CN110482879B - Glass fiber impregnating compound for extra-high voltage composite insulator, preparation method, product and application - Google Patents
Glass fiber impregnating compound for extra-high voltage composite insulator, preparation method, product and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/25—Non-macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/40—Organo-silicon compounds
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Abstract
The invention discloses a glass fiber impregnating compound for an extra-high voltage composite insulator, wherein the solid mass of the impregnating compound accounts for 4-12% of the total mass of the impregnating compound, and the balance is water; the solid mass of each component of the impregnating compound accounts for the percentage of the solid mass of the impregnating compound and is represented as follows: 14-25% of a coupling agent, 5-12% of a lubricant, 60-78% of a film forming agent, 0.5-4% of a surfactant and 2-10% of a pH value regulator; wherein the film forming agent consists of a first film forming agent and a second film forming agent; the first film forming agent is one of bisphenol A epoxy resin emulsion or bisphenol F epoxy resin emulsion, and the second film forming agent is phenolic epoxy resin emulsion; the mass ratio of the first film forming agent to the second film forming agent is 2.5: 1-1: 1. the glass fiber yarn produced by coating the impregnating compound has good compatibility and good soaking with target resin, namely epoxy resin, can ensure that the product has high mechanical property and good electrical insulating property, and meets the requirements of the standard of the extra-high voltage power transmission and transformation industry.
Description
Technical Field
The invention relates to the technical field of glass fiber reinforced thermosetting resin, in particular to a glass fiber impregnating compound for an extra-high voltage composite insulator, and a preparation method, a product and application thereof.
Background
With the expansion of power systems and transmission scales, the development of high and new technologies in the world, including the continuous innovation of composite insulator design and production technology and the improvement of performance, promotes the research of extra-high voltage (the alternating voltage grade is more than or equal to 1000kV, and the direct voltage grade is more than or equal to +/-800 kV) transmission technology. The ultra-high voltage transmission is developed on the basis of ultra-high voltage (the alternating voltage class of 330kV (inclusive) -1000 kV is called ultra-high voltage, and the direct voltage class of +/-800 kV is called high voltage) transmission, and the purpose is to continuously improve the transmission capability, realize high-power medium and long-distance transmission, realize long-distance power system interconnection and build a combined power system, thereby bringing obvious economic benefit.
In 2009, the first 1000kv high-voltage ac transmission line in China was built, which is also the first commercial extra-high voltage transmission line in the world, and more than 100 world records were created, and the extra-high voltage transmission voltage recommended by China was established as the world standard voltage. With the extra-high voltage alternating current test demonstration project as a starting point, national grid companies are promoting the construction of extra-high voltage power grids integrally and quickly. The plan is that around 2020, ultra-high voltage power grids covering the areas north China, China and east China are basically formed, and 'West-east power transmission and mutual supply between south and north' are realized. Meanwhile, the extra-high voltage can reduce the loss of long-distance power transmission, and has wide application prospect in other regions in the world. The current China ultra-high voltage transmission technology is at a leading level in the world, and as an international standard voltage, the China ultra-high voltage alternating current voltage standard is popularized to the world, so that the market prospect is very wide. At present, countries such as India, Brazil, south Africa and the like are actively promoting extra-high voltage alternating current and direct current engineering construction, and Brazil and the like adopt the extra-high voltage technology of China.
Compared with porcelain insulators, the composite insulator has the advantages of light weight, good explosion-proof performance, stable mechanical performance, excellent pollution flashover resistance, convenience in installation, transportation and maintenance and the like in all systems of power generation, power transmission, power transformation and power distribution of an extra-high voltage power system, and is widely applied at present. According to the type difference of the insulator product that involves among the extra-high voltage transmission and transformation circuit, composite insulator can divide into: composite insulators for lines, power stations and electrical appliances; and can also be classified into rod-shaped suspension type composite insulators, pin type composite insulators, cross arm composite insulators, post composite insulators, windage yaw prevention composite insulators and the like.
