CN113213779B - Glass fiber impregnating compound for high-penetration SMC (sheet molding compound) and preparation method and application thereof - Google Patents
Glass fiber impregnating compound for high-penetration SMC (sheet molding compound) and preparation method and application thereof Download PDFInfo
- Publication number
- CN113213779B CN113213779B CN202110507586.0A CN202110507586A CN113213779B CN 113213779 B CN113213779 B CN 113213779B CN 202110507586 A CN202110507586 A CN 202110507586A CN 113213779 B CN113213779 B CN 113213779B
- Authority
- CN
- China
- Prior art keywords
- coupling agent
- emulsion
- polyvinyl acetate
- coagulant
- glass fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C03C25/24—Coatings containing organic materials
- C03C25/40—Organo-silicon compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The application provides a glass fiber impregnating compound for high-penetration SMC, which comprises effective components and water; the solid content of the impregnating compound is 6-16%; the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows: 14-25% of coupling agent, 3.0-6.0% of lubricant, 54-72% of film forming agent, 4.0-14% of coagulant and 2.0-6.0% of pH value regulator; wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane emulsion to the silane modified polyvinyl acetate emulsion is 1: 3-1: 10. The glass fiber yarn produced by coating the impregnating compound has good compatibility with polyester resin and good soaking effect; and has obvious advantages in the aspect of penetration performance, and is suitable for preparing SMC sheets with high glass fiber content, high viscosity and high thickness.
Description
Technical Field
The application relates to the technical field of glass fiber reinforced resin, in particular to a glass fiber impregnating compound for high-penetrability SMC, and a preparation method and application thereof.
Background
Since the development and use in the last 60 years, sheet molding compound (hereinafter referred to as SMC) products have been widely used in many fields such as buildings, interior decoration, automobiles, rail transit and the like to date due to the advantages of light weight, high strength, corrosion resistance, lower cost, stronger industrial designability, higher molding efficiency and the like. The SMC is prepared by chopping special glass fiber twisted yarns, uniformly laying the chopped glass fiber twisted yarns on a PE film which is coated with resin paste (containing polyester resin, a curing agent and a filler in a certain proportion), then covering another layer of PE film coated with the same resin paste on the PE film, and then compacting the PE film by a series of compression rollers. For SMC products, the mechanical property of the products can be obviously improved by increasing the content of the glass fiber; at the same time, increasing the sheet thickness of the SMC as much as possible is one of the important means for improving the SMC production efficiency.
In combination with the production process of SMC, it is not difficult to find out that the biggest problem in obtaining a sheet with high glass fiber content and high thickness is how to ensure that the glass fibers are completely impregnated with resin. In fact, when the glass fiber layer is thick, the resin is easily and completely absorbed by the glass fiber on the surface layer, and the middle layer is very easy to generate white filaments because the middle layer cannot contact with enough resin, which is called that the resin cannot be penetrated, namely the penetrating performance of the glass fiber layer is not enough.
According to the invention, through the optimized design of the formula of the impregnating compound, the good compatibility and the rapid soaking performance of the glass fiber and the resin are ensured, and meanwhile, the glass fiber resin has lower adsorption capacity, so that the soaking penetration performance of the glass fiber resin is far superior to that of the common glass fiber for SMC.
Disclosure of Invention
The glass fiber impregnating compound has the advantages of high yarn stiffness, short impregnating time of a glass fiber layer, good compatibility with target unsaturated polyester resin, good resin impregnating effect, good cutting dispersibility, less hairiness in production and use and the like.
In order to achieve the technical effects, the following technical scheme is adopted in the application:
according to one aspect of the application, a glass fiber impregnating compound for high-penetrability SMC is provided, which is characterized in that the impregnating compound comprises an effective component and water; wherein the effective components comprise a coupling agent, a lubricating agent, a film forming agent, a coagulating agent and a pH value regulator; the solid content of the impregnating compound is 6-16%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
14-25% of a coupling agent;
3.0-6.0% of a lubricant;
54-72% of a film forming agent;
4.0 to 14% of a coagulant;
2.0-6.0% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 3-1: 10.
Preferably, the coagulant is one or a mixture of more of an alcohol ester coagulant, an alcohol ether coagulant or an aromatic alcohol coagulant; more preferably, the coagulant is an aromatic alcohol coagulant.
Preferably, the polyurethane modified epoxy emulsion is one or a mixture of more of polyester polyurethane modified epoxy emulsion, polyether polyurethane modified epoxy emulsion and butadiene polyurethane modified epoxy emulsion.
The polyurethane modified epoxy emulsion is prepared by dispersing polyurethane and epoxy resin in water after chemical bonding.
