realized.
In order to further illustrate the beneficial effects of the present application, two glass fiber sizing agents (comparative example 1 and comparative example 2) which are commonly used at present are selected as comparative examples, the sizing agents of the comparative example 1 and the comparative example 2 both contain effective components and water, the mass of the effective components accounts for 6.5% of the total mass of the sizing agent, and the percentage of the content of each effective component in the total content of the effective components of the sizing agent is as follows:
comparative example 1
11 percent of silane coupling agent
6 percent of lubricant
135 percent of film forming agent
Film-forming agent 248%
Comparative example 2
9 percent of silane coupling agent
6 percent of lubricant
155 percent of film forming agent
230 percent of film forming agent
In comparative examples 1 to 2, the silane coupling agent was γ -aminopropyltrimethoxysilane and the lubricant was a fatty amine lubricant. In comparative example 1, the film-forming agent 1 is linear polyvinyl acetate emulsion, and the film-forming agent 2 is macromolecular bisphenol A type epoxy emulsion. In comparative example 2, the film-forming agent 1 is a medium cross-linked polyvinyl acetate emulsion, and the film-forming agent 2 is a macromolecular bisphenol F epoxy resin emulsion.
Table 2 shows the performance test results of the glass fiber twisted yarn products produced by using the impregnating compounds described in examples 1 to 6 and comparative examples 1 to 2, and in order to ensure the comparability of the test results, the combustible content of the glass fibers prepared in each example and comparative example is ensured to be substantially the same in the sample preparation process, that is: in the examples and comparative examples, the mass of the solid of the sizing applied to the surface of the glass fibers was substantially the same as the mass of the glass fibers. In addition, it was ensured that the SMC process of the glass fiber reinforced unsaturated polyester resin prepared in each example and comparative example was completely consistent to facilitate parallel comparison of mechanical properties.
Table 2 results of property testing of glass fibers produced by coating the sizing materials described in examples and comparative examples
Figure 308438DEST_PATH_IMAGE002
Note:
Figure DEST_PATH_IMAGE003
from the test results of the above examples, it can be seen that the glass fiber coated with the sizing agent of the present application has significant advantages in the aspects of strand tensile breaking strength, bending strength and tensile strength of products, wherein the glass fiber prepared in examples 3 and 4 has the advantages of outstanding performance, good bundling property, less generation of hairiness during production and use, good soaking effect in polyester resin, etc.
Therefore, the formula and the process of the glass fiber impregnating compound provided by the application are scientific and reasonable, and the glass fiber coated by the impregnating compound has better processability and higher mechanical property, so that the application requirement in the field of light weight of automobiles can be met.
Finally, it should be noted that: in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only for illustrating the technical solutions of the present application, and are not limited thereto. Although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.

Claims (9)

1. The glass fiber impregnating compound with high mechanical property is characterized by comprising effective components and water; wherein the effective components comprise a silane coupling agent, a lubricant, a film forming agent, a dispersing agent and a pH value regulator; the mass of the effective component accounts for 2.5-10.5% of the total mass of the impregnating compound;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
7.0-19% of a silane coupling agent;
3.0-8.0% of a lubricant;
59-87% of a film forming agent;
2.0-10% of a dispersant;
1.0-4.0% of a pH value regulator;
wherein the film forming agent consists of a nano material modified epoxy emulsion and an unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1-1: 4;
the nano material modified epoxy emulsion is self-emulsifying water-based epoxy emulsion grafted by one or a mixture of any more of nano silicon oxide, nano titanium oxide, graphene and carbon nano tubes;
the nano material modified epoxy emulsion is a nano material modified bisphenol F type epoxy emulsion and/or a nano material modified bisphenol S type epoxy emulsion;
the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent; the first silane coupling agent is an aminoethyl silane coupling agent; the second silane coupling agent is a silane coupling agent containing vinyl and ester groups;
the dispersing agent is polyethylene glycol and/or polypropylene glycol;
the lubricant is one or a mixture of any more of fatty acid lubricant, fatty amide lubricant and polyol ester lubricant.
2. The sizing agent according to claim 1, wherein the unsaturated polyester emulsion is a branched unsaturated polyester emulsion having an unsaturation degree of 200 to 1500.
3. The sizing agent according to claim 1, wherein the mass ratio of the first silane coupling agent to the second silane coupling agent is 1:1 to 1: 5.
4. The sizing agent according to claim 1, wherein the first silane coupling agent is one or a mixture of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, and N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane;
the second silane coupling agent is one or a mixture of more of vinyl trimethoxy silane, vinyl triethoxy silane, gamma- (methacryloyloxy) propyl trimethoxy silane, gamma- (methacryloyloxy) propyl methyl dimethoxy silane and gamma- (methacryloyloxy) propyl triethoxy silane.
5. The sizing agent according to claim 1, wherein the polyethylene glycol has a molecular weight of 500 to 3000; the molecular weight of the polypropylene glycol is 500-3000.
6. The sizing agent according to claim 1, wherein said sizing agent comprises an active ingredient and water; wherein the effective components comprise a silane coupling agent, a lubricant, a film forming agent, a dispersing agent and a pH value regulator; the mass of the effective component accounts for 3-10% of the total mass of the impregnating compound;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
8.0-18% of a silane coupling agent;
3.5-7.8% of a lubricant;
63-83% of a film forming agent;
3.0-9.0% of a dispersant;
1.2-3.8% of a pH value regulator;
wherein the film forming agent consists of a nano material modified epoxy emulsion and an unsaturated polyester emulsion; the mass ratio of the nano material modified epoxy emulsion to the unsaturated polyester emulsion is 1: 1.2-1: 3.5; the dispersing agent is polyethylene glycol and/or polypropylene glycol;
the nano material modified epoxy emulsion is self-emulsifying water-based epoxy emulsion grafted by one or a mixture of any more of nano silicon oxide, nano titanium oxide, graphene and carbon nano tubes; the unsaturated polyester emulsion is a branched chain type unsaturated polyester emulsion with the unsaturation degree of 400-1200.
7. The preparation method of the high-mechanical-property glass fiber impregnating compound according to any one of claims 1 to 6, characterized by comprising the following steps:
s1: adding a pH value regulator into water for pre-dispersion to prepare a solution;
s2: dispersing a silane coupling agent in the solution obtained in the step S1;
s3: respectively pre-dissolving the lubricant and the dispersant, and adding the pre-dissolved lubricant and dispersant into the solution obtained in the step S2;
s4: diluting the nano material modified epoxy emulsion with water of which the volume is 5-10 times that of the nano material modified epoxy emulsion; diluting the unsaturated polyester emulsion with water with the volume 7-12 times that of the unsaturated polyester emulsion; and (4) sequentially adding the diluted nano material modified epoxy emulsion and the unsaturated polyester emulsion into the solution obtained in the step S3, and uniformly mixing.
8. A glass fiber product produced by coating the high-mechanical-property glass fiber impregnating agent defined in any one of claims 1-6.
9. Use of a glass fiber product according to claim 8 in the field of automotive manufacturing.
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