The composite insulator core rod is made of glass fiber reinforced plastic composite material by using glass fiber as reinforcing material and epoxy resin as matrix and through pultrusion process, and the end hardware is carbon cast steel or carbon structural steel with hot galvanized coating on the outer surface. The composite insulator has the advantages that the mechanical strength and the external insulation performance are separated, and the core rod and the shed sheath bear mechanical and electrical loads respectively, so that the advantages of superior atmospheric aging resistance of the shed sheath material and good tensile mechanical performance of the core rod material are integrated.
From the analysis of the use environment, the composite insulator needs to bear the chemical actions of mechanical stress, electrical stress, sulfur hexafluoride and its decomposer at the same time. Moisture in the atmosphere may enter the interior due to design defects, quality defects, and the like, and the glass fiber-reinforced composite insulator may be deteriorated. Therefore, the composite insulator applied to the field of extra-high voltage power transmission and transformation has extremely high requirements on the quality and stability of glass fiber products, and needs to pass a series of industry standard tests of extra-high voltage industry on electrical performance, mechanical performance and the like. The relevant performance requirements are as follows (using epoxy resin, glass fiber content 80%, for example, direct yarn 4800 tex):
performance indexes are as follows:
| test items | Unit of | Test standard | Index requirement |
| Tensile strength | MPa | GB/T 19519-2004 | ≥1400 |
| Dye penetration test | min | GB/T 19519-2004 | ≥15 |
| Leakage current | μA | GB/T 19519-2004 | ≤100 |
| Breakdown voltage of DC | kV | GB/T1408.1-2006 | ≥50 |
Therefore, in order to meet the performance requirements of the composite insulator for the extra-high voltage power transmission and transformation, a novel impregnating compound needs to be developed, so that the glass fiber prepared by coating the impregnating compound and the target resin have excellent compatibility, the interface bonding effect is improved, and the index requirements of mechanical properties and electrical properties are met.
Disclosure of Invention
The invention aims to solve the technical problem of providing the glass fiber impregnating compound for the extra-high voltage composite insulator, and the glass fiber yarns produced by coating the impregnating compound have good compatibility and good permeation with target resin, namely epoxy resin, can ensure that the product has high mechanical property and good electrical insulating property, and meets the requirements of the standard of the extra-high voltage power transmission and transformation industry.
According to one aspect of the invention, the glass fiber impregnating compound for the extra-high voltage composite insulator is provided, wherein the solid mass of the impregnating compound accounts for 4-12% of the total mass of the impregnating compound, and the balance is water; the impregnating compound comprises the following components, and the solid mass of each component accounts for the following percentage of the solid mass of the impregnating compound:
the film forming agent consists of a first film forming agent and a second film forming agent; the first film forming agent is one of bisphenol A epoxy resin emulsion or bisphenol F epoxy resin emulsion, and the second film forming agent is phenolic epoxy resin emulsion;
the mass ratio of the first film forming agent to the second film forming agent is 2.5: 1-1: 1.
wherein the solid mass of each component accounts for the solid mass of the impregnating compound, and the percentage of the solid mass of each component to the solid mass of the impregnating compound is as follows:
the mass ratio of the first film forming agent to the second film forming agent is 2.4: 1-1.2: 1.
wherein the molecular weight of the first film forming agent is 500-1400, and the average particle size of a dispersed phase
0.2 to 2.0 μm; the molecular weight of the second film forming agent is 300-700, and the average particle size of a dispersed phase
0.2～2.0μm。
The molecular weight of the first film forming agent is 600-1200, and the molecular weight of the second film forming agent is 400-600.
Wherein the coupling agent consists of a first coupling agent and a second coupling agent; the first coupling agent is one of silane coupling agents with epoxy groups, amino groups or vinyl groups, and the second coupling agent is a silane coupling agent with polyamino groups;
the mass ratio of the first coupling agent to the second coupling agent is 4: 1-1: 1.
the impregnating compound comprises the following components, and the solid mass of each component accounts for the solid mass of the impregnating compound, and the percentage of the solid mass of each component is as follows:
the surfactant is a cationic surfactant and adopts one of alkyl pyridinium, quaternary ammonium salt and amine salt.