Preferably, the polyurethane modified epoxy emulsion is a polyurethane modified bisphenol A epoxy emulsion and/or a polyurethane modified bisphenol F epoxy emulsion.
Preferably, the epoxy equivalent of the polyurethane modified bisphenol A epoxy emulsion is 900-4000 g/eq.
Preferably, the epoxy equivalent of the polyurethane modified bisphenol F epoxy emulsion is 900-4000 g/eq.
Preferably, the solid content of the polyurethane modified epoxy emulsion is 35-50%.
Preferably, the silane modified polyvinyl acetate emulsion is a vinyl-containing siloxane modified polyvinyl acetate emulsion and/or an ester-containing siloxane modified polyvinyl acetate emulsion.
The silane modified polyvinyl acetate emulsion is prepared by dispersing siloxane and polyvinyl acetate resin in water after chemical bonding.
Preferably, the solid content of the silane modified polyvinyl acetate emulsion is 30-40%.
Preferably, the coupling agent includes a silane coupling agent and a titanate coupling agent.
Preferably, the silane coupling agent is an amino silane coupling agent; the titanate coupling agent is an alcohol amine titanate coupling agent.
Preferably, the mass ratio of the silane coupling agent to the titanate coupling agent is 1: 1-5: 1.
Preferably, the silane coupling agent is one or a mixture of more of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane; more preferably, the silane coupling agent is N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
Preferably, the titanate coupling agent is one or a mixture of more of di (triethanolamine) diisopropyl titanate, tri (triethanolamine) monoisopropyl titanate, di (diethanolamine) diisopropyl titanate and tri (diethanolamine) monoisopropyl titanate; more preferably, the titanate coupling agent is di (triethanolamine) diisopropyl titanate.
Preferably, the lubricant is one or a mixture of any more of a long-chain alkyl amide lubricant, a long-chain alkyl imidazole lubricant and a cationic amine lubricant; more preferably, the lubricant is a cationic amine lubricant.
Preferably, the pH regulator is an organic polyacid.
Preferably, the pH regulator is citric acid and/or maleic acid.
Preferably, the impregnating agent comprises an effective component and water; wherein the effective components comprise a coupling agent, a lubricant, a film forming agent, a coagulating agent and a pH value regulator; the solid content of the impregnating compound is 7% -15%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
15-24% of a coupling agent;
3.3-5.8% of a lubricant;
57-70% of a film forming agent;
5.0-13% of a coagulant;
2.5-5.5% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 4-1: 9; the coagulant is one or a mixture of more of alcohol ester coagulant, alcohol ether coagulant and aromatic alcohol coagulant; the polyurethane modified epoxy emulsion is one or a mixture of more of polyester polyurethane modified epoxy emulsion, polyether polyurethane modified epoxy emulsion and butadiene polyurethane modified epoxy emulsion; the silane modified polyvinyl acetate emulsion is siloxane modified polyvinyl acetate emulsion containing vinyl and/or siloxane modified polyvinyl acetate emulsion containing ester groups; the coupling agent comprises a silane coupling agent and a titanate coupling agent; the mass ratio of the silane coupling agent to the titanate coupling agent is 1.5: 1-4.5: 1.
In the glass fiber impregnating compound for the high-penetration SMC, the film-forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion. The former has good bonding effect on glass fibers and plays a toughening role at the same time, and the glass fibers can reduce abrasion in the using process; the polyvinyl acetate-polyvinyl acetate resin has high crosslinking degree during film forming, so that the glass fiber has less adsorption to resin when the resin is soaked, and simultaneously, the polyvinyl acetate-polyvinyl acetate resin has good compatibility with the target unsaturated polyester resin, so that the soaking effect of the resin on the glass fiber can be ensured to a certain extent. In addition, the coagulant added in the application can effectively reduce the film forming temperature of the film forming agent, so that the film forming uniformity is greatly improved. Therefore, the glass fiber produced by coating the impregnating compound has the advantages of high yarn stiffness, short glass fiber layer penetration time, good resin soaking effect, good interface bonding property with target unsaturated polyester resin and the like. In addition, the sizing agent also comprises a coupling agent, a lubricant and a pH regulator, so that the glass fiber yarn coated with the sizing agent has good bundling property and less hairiness in production.
The functions and contents of the components in the glass impregnating compound for the high-penetration SMC are described as follows:
the glass fiber impregnating compound for the high-penetration SMC comprises an effective component and water; wherein the effective components comprise a coupling agent, a lubricant, a film forming agent, a coagulating agent and a pH value regulator; the solid content of the impregnating compound is 6-16%; the solid content of the preferable impregnating compound is 7% -15%; further preferably, the solid content of the impregnating compound is 8-14%.