The impregnating compound is prepared from a coupling agent, a lubricant, a film-forming agent, a surfactant, a pH value regulator and deionized water, and the solid mass of the impregnating compound accounts for 4-12% of the total mass of the impregnating compound.
Wherein the coupling agent is silane coupling agent, the silane coupling agent is organosilicon compound containing two groups with different chemical properties in molecule, and its classical product can be represented by general formula YSiX3And (4) showing. Wherein Y is a non-hydrolyzable group including an alkenyl group (mainly vinyl group), and a terminal group having Cl, NH2SH, epoxy, N3A hydrocarbon group having a functional group such as a (meth) acryloyloxy group or an isocyanate group, i.e., a carbon functional group; x is a hydrolyzable group, including Cl, OMe, OC2H4OCH3，OSiMe3And OAc, etc. Because the silane coupling agent has a special structure, and has a reactive group capable of chemically bonding with inorganic materials (such as glass, silica sand, metal and the like) and a reactive group capable of chemically bonding with organic materials (synthetic resin and the like) in the molecule, the silane coupling agent plays a role in coupling with glass fibers and matrix resin, and is a key factor influencing the strength of the glass fibers and the strength and the electrical performance of glass fiber reinforced plastic products, and therefore, the selection of the silane coupling agent is one of the key points of the invention. In order to achieve the purpose that the glass fiber has various characteristics, the coupling agent used by the invention is a blend of a first coupling agent and a second coupling agent; specifically, the first coupling agent is one of epoxy group, amino group or vinyl silane coupling agents; preferably, a coupling agent with amino is selected; the second coupling agent is a silane coupling agent with polyamino groups. Wherein, the first coupling agent applicable to the invention can be selected from gamma-aminopropyl trimethoxy silane coupling agent, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, vinyl tri (b-methoxyethoxy) silane and the like; suitable second coupling agents include N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-diethylenetriaminopropyltrimethoxysilane and the like.
The first coupling agent can improve the wet tensile strength and the dry tensile strength and the modulus of the composite material and improve the transparency of the glass fiber reinforced composite material. The second coupling agent is applied to the surface treatment of the glass fiber, can improve the bundling property, the protection property and the processing technology of the glass fiber, is easy to hydrolyze and disperse in aqueous solution, has high amino activity, can improve the compatibility of inorganic filler and epoxy resin, and improves the bonding force between a product and a base material; when the epoxy resin is reinforced, the physical and mechanical properties such as dry-wet bending strength, compressive strength, shear strength and the like and the electrical properties of the reinforced plastic in dry and wet states can be greatly improved, and the wettability and the dispersibility of the filler in the polymer are improved. In the technical scheme of the invention, the content of the coupling agent is 14-25% by mass of solid, preferably 15-24%, and more preferably 10-16% by mass of the first coupling agent; 4-10% of a second coupling agent. In the research, the first coupling agent and the second coupling agent are matched for use, and the mass ratio relation of the first coupling agent and the second coupling agent is controlled to be 4: 1-1: 1, the produced alkali-free glass fiber product for the extra-high voltage power transmission and transformation has better mechanical property and electrical property; and the conditions of hardening of the glass fiber yarn, yellowing of yarn groups and the like are easy to occur when the proportion of the second coupling agent is too high. Preferably, the mass ratio of the first coupling agent to the second coupling agent is 3.8: 1-1.2: 1.