The film-forming agent is the main component of the glass fiber impregnating compound, 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 a decisive influence on the continuous production and subsequent application of the glass fibers. In the glass fiber impregnating compound for the high-penetration SMC, the film-forming agent is limited to occupy 54-72% of the total mass of effective components; preferably, the film-forming agent accounts for 57-70% of the total mass of the effective components; more preferably, the film forming agent accounts for 59-69% of the total mass of the effective components.
The first film forming agent is polyurethane modified epoxy emulsion which is prepared by uniformly dispersing a product (polyurethane modified epoxy resin) of block copolymerization of polyurethane and epoxy resin in water. Compared with the common epoxy emulsion, the polyurethane modified epoxy emulsion maintains the good bonding effect of the epoxy film forming agent on the glass fiber after forming the film on the surface of the glass fiber, and plays a toughening role at the same time, so that the toughness of the glass fiber is enhanced. In the subsequent processing process, the good yarn toughness can ensure the integrity of the glass fiber, keep higher stiffness and reduce the generation of hairiness. Preferably, the polyurethane is selected from polyester polyurethane, polyether polyurethane and/or butadiene polyurethane; further preferably, the polyurethane is selected from polyester polyurethane. Preferably, the epoxy resin is bisphenol A type epoxy resin and/or bisphenol F type epoxy resin; further preferably, the epoxy equivalent of the bisphenol A type epoxy resin and the bisphenol F type epoxy resin is 900 to 4000 g/eq. Preferably, the solid content of the polyurethane modified epoxy emulsion is 35-50%.
The second film forming agent is prepared by selecting silane modified polyvinyl acetate emulsion and uniformly dispersing a product (silane modified polyvinyl acetate) in water after silane is chemically bonded with polyvinyl acetate resin. The introduction of silane enables polyvinyl acetate to carry out condensation reaction through hydroxyl groups rich in silane molecules when forming a film, and simultaneously other active organic groups (such as vinyl and ester groups) on the silane can also carry out chemical reaction with other film forming agent components, thereby greatly improving the crosslinking degree of the film, reducing the gaps of the film, further reducing the adsorption capacity when resin soaks glass fibers and improving the stiffness of the glass fibers. Because the polyvinyl acetate has better compatibility with the target unsaturated polyester resin, the soaking effect of the unsaturated polyester resin on glass fibers can be ensured to a certain extent. Preferably, the silane modified polyvinyl acetate emulsion is siloxane modified polyvinyl acetate emulsion containing vinyl and/or siloxane modified polyvinyl acetate emulsion containing ester group; further preferably, the solid content of the silane modified polyvinyl acetate emulsion is 30-40%.
In the research process, the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 3-1: 10, the yarn bundling property is good, the hairiness is less, the stiffness is high, the resin soaking speed is moderate, and the soaking speed is high. When the proportion of the polyurethane modified epoxy emulsion is too high, the hardness of a glass fiber product is easily reduced, and the penetration performance is easily reduced; when the proportion of the silane modified polyvinyl acetate 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 polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 4-1: 9; further preferably, the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 5-1: 8.
The lubricant used in the application is mainly used for ensuring the lubricating effect of the glass fiber in the processes of wire drawing, post-treatment and use, the lubricating effect cannot be achieved when the content of the lubricant is too low, the film formation of the impregnating compound on the surface of the glass fiber can be influenced when the content of the lubricant is too high, and the permeation and the compatibility of the glass fiber in the reinforced matrix resin are finally influenced. Wherein the lubricant accounts for 3.0-6.0% of the total mass of the effective components; preferably, the lubricant accounts for 3.3-5.8% of the total mass of the effective components; more preferably, the lubricant accounts for 3.5-5.5% of the total mass of the effective components.
The coagulant is a solvent having a very low volatility and a very high solubility, and is miscible with water. The main function of the emulsion is to swell and deform the polymer particles under pressure, thereby lowering the minimum film-forming temperature of the emulsion. Meanwhile, the coagulant has a wet lubrication effect to a certain extent, namely, plays a role in lubricating the precursor in the wire drawing process. Preferably, the coagulant selected by the application is one or a mixture of more of alcohol ester coagulants, alcohol ether coagulants or aromatic alcohol coagulants; more preferably, the coagulant is aromatic alcohol coagulant. Wherein the coagulant accounts for 4.0-14% of the total mass of the effective components; preferably, the coagulant accounts for 5.0-13% of the total mass of the effective components; more preferably, the coagulant accounts for 6.0-12% of the total mass of the effective components
The coupling agent can generate hydroxyl condensation reaction with the surface of the glass fiber and is firmly fixed on the surface of the glass fiber. Furthermore, the coupling agent of the application is selected from silane coupling agents (with the structural general formula of YSiX) 3 ) And titanate coupling agent (with the structural general formula of Y) M TiX N Where M + N, where N is less than or equal to 4 and M + N is less than or equal to 6). Wherein, Y in the general formula is an organic terminal, usually an alkene or a hydrocarbon group with functional groups such as amino, sulfydryl, epoxy, azido and isocyanate at the terminal; x is a hydrolyzable group such as chlorine, alkoxy, or the like. Due to the special chemical structure, the silane coupling agent and the titanate 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 the glass fiber is kept to have better bundling property, toughness and stiffness in the processing or cutting process. The silane coupling agent has a certain function of repairing microcracks on the surface of the glass fiber, so that the tensile strength of the glass fiber can be improved; the titanate coupling agent focuses on improving the flexural resistance (one of bending strengths) of the glass fiber, thereby improving the stiffness of the glass fiber. The coupling agent accounts for 14-25% of the total mass of the effective components; preferably, the coupling agent accounts for 15-24% of the total mass of the effective components; more preferably, the coupling agent accounts for 17-22% of the total mass of the effective components.
The application further defines that the silane coupling agent is an amino silane coupling agent and the titanate coupling agent is an alcamines titanate coupling agent. In the research process, the comprehensive performance of the glass fiber is better when the mass ratio of the silane coupling agent to the titanate coupling agent is 1: 1-5: 1, namely the glass fiber has higher stiffness and tensile strength. When the proportion of the silane coupling agent is too high, the glass fiber flexibility resistance is poor, and the surface film is easily damaged in the processing process, so that the stiffness is obviously reduced; when the proportion of the titanate coupling agent is too high, the tensile strength of the glass fiber is easy to reduce, and monofilament breakage is easy to cause in the processing process, so that the problems of flying filaments, increasing hairiness and the like are caused. Preferably, the mass ratio of the silane coupling agent to the titanate coupling agent is 1.5: 1-4.5: 1; further preferably, the mass ratio of the silane coupling agent to the titanate coupling agent is 2: 1-4: 1.
The impregnating compound system is suitable for an acid environment, so that the pH value of the impregnating compound is adjusted by adopting a 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 2.0-6.0% of the total mass of the effective components; preferably, the pH value regulator accounts for 2.5-5.5% of the total mass of the effective components; more preferably, the pH value regulator accounts for 3.0-5.0% of the total mass of the effective components.
The water in the application is the disperse phase of each component of the effective components in the impregnating compound. Among them, deionized water is preferred.
In the present application, the mass of each component of the active ingredient and the total mass of the active ingredients are solid masses.
According to a second aspect of the present application, there is provided a method for preparing said glass fiber sizing for high-penetration SMC, comprising the steps of:
s1: adding a pH value regulator into water for pre-dispersion to prepare a solution;
s2: dispersing a coupling agent in the solution obtained in the step S1;
s3: respectively pre-dissolving the lubricant and the coagulant, and adding the pre-dissolved lubricant and the coagulant into the solution obtained in the step S2;
s4: diluting the polyurethane modified epoxy emulsion with water of which the volume is 6-10 times that of the polyurethane modified epoxy emulsion; diluting the silane modified polyvinyl acetate emulsion with water of which the volume is 8-15 times that of the silane modified polyvinyl acetate emulsion; and (4) sequentially adding the diluted polyurethane modified epoxy emulsion and the silane modified polyvinyl acetate emulsion into the solution obtained in the step S3, uniformly mixing, and supplementing water.
Preferably, the specific operation of step S4 is: diluting the polyurethane modified epoxy emulsion with water of which the volume is 6-10 times that of the polyurethane modified epoxy emulsion to prepare emulsion with the average particle size of a dispersed phase being 0.5-4.0 mu m; diluting the silane modified polyvinyl acetate emulsion with water with the volume of 8-15 times that of the silane modified polyvinyl acetate emulsion to prepare emulsion with the average particle size of a dispersed phase of 0.7-5.5 mu m; and (4) sequentially adding the diluted polyurethane modified epoxy emulsion and the silane modified polyvinyl acetate emulsion into the solution obtained in the step S3, uniformly mixing, and supplementing water.
According to a third aspect of the present application, there is provided a fiberglass product produced by coating the high-penetration SMC with a fiberglass sizing.
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 glass fiber impregnating compound for the high-penetration SMC is unsaturated polyester resin and/or vinyl resin.
The advantageous effects of selecting the above ranges of the contents of the components in the high-penetration SMC glass fiber impregnating compound of the present application 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 invention.