the film forming agent as the main component of the sizing agent can play a role in protecting fibers, meet the continuous production of the fibers and have a decisive influence on the mechanical strength and the electrical performance of a final product of the glass fiber. Therefore, the choice of film former is another focus of the present invention. The film forming agent used in the present invention is a combination of a first film forming agent and a second film forming agent. Wherein the first film forming agent can be one of bisphenol A epoxy resin emulsion or bisphenol F epoxy resin emulsion, the molecular weight is 500-1400, preferably 600-1200, and the average particle size of the dispersed phase is 0.2-2.0 μm; the second film former is phenolic epoxy resin emulsion, the molecular weight is 300-700, preferably 400-600, and the average particle size of a dispersed phase is 0.2-2.0 mu m. Meanwhile, epoxy emulsion with relatively small molecular weight is selected, and the corresponding glass fiber yarn is soft, has high soaking speed and poor bundling property; and the epoxy emulsion with relatively large molecular weight is used, the corresponding glass fiber has good bundling property, but the yarn is hard and has slow permeation speed. According to the invention, the bisphenol A type epoxy resin emulsion or the bisphenol F type epoxy resin emulsion is selected to be compatible with the phenolic epoxy resin emulsion, so that the bundling property and the yarn quality of the glass fiber yarn can be considered, the feasibility of fiber production can be met, and the generation of hairiness, hairline and other conditions can be avoided; the compatibility with the target resin is improved, so that the mechanical strength and the electrical property of the glass fiber reinforced plastic product are improved. Compared with other epoxy resin emulsion combinations (such as aqueous epoxy resin and bisphenol A epoxy resin combination), the cross-linking density after curing is high, and the heat resistance, solvent resistance, chemical corrosion resistance and water resistance of the product are better.
The film forming agent is used as the most main component in the impregnating compound, and the proportion of the film forming agent is highest. The total content of the film forming agents is 60-78%, preferably 61-75%, and further preferably 30-50% of the first film forming agent; and 20-30% of a second film forming agent. The epoxy emulsion of the present invention can be prepared by itself according to the existing literature or a commercially available product can be used. In the research, the first film forming agent is excessively used, so that the yarn is hard, and the permeation speed of the yarn in the resin is influenced; if the proportion of the second film forming agent is too high, the yarn is too soft, easy to scatter and poor in bundling property, and the use manufacturability of a client is influenced. Therefore, in the present invention, the mass ratio of the first film forming agent to the second film forming agent is controlled to be 2.5: 1-1: 1, preferably 2.4: 1-1.2: 1.
experiments show that the compatibility of the selected film forming agent and the coupling agent is obviously superior to other film forming agents and coupling agents in the aspects of heat resistance, water resistance and electrical performance; under the condition of proper film forming agent, coupling agent types and content proportion, the glass fiber has good bundling property, moderate yarn hardness and good soaking property, and has good compatibility and interface bonding property with matrix resin; can obviously improve the mechanical property and the electrical property of the glass fiber reinforced plastic product.
The lubricant used in the invention can adopt water-soluble PEG lubricant or silicone oil lubricant, such as PEG400, PEG600, PEG1000, PEGMO, dimethyl silicone oil lubricant, etc.; water soluble PEG-based lubricants are preferred. The lubricant is mainly used for meeting the lubricating effect of the glass fiber in the processes of drawing, post-treatment and use, but the excessive lubricant can affect the bundling property of the glass fiber yarn and the mechanical property of the final glass fiber reinforced plastic product, so the content of the lubricant in the invention is 5-12%, preferably 6-11%, and more preferably 6.5-10%.
The surfactant is a substance which is added with a small amount of surfactant and can obviously change the interface state of a solution system of the surfactant, has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution. The molecular structure of the surfactant has amphipathy: one end is a hydrophilic group, and the other end is a hydrophobic group; the hydrophilic group is often a polar group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amino groups and salts thereof, hydroxyl, amide, ether linkages, and the like may also be used as the polar hydrophilic group; and the hydrophobic group is often a non-polar hydrocarbon chain, such as a hydrocarbon chain of 8 or more carbon atoms. The surfactant is divided into cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, compound surfactant, other surfactants and the like. The surfactant can reduce the oil-water interfacial tension, thereby reducing the interfacial free energy and improving the stability of the impregnating compound solution. The surfactant used in the present invention is a cationic surfactant, and preferably one of an alkyl pyridinium salt, a quaternary ammonium salt and an amine salt is used. After the cationic surfactant molecules are dissolved in water and ionized, the hydrophilic group connected with the lipophilic group carries positive charges and has strong adsorption force, and the hydrophilic group and the lipophilic group can form a hydrophobic oil film on the surface of fibers, reduce the friction coefficient of the fibers and enable the fibers to have the effects of softness and smoothness. Preferably, the surfactant can be quaternary ammonium salt cationic surfactant, and has certain antistatic performance besides the characteristics. In the present invention, when the content of the cationic surfactant is 0.5 to 4%, a relatively good effect can be achieved, preferably 0.6 to 3.5%, and more preferably 0.8 to 3%.
The pH value regulator adopts organic acid, such as citric acid, acetic acid, formic acid and the like; specifically, citric acid having oxidation resistance and yellowing resistance may be used. The pH value regulator is mainly used for assisting the dispersion of the coupling agent and regulating the pH value of the prepared impregnating compound, the content range of the pH value regulator of the impregnating compound is 2-10%, and preferably, the content range of the pH value regulator is 3-8%.
According to another aspect of the invention, the preparation method of the glass fiber impregnating compound for the extra-high voltage composite insulator comprises the following steps:
1S: adding a pH value regulator and a coupling agent into a container, and then adding water for pre-dispersion;
2S: respectively carrying out pre-dissolving treatment on the lubricant and the surfactant, and then adding the lubricant and the surfactant into the container;
3S: and respectively diluting the first film forming agent and the second film forming agent, and then adding the diluted first film forming agent and the second film forming agent into the container.
In the step 1S, the coupling agent includes a first coupling agent and a second coupling agent, and a pH adjuster is added during the pre-dispersion operation of the coupling agent.
Further, the preparation method of the glass fiber impregnating compound for the extra-high voltage composite insulator comprises the following steps:
1S: adding water accounting for 40-50% of the total amount of the impregnating compound into a container, then adding a pH value regulator, stirring for 3-5 minutes, slowly adding a first coupling agent, stirring for 20-30 minutes, slowly adding a second coupling agent, and continuously stirring for 20-30 minutes until the first coupling agent and the second coupling agent are uniformly dispersed;
wherein, the slow addition of the coupling agent helps the coupling agent to be uniformly dispersed, and simultaneously prevents the coupling agent from splashing during the rapid addition, and the coupling agent is continuously added at a speed of 100-200 g/s.
2S: dissolving a lubricant and a surfactant in water with the temperature of 40-50 ℃ which is 5-10 times of the amount of the lubricant and the surfactant, stirring and diluting the mixture, and adding the mixture into a container;
3S: diluting the first film forming agent and the second film forming agent respectively by using water with the amount of 1.5-2 times of that of the first film forming agent and the second film forming agent, and then adding the diluted first film forming agent and the second film forming agent into a container;
according to a third aspect of the invention, a glass fiber product produced by coating the glass fiber impregnating compound for the extra-high voltage composite insulator is provided. Further, an alkali-free glass fiber direct yarn or twisted yarn product produced by coating the glass fiber impregnating compound for the extra-high voltage composite insulator is provided.
According to a fourth aspect of the invention, the application of the glass fiber treated by the glass fiber impregnating compound for the extra-high voltage composite insulator in the field of extra-high voltage power transmission and transformation is provided.
The impregnating compound of the formula adopts different types of silane coupling agents and epoxy emulsions with different molecular weights and different types, has good compatibility and good soaking with target resin and epoxy resin, and simultaneously has better mechanical property and electrical property.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention, and it is obvious that the described embodiments are some but not all embodiments of the present invention. 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 invention. 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 glass fiber impregnating compound for the extra-high voltage composite insulator disclosed by the invention has the advantages that the solid mass accounts for 4-12% of the total mass of the impregnating compound, and the balance is water; the solid mass of each component in the impregnating compound accounts for the following percentage of the solid mass of the impregnating compound: 14-25% of a coupling agent; 5-12% of a lubricant; 60-78% of a film forming agent; 0.5-4% of a surfactant; 2-10% of a pH value regulator;
preferably, 15-24% of a coupling agent; 6-11% of a lubricant; 61-75% of a film forming agent; 0.6-3.5% of a surfactant; 3-8% of a pH value regulator.