Preferred example 1
The glass fiber impregnating compound for the high-penetration SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 6% -16%;
the mass of each component of the effective component accounts for the following percentage of the total mass of the effective component:
14-25% of a coupling agent;
3.0-6.0% of a lubricant;
54-72% of a film forming agent;
4.0 to 14% of a coagulant;
2.0-6.0% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 3-1: 10.
Preferred example two
The glass fiber impregnating compound for the high-penetration SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 7-15%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
15-24% of a coupling agent;
3.3-5.8% of a lubricant;
57-70% of a film forming agent;
5.0-13% of a coagulant;
2.2-5.8% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 4-1: 9.
Preferred example three
The glass fiber impregnating compound for the high-penetration SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 6-16%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
14-25% of a coupling agent;
3.0-6.0% of a lubricant;
54-72% of a film forming agent;
4.0 to 14% of a coagulant;
2.0-6.0% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 3-1: 10;
the coagulant is one or more of alcohol ester coagulant, alcohol ether coagulant or aromatic alcohol coagulant.
Preferred example four
The glass fiber impregnating compound for the high-penetration SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 7-15%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
15-24% of a coupling agent;
3.3-5.8% of a lubricant;
57-70% of a film forming agent;
5.0-13% of a coagulant;
2.2-5.8% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 4-1: 9;
the coupling agent comprises a silane coupling agent and a titanate coupling agent; the mass ratio of the silane coupling agent to the titanate coupling agent is 1.5: 1-4.5: 1.
Preferred example five
The glass fiber impregnating compound for the high-penetration SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 8-14%;
the mass of each component of the effective component accounts for the following percentage of the total mass of the effective component:
17-22% of a coupling agent;
3.5-5.5% of a lubricant;
59-69% of a film forming agent;
6.0 to 12 percent of flocculant;
3.0-5.0% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 5-1: 8;
the coagulant is one or a mixture of more of alcohol ester coagulant, alcohol ether coagulant or aromatic alcohol coagulant;
the coupling agent comprises a silane coupling agent and a titanate coupling agent; the mass ratio of the silane coupling agent to the titanate coupling agent is 2: 1-4: 1.
Preferred example six
The glass fiber impregnating compound for the high-penetration SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 9% -13%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
18-21% of a coupling agent;
3.8-5.2% of a lubricant;
60-68% of film forming agent;
6.5 to 11.5 percent of coagulant;
3.2-4.8% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 5.2-1: 7.5;
the coagulant is one or a mixture of more of alcohol ester coagulant, alcohol ether coagulant or aromatic alcohol coagulant;
the coupling agent comprises a silane coupling agent and a titanate coupling agent; the mass ratio of the silane coupling agent to the titanate coupling agent is 2.4: 1-3.6: 1.
Preferred example seven
The glass fiber impregnating compound for the high-penetration SMC comprises effective components and water, wherein the solid content of the impregnating compound is 6-16%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
14-25% of a coupling agent;
3.0-6.0% of a lubricant;
54-72% of a film forming agent;
4.0 to 14% of a coagulant;
2.0-6.0% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 3-1: 10;
the polyurethane modified epoxy emulsion is one or a mixture of more of polyester polyurethane modified epoxy emulsion, polyether polyurethane modified epoxy emulsion and butadiene polyurethane modified epoxy emulsion; the silane modified polyvinyl acetate emulsion is siloxane modified polyvinyl acetate emulsion containing vinyl and/or siloxane modified polyvinyl acetate emulsion containing ester group;
the coagulant is one or a mixture of more of alcohol ester coagulant, alcohol ether coagulant or aromatic alcohol coagulant;
the coupling agent comprises a silane coupling agent and a titanate coupling agent; the mass ratio of the silane coupling agent to the titanate coupling agent is 1.5: 1-4.5: 1.
Preferred example eight
The glass fiber impregnating compound for the high-penetration SMC comprises an effective component and water, wherein the solid content of the impregnating compound is 7-15%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
15-24% of a coupling agent;
3.3-5.8% of a lubricant;
57-70% of a film forming agent;
5.0-13% of a coagulant;
2.2-5.8% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 4-1: 9;
the polyurethane modified epoxy emulsion is one or a mixture of more of polyester polyurethane modified epoxy emulsion, polyether polyurethane modified epoxy emulsion and butadiene polyurethane modified epoxy emulsion; the silane modified polyvinyl acetate emulsion is siloxane modified polyvinyl acetate emulsion containing vinyl and/or siloxane modified polyvinyl acetate emulsion containing ester groups;
the coagulant is one or a mixture of more of alcohol ester coagulant, alcohol ether coagulant or aromatic alcohol coagulant;
the coupling agent comprises a silane coupling agent and a titanate coupling agent; the mass ratio of the silane coupling agent to the titanate coupling agent is 1.5: 1-4.5: 1;
the silane coupling agent is amino silane coupling agent, and the titanate coupling agent is alcohol amine titanate coupling agent;
the lubricant is one or a mixture of any more of a long-chain alkyl amide lubricant, a long-chain alkyl imidazole lubricant and a cationic amine lubricant.
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, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within 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 formula raw materials of the impregnating compound used in the embodiments 1-18 of the application are shown in table 1:
the components in the examples of the glass fiber sizing for high-penetration SMC of the present application are shown in table 1 in terms of the total mass percentage of solids.
TABLE 1 formulation of glass fiber sizing for high penetration SMC
TABLE 1 formulation of glass fiber sizing for (continuous) high penetration SMC
TABLE 1 formulation of glass fiber sizing for (continuous) high penetration SMC
The preparation method of examples 1 to 18 is as follows:
s1: adding deionized water with the mass 50-60 times that of the 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 silane coupling agent and a titanate coupling agent into the solution obtained in the step S1, adding each coupling agent, and then respectively stirring for 20-30 minutes until the silane coupling agent and the titanate coupling agent are uniformly dispersed to form a clear aqueous solution without oily streaks on the surface;
s3: respectively dissolving a lubricant and a coagulant in hot water with the temperature of 70-80 ℃ which is 5-10 times of the mass of each lubricant and coagulant, stirring and diluting the mixture, and adding the mixture into the aqueous solution obtained in the step S2;
s4: diluting the polyurethane modified epoxy emulsion with water of which the volume is 6-10 times that of the polyurethane modified epoxy emulsion to prepare emulsion with the average particle size of a dispersed phase being 0.8-4.0 mu m; diluting the silane modified polyvinyl acetate emulsion with water with the volume of 8-15 times that of the silane modified polyvinyl acetate emulsion to prepare emulsion with the average particle size of a dispersed phase of 0.2-3.0 mu m; and (4) sequentially adding the two emulsions into the solution obtained in the step S3, uniformly mixing, and supplementing water to obtain the impregnating compound.
In order to further illustrate the beneficial effects of the application, two glass fiber impregnating compounds (comparative example 1 and comparative example 2) which are commonly used at present are selected as comparative examples, and the percentage of the content of each effective component in the comparative examples 1-2 to the total content of the effective components of the impregnating compounds is as follows:
comparative example 1
12 percent of silane coupling agent
8 percent of lubricant
132 percent of film forming agent
248 percent of film forming agent.
Comparative example 2
Silane coupling agent 8%
Lubricant 7%
Film-forming agent 158%
The film forming agent is 227%.
In comparative examples 1 to 2, the silane coupling agent was gamma-aminopropyltrimethoxysilane and the lubricant was an aliphatic amine lubricant. In comparative example 1, the film-forming agent 1 was a linear polyvinyl acetate emulsion, and the film-forming agent 2 was a macromolecular bisphenol A type epoxy emulsion, with a solid content of 12.0%. In comparative example 2, the film-forming agent 1 is a medium-crosslinked polyvinyl acetate emulsion, the film-forming agent 2 is a macromolecular bisphenol F epoxy resin emulsion, and the solid content is 10.5%.
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 18 and comparative examples 1 to 2, and in order to ensure the comparability of the test results, the combustible content of the glass fiber 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 types of unsaturated polyester resins and temperatures used when the glass fibers prepared in each of the examples and comparative examples were subjected to the penetration and soak-through tests were consistent in order to compare the properties of the glass fibers in parallel.
Table 2 results of property testing of glass fibers produced by coating the sizing materials described in examples and comparative examples
TABLE 2 test results of Properties of glass fibers produced by coating the sizing agent described in (subsequent) examples and comparative examples
Note:
the polyester resin penetration test is carried out according to the standard Q/JS J4972 of Jushi group, Inc., and the basic principle is as follows: uniformly spreading a certain amount of chopped yarns on a glass flat plate, pouring a certain amount of unsaturated resin into the limited area, and starting timing; the resin penetration rate of the glass fiber twisted yarn is measured by testing the time required for the resin to reach the surface of a glass plate after penetrating through the yarn, namely the shorter the penetration time, the better the penetration of the glass fiber layer.
From the test results of the above examples, it can be seen that the glass fibers coated with the sizing of the present application have significant advantages in terms of stiffness and resin penetration time, and the like, and the glass fibers prepared with the sizing of examples 4 and 5 are particularly excellent; in addition, the polyester resin has the advantages of good bundling property, less hairiness generated in the production and use processes, good soaking effect in the polyester resin and the like.