Wherein the film forming agent consists of a first film forming agent and a second film forming agent; the first film forming agent is one of bisphenol A epoxy resin emulsion or bisphenol F epoxy resin emulsion, and the second film forming agent is phenolic epoxy resin emulsion; the mass ratio of the first film forming agent to the second film forming agent is 2.5: 1-1: 1; preferably, the mass ratio is 2.4: 1-1.2: 1.
wherein the molecular weight of the first film forming agent is 500-1400, preferably 600-1200, and the average particle size of the dispersed phase is 0.2-2.0 μm; the molecular weight of the second film forming agent is 300-700, preferably 400-600, and the average particle size of the dispersed phase is 0.2-2.0 μm.
The coupling agent consists of a first coupling agent and a second coupling agent; the first coupling agent is one of epoxy group, amino or vinyl silane coupling agent, and the second coupling agent is silane coupling agent with polyamino; preferably, the first coupling agent can be selected from gamma-aminopropyltrimethoxysilane coupling agent, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, vinyl tri (b-methoxyethoxy) silane and the like; the second coupling agent can be N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, 3-diethylenetriaminopropyltrimethoxysilane or the like. The mass ratio of the first coupling agent to the second coupling agent is 4: 1-1: 1, preferably 3.8: 1-1.2: 1.
the lubricant is water-soluble PEG lubricant or silicone oil lubricant; the surfactant is a cationic surfactant and adopts one of alkyl pyridinium, quaternary ammonium salt and amine salt; the pH value regulator is organic acid.
The preparation method of the glass fiber impregnating compound for the extra-high voltage composite insulator comprises the following steps:
1S: adding water accounting for 40-50% of the total amount of the impregnating compound into a container, then adding a pH value regulator, stirring for 3-5 minutes, and then adding a first coupling agent; stirring for 20-30 minutes, and then adding a second coupling agent; continuously stirring for 20-30 minutes until the first coupling agent and the second coupling agent are uniformly dispersed;
2S: dissolving a lubricant and a surfactant in water with the temperature of 40-50 ℃ which is 5-10 times of the amount of the lubricant and the surfactant, stirring and diluting the mixture, and adding the mixture into a container;
3S: diluting the first film forming agent and the second film forming agent respectively by using water with the amount of 1.5-2 times of that of the first film forming agent and the second film forming agent, and then adding the diluted first film forming agent and the second film forming agent into a container;
the following lists some specific examples of the glass fiber impregnating compound for the extra-high voltage composite insulator.
Examples
The impregnating compound used in the embodiment of the invention comprises the following components:
coupling agent:
the product of the gamma-aminopropyl trimethoxy silane coupling agent has the product brand of A-1100;
n-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane coupling agent with the product brand of A-1120;
lubricant: PEGMO;
film-forming agent:
bisphenol A epoxy resin emulsion, product number Neoxil 965 (manufacturer: Dutch DSM company);
bisphenol F epoxy resin emulsion with a product brand of Neoxil 962/D (manufacturer: Dutch DSM company);
the novolac epoxy resin emulsion can be prepared by itself according to the existing literature or a commercial product can be used. (can adopt the chemical modification method, choose polyfunctional group phenolic aldehyde epoxy resin and p-aminobenzoic acid (PABA) to carry on the quantitative addition reaction, then aid the emulsification with emulsifier sodium dodecyl sulfate, use diethanolamine to form salt, add aqueous phase reversal to get phenolic aldehyde epoxy resin emulsion, its preparation method can refer to the literature [ Linweichuang, Wenxu, Pilaihui, Caizhi, Chengjiang, Yanzhuo, preparation and performance study of environment-protecting type phenolic aldehyde epoxy resin emulsion [ A ] electroplating and coating, 12 th 2010);
surfactant (b): organic quaternary ammonium salts 1631;
pH value regulator: and (4) citric acid.
It should be noted that the specific types and contents of the above selected components do not limit the protection scope of the present application.
Table 1 shows some examples of the glass fiber sizing for extra-high voltage composite insulators according to the present invention.