Therefore, the formula and the process of the glass fiber impregnating compound provided by the application are scientific and reasonable, the glass fiber coated by the impregnating compound has better processability, especially better penetration performance, and the production requirements of SMC sheets with high glass fiber content, high viscosity and high thickness 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 (6)
1. The glass fiber impregnating compound for the high-penetration SMC is characterized by comprising an effective component and water; wherein the effective components comprise a coupling agent, a lubricant, a film forming agent, a coagulating agent and a pH value regulator; the solid content of the impregnating compound is 6-16%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
14-25% of a coupling agent;
3.0-6.0% of a lubricant;
54-72% of a film forming agent;
4.0 to 14% of a coagulant;
2.0-6.0% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 3-1: 10;
the coagulant is one or a mixture of more of alcohol ester coagulant, alcohol ether coagulant and aromatic alcohol coagulant;
the polyurethane modified epoxy emulsion is one or a mixture of more of polyester polyurethane modified epoxy emulsion, polyether polyurethane modified epoxy emulsion and butadiene polyurethane modified epoxy emulsion;
the silane modified polyvinyl acetate emulsion is siloxane modified polyvinyl acetate emulsion containing vinyl and/or siloxane modified polyvinyl acetate emulsion containing ester groups;
the coupling agent comprises a silane coupling agent and a titanate coupling agent;
the mass ratio of the silane coupling agent to the titanate coupling agent is 1: 1-5: 1;
the silane coupling agent is one or a mixture of more of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane;
the titanate coupling agent is one or a mixture of more of di (triethanolamine) diisopropyl titanate, tri (triethanolamine) monoisopropyl titanate, di (diethanolamine) diisopropyl titanate and tri (diethanolamine) monoisopropyl titanate;
the lubricant is one or a mixture of any more of a long-chain alkyl amide lubricant, a long-chain alkyl imidazole lubricant and a cationic amine lubricant.
2. The sizing agent according to claim 1, wherein said urethane-modified epoxy emulsion is a urethane-modified bisphenol A type epoxy emulsion and/or a urethane-modified bisphenol F type epoxy emulsion.
3. The sizing agent according to claim 1, wherein said sizing agent comprises an active ingredient and water; wherein the effective components comprise a coupling agent, a lubricant, a film forming agent, a coagulating agent and a pH value regulator; the solid content of the impregnating compound is 7-15%;
the mass percentage of each component of the effective component in the total mass of the effective component is expressed as follows:
15-24% of a coupling agent;
3.3-5.8% of a lubricant;
57-70% of a film-forming agent;
5.0-13% of a coagulant;
2.2-5.8% of a pH value regulator;
wherein the film forming agent consists of polyurethane modified epoxy emulsion and silane modified polyvinyl acetate emulsion; the mass ratio of the polyurethane modified epoxy emulsion to the silane modified polyvinyl acetate emulsion is 1: 4-1: 9; the coagulant is one or a mixture of more of alcohol ester coagulant, alcohol ether coagulant and aromatic alcohol coagulant; the polyurethane modified epoxy emulsion is one or a mixture of more of polyester polyurethane modified epoxy emulsion, polyether polyurethane modified epoxy emulsion and butadiene polyurethane modified epoxy emulsion; the silane modified polyvinyl acetate emulsion is siloxane modified polyvinyl acetate emulsion containing vinyl and/or siloxane modified polyvinyl acetate emulsion containing ester groups; the coupling agent comprises a silane coupling agent and a titanate coupling agent; the mass ratio of the silane coupling agent to the titanate coupling agent is 1.5: 1-4.5: 1.
4. A method for preparing the glass fiber impregnating compound for the high-penetrability SMC as recited in any of claims 1-3, characterized by comprising the following steps:
s1: adding a pH value regulator into water for pre-dispersion to prepare a solution;
s2: dispersing a coupling agent in the solution obtained in the step S1;
s3: respectively pre-dissolving the lubricant and the coagulant, and adding the pre-dissolved lubricant and the coagulant into the solution obtained in the step S2;
s4: diluting the polyurethane modified epoxy emulsion with water of which the volume is 6-10 times that of the polyurethane modified epoxy emulsion; diluting the silane modified polyvinyl acetate emulsion with water of which the volume is 8-15 times that of the silane modified polyvinyl acetate emulsion; and (4) sequentially adding the diluted polyurethane modified epoxy emulsion and the silane modified polyvinyl acetate emulsion into the solution obtained in the step S3, uniformly mixing, and supplementing water.
5. A glass fiber product produced by coating the high-penetrability SMC with the glass fiber impregnating compound according to any one of claims 1 to 3.