TABLE 1 wetting agent part detailed example List
It should be noted that the combustible content (i.e. the proportion of the amount of the impregnating compound coated on the glass fibers to the mass of the glass fibers) in table 1 is generally controlled to be 0.3-1.2%, and the specific value needs to be determined according to the performance of the raw material itself; according to performance indexes and experimental test results which need to be achieved by the product, the mechanical strength of the product produced with the combustible content of 0.4-0.9% can meet the requirements.
Test example
Test example 1
The formula of the impregnating compound in the embodiment 3 is selected (except for the film forming agent, the types and the contents of other components are the same as the data in the embodiment 3), and the performance test result of the 4800tex direct yarn reinforced epoxy pultrusion core rod with the diameter of 18mm produced by the impregnating compound with different film forming agent combinations is researched.
The different film former combination formulations are represented as follows:
a: only the first film forming agent is selected
B: aqueous epoxy resin emulsion: bisphenol a epoxy resin emulsion 1: 1
C: a first film forming agent: second film forming agent ═ 3: 1
D: a first film forming agent: second film forming agent ═ 2.5: 1
E: a first film forming agent: second film forming agent ═ 2: 1
F: a first film forming agent: second film forming agent ═ 1: 1
G: a first film forming agent: second film forming agent ═ 1: 1.2;
wherein, the first film forming agent is bisphenol F type epoxy resin emulsion.
Table 2 results of performance test of different film forming agents combined impregnating compound products
The data show that the impregnating compound formula adopting the film-forming agent combination defined by the application is applied to the extra-high voltage power transmission and transformation industry, and the product has outstanding mechanical property and electrical property and excellent comprehensive performance.
Test example two
In order to further illustrate the beneficial effects of the invention, the impregnating compound formulas with different content ratios are adopted as comparative examples, and the performance of the products in the examples and the comparative examples is compared and tested.
Comparative example 1：
Coupling agent:
the product brand of the methyl propyl acyloxy silane coupling agent is A-174, 13%;
the product brand of the gamma-aminopropyl trimethoxy silane coupling agent is A-1100, 6%;
lubricant: PEGMO 9%;
film-forming agent:
bisphenol A epoxy resin emulsion, product trade name Neoxil 965, Netherlands DSM company, 41%;
polyester emulsion, designation DSM Neoxil 958, DSM, netherlands, 24%;
surfactant (b): 16312% of organic quaternary ammonium salt;
pH value regulator: 5 percent of acetic acid.
Comparative example 2：
Coupling agent:
the product brand of the gamma-aminopropyl trimethoxy silane coupling agent is A-1100, 13%;
n-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane coupling agent with the product brand of A-1120, 6%;
lubricant: PEGMO 9%;
film-forming agent:
bisphenol F type epoxy resin emulsion with a product brand of Neoxil 962/D, Dutch DSM company, 41%;
unsaturated polyester emulsion JS-111, product brand JS-111, Italy COIM company, 24%;
surfactant (b): 16312% of organic quaternary ammonium salt;
pH value regulator: 5 percent of acetic acid.
Comparative example 3：
Coupling agent:
the product brand of the gamma-aminopropyl trimethoxy silane coupling agent is A-1100, 6%;
n-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane coupling agent with the product brand of A-1120, 11%;
lubricant: PEGMO, 10%;
film-forming agent:
bisphenol F type epoxy resin emulsion with a product brand of Neoxil 962/D (manufacturer: Dutch DSM company), 40%;
phenolic epoxy resin emulsion, which can be prepared according to the prior literature or can be prepared by using a commercial product, 25 percent;
surfactant (b): organic quaternary ammonium salts 1631, 4%;
pH value regulator: citric acid, 4%.
The following are the results of specific tests of 4800tex direct strand produced using a certain fiberglass manufacturing process using the sizing produced according to the formulations of the examples and comparative example data.
TABLE 3 Performance test results for epoxy pultruded core rods of different glass fiber reinforced diameters of 18mm
According to the formula test examples, the components and the component contents are designed, so that the glass fiber impregnating compound for the extra-high voltage composite insulator is superior to comparative example data in all performances, and the quality and the stability of a glass fiber product are high; the electrical property and the mechanical property of the glass fiber product produced by the impregnating compound of the application far exceed the industrial test standard.
In conclusion, the glass fiber produced by the glass fiber impregnating compound for the extra-high voltage composite insulator has good compatibility with target resin and good permeation, and can ensure that the product has high mechanical property and good electrical property, thereby meeting the requirements of the standard of the extra-high voltage power transmission and transformation industry.
The above-described aspects may be implemented individually or in various combinations, and such variations are within the scope of the present invention.
Finally, it should be noted that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will 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 of the embodiments of the present invention.
Claims (9)
1. The glass fiber impregnating compound for the extra-high voltage composite insulator is characterized in that the solid mass of the impregnating compound accounts for 4-12% of the total mass of the impregnating compound, and the balance is water; the impregnating compound comprises the following components, and the solid mass of each component accounts for the following percentage of the solid mass of the impregnating compound:
the film forming agent consists of a first film forming agent and a second film forming agent; the first film forming agent is one of bisphenol A epoxy resin emulsion or bisphenol F epoxy resin emulsion, and the second film forming agent is phenolic epoxy resin emulsion;
the coupling agent consists of a first coupling agent and a second coupling agent; the first coupling agent is one of silane coupling agents with epoxy groups, amino groups or vinyl groups, and the second coupling agent is a silane coupling agent with polyamino groups;
the mass ratio of the first film forming agent to the second film forming agent is 2.5: 1-1: 1;
the mass ratio of the first coupling agent to the second coupling agent is 4: 1-1: 1.
2. the glass fiber impregnating compound for the extra-high voltage composite insulator, as set forth in claim 1, is characterized in that the solid mass of each component in the impregnating compound is expressed as follows:
the mass ratio of the first film forming agent to the second film forming agent is 2.4: 1-1.2: 1.
3. the glass fiber impregnating compound for the extra-high voltage composite insulator, as recited in claim 1 or 2, wherein the molecular weight of the first film forming agent is 500-1400, and the average particle size of the dispersed phase is 0.2-2.0 μm; the molecular weight of the second film forming agent is 300-700, and the average particle size of a dispersed phase is 0.2-2.0 mu m.
4. The glass fiber impregnating compound for the extra-high voltage composite insulator, as recited in claim 3, wherein the molecular weight of the first film forming agent is 600-1200, and the molecular weight of the second film forming agent is 400-600.
5. The glass fiber impregnating compound for the extra-high voltage composite insulator, as set forth in claim 1, is characterized in that the impregnating compound comprises the following components, and the solid mass of each component accounts for the solid mass of the impregnating compound, and is expressed as follows:
6. the glass fiber impregnating compound for the extra-high voltage composite insulator as claimed in claim 1 or 2, wherein the surfactant is a cationic surfactant and adopts one of alkyl pyridinium, quaternary ammonium salt and amine salt.
7. The preparation method of the glass fiber impregnating compound for the extra-high voltage composite insulator as claimed in any one of claims 1 to 6, comprising the following steps:
1S: adding a pH value regulator and a coupling agent into a container, and then adding water for pre-dispersion;
2S: respectively carrying out pre-dissolving treatment on the lubricant and the surfactant, and then adding the lubricant and the surfactant into the container;
3S: and respectively diluting the first film forming agent and the second film forming agent, and then adding the diluted first film forming agent and the second film forming agent into the container.
8. A glass fiber product produced by coating the glass fiber impregnating agent for the extra-high voltage composite insulator as defined in any one of claims 1 to 6.
9. The application of the glass fiber treated by the glass fiber impregnating compound for the extra-high voltage composite insulator disclosed by any one of claims 1-6 in the field of extra-high voltage power transmission and transformation.
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| CN110818284A (en) * | 2019-12-16 | 2020-02-21 | 巨石集团有限公司 | Glass fiber strand twistless roving impregnating compound, preparation method, product and application |
| CN111663332B (en) * | 2020-06-05 | 2021-06-18 | 巨石集团有限公司 | Direct yarn impregnating compound for glass fiber multi-axial fabric and preparation method and application thereof |
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