6. Use of a glass fiber product according to claim 5 in the automotive field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110507586.0A CN113213779B (en) | 2021-05-10 | 2021-05-10 | Glass fiber impregnating compound for high-penetration SMC (sheet molding compound) and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110507586.0A CN113213779B (en) | 2021-05-10 | 2021-05-10 | Glass fiber impregnating compound for high-penetration SMC (sheet molding compound) and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113213779A CN113213779A (en) | 2021-08-06 |
| CN113213779B true CN113213779B (en) | 2022-08-09 |
Family
ID=77094399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110507586.0A Active CN113213779B (en) | 2021-05-10 | 2021-05-10 | Glass fiber impregnating compound for high-penetration SMC (sheet molding compound) and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113213779B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116119948A (en) * | 2023-02-01 | 2023-05-16 | 巨石集团有限公司 | Glass fiber impregnating compound and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3922466A (en) * | 1974-09-16 | 1975-11-25 | Owens Corning Fiberglass Corp | Silane coupling agents |
| JP2006327860A (en) * | 2005-05-25 | 2006-12-07 | Owens Corning Seizo Kk | Glass fiber for reinforcement and fiber-reinforced unsaturated polyester resin composition using the same |
| CN108975730A (en) * | 2018-08-24 | 2018-12-11 | 巨石集团有限公司 | A kind of glass fiber infiltration agent and its application |
| CN112521030A (en) * | 2020-12-07 | 2021-03-19 | 巨石集团有限公司 | High-mechanical-property glass fiber impregnating compound and preparation method and application thereof |
-
2021
- 2021-05-10 CN CN202110507586.0A patent/CN113213779B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3922466A (en) * | 1974-09-16 | 1975-11-25 | Owens Corning Fiberglass Corp | Silane coupling agents |
| JP2006327860A (en) * | 2005-05-25 | 2006-12-07 | Owens Corning Seizo Kk | Glass fiber for reinforcement and fiber-reinforced unsaturated polyester resin composition using the same |
| CN108975730A (en) * | 2018-08-24 | 2018-12-11 | 巨石集团有限公司 | A kind of glass fiber infiltration agent and its application |
| CN112521030A (en) * | 2020-12-07 | 2021-03-19 | 巨石集团有限公司 | High-mechanical-property glass fiber impregnating compound and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113213779A (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111499221B (en) | Low-odor glass fiber impregnating compound and preparation method and application thereof | |
| CN110950548B (en) | High-permeability glass fiber impregnating compound for epoxy resin and preparation method and application thereof | |
| US5604270A (en) | Chemical treating composition for glass fibers having emulsified epoxy with good stability and the treated glass fibers | |
| CN112521030B (en) | High-mechanical-property glass fiber impregnating compound and preparation method and application thereof | |
| CN110255928B (en) | Film forming agent suitable for glass fiber, impregnating compound containing film forming agent, and preparation method and application of impregnating compound | |
| CN101100355B (en) | Soaking agent capable of increasing glass fiber acid resistance | |
| CN107829306B (en) | Coated carbon fiber precursor oiling agent and preparation method thereof | |
| CN108503238B (en) | Glass fiber impregnating compound for pipeline and preparation method and application thereof | |
| CN108503239B (en) | Glass fiber impregnating compound and preparation method and application thereof | |
| CN101886336B (en) | Polyalcohol modified epoxy resin carbon fiber emulsion sizing agent component and preparation method thereof | |
| CN111073218A (en) | Environment-friendly flame-retardant chopped carbon fiber mat prepreg and preparation method thereof | |
| CN108975730B (en) | Glass fiber impregnating compound and application thereof | |
| CN113213779B (en) | Glass fiber impregnating compound for high-penetration SMC (sheet molding compound) and preparation method and application thereof | |
| CN109502995B (en) | Glass fiber impregnating compound and application thereof | |
| CN112777950B (en) | Glass fiber impregnating compound and preparation method and application thereof | |
| CN112062481B (en) | Basalt fiber impregnating compound and preparation method thereof | |
| CN114539917B (en) | Self-repairing anti-pollution flashover RTV coating and preparation method thereof | |
| CN113800785B (en) | Impregnating compound for glass fiber, and preparation method, product and application thereof | |
| CN114622409A (en) | Treating agent for glass fiber electronic cloth and preparation method and application thereof | |
| CN103724952A (en) | PET/PPO (Polyethylene terephthalate/poly-p-phenylene oxide) alloy material and preparation method thereof | |
| CN114538797B (en) | Glass fiber impregnating compound, and preparation method and application thereof | |
| CN110924171A (en) | Oil agent for para-aramid fiber and preparation method and use method thereof | |
| EP1560858A1 (en) | Adhesion promoters for glass-containing systems | |
| CN112029375A (en) | Inorganic-organic hybrid polymer anticorrosive paint and preparation method thereof | |
| CN109722899A (en) | A kind of polyetherimide resin base carbon fibre suspension sizing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |