CN110482879A - A kind of extra-high voltage combined insulator glass fiber infiltration agent and preparation method, product and application - Google Patents
A kind of extra-high voltage combined insulator glass fiber infiltration agent and preparation method, product and application Download PDFInfo
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- CN110482879A CN110482879A CN201910767059.6A CN201910767059A CN110482879A CN 110482879 A CN110482879 A CN 110482879A CN 201910767059 A CN201910767059 A CN 201910767059A CN 110482879 A CN110482879 A CN 110482879A
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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 kind of extra-high voltage combined insulator glass fiber infiltration agent, the solid masses of size accounts for the 4~12% of size gross mass, and surplus is water；The percentage that the solid masses of size each component accounts for size solid masses indicates are as follows: coupling agent 14~25%, lubricant 5~12%, film forming agent 60~78%, surfactant 0.5~4%, pH adjusting agent 2~10%；Wherein film forming agent is made of the first film forming agent and the second film forming agent；First film forming agent selects one of bisphenol a epoxy resin emulsion or bisphenol f type epoxy resin lotion, and the second film forming agent selects novolac epoxy resin emulsion；The mass ratio of first film forming agent and the second film forming agent is 2.5:1~1:1.Using the glass fiber yarn of size coating production, not only with target resin, that is, epoxy resin compatibility is good, is impregnated with, and the mechanical performance of product can be made high, electrical insulation properties are good, meet the requirement of extra-high voltage electric transmission and transformation professional standard.
Description
Technical field
The present invention relates to glass-fiber reinforced thermo-setting resin technical field, in particular to a kind of extra-high voltage combined insulator
With glass fiber infiltration agent and preparation method, product and application.
Background technique
With the expansion of electric system and transmission of electricity scale, the development of world's new and high technology, including composite insulator design, life
Production technology constantly bring forth new ideas and performance on promotion, pushed extra-high voltage (alternating voltage grade >=1000kV, DC voltage etc.
Grade >=± 800kV) technology of transmission of electricity research.UHV transmission is in super-pressure (alternating voltage grade 330kV (containing)~1000kV
Referred to as super-pressure, DC voltage level < ± 800kV be known as high pressure) develop on the basis of transmission of electricity, purpose is still to continue with and mentions
High ability to transmit electricity is realized in powerful, long distance power transmission, and realizes remote Power System Interconnection, and joint electricity is built up
Force system, to bring apparent economic benefit.
2009, first, China, 1000 kilovolts of ultrahigh voltage alternating current transmission lines were built up, this is also that the first item in the world is commercial special
Ultra-high-tension power transmission line creates 100 multinomial world records, is established as world standard electricity by the UHV transmission voltage that China is recommended
Pressure.Using UHVAC demonstration project as starting point, positive " whole, quick " the propulsion extra-high voltage grid of State Grid Corporation of China is built
If.Plan before and after the year two thousand twenty, basically forms the extra-high voltage grid in covering North China, Central China, East China, realize " transferring electricity from the west to the east,
North and south supply mutually ".Meanwhile extra-high voltage can reduce the loss of long distance powedr transmission, other areas, which also have, in the world widely answers
Use prospect.The UHV transmission technology of China is at the leading level in the world at present, as international standard voltage, Chinese spy
High AC voltage standard will be promoted to the world, and market prospects are boundless.Currently, the states such as India, Brazil, South Africa are positive
The engineering construction of extra-high voltage AC and DC is promoted, and Brazil etc. will be using the extra-high voltage technology in China.
In each system of the power generation of extra-high voltage electric power system, transmission of electricity, power transformation and distribution, composite insulator is compared to porcelain
Insulator has good light weight, explosion-proof performance, stable mechanical performance, anti-fouling flashover performance are excellent and installation and transportation are easy to maintain etc.
Advantage has been widely used at present.It is different according to the type of insulator product involved in extra-high voltage electric transmission and transformation route, it is compound
Insulator can be divided into: Composite Insulators, power station, electric appliance composite insulator；Composite rod insulator, needle can also be divided into
Formula composite insulator, cross-arm composite insulator, post composite insulator, windage yaw preventing composite insulator etc..
Composite electric insulator core bar be make reinforcing material using glass fibre, epoxy resin makees matrix, pass through pultrusion work
Glass fiber reinforced plastics composite material made of skill, end metal fitting are the carbon cast steel or structural carbon steel that outer surface is coated with hot galvanized layer.It is multiple
This structure for closing insulator separates mechanical strength and external insulation performance, and plug and umbrella sheath undertake mechanically and electrically respectively
Load, to combine the advantage that umbrella sheath material resistance to weathering can be superior and mandrel material drawing mechanical performance is good.
It is analyzed from use environment, composite insulator need to bear mechanical stress, electric stress, sulfur hexafluoride and its decomposition product simultaneously
Chemical action.Moisture in atmosphere is possible to that glass fiber reinforcement can be made because design defect, mass defect etc. enter inside
Composite insulator deteriorate.Therefore, the composite insulator applied to extra-high voltage electric transmission and transformation field is to glass fiber product
Quality and stability requirement are high, need to be tested by extra-high voltage industry a series of professional standards such as electrical property, mechanical performance.Phase
It is following (using epoxy resin, content of glass fiber 80%, by taking direct yarn 4800tex as an example) to close performance requirement:
Performance indicator:
| Test item | Unit | Testing standard | Index request |
| Tensile strength | MPa | GB/T 19519-2004 | ≥1400 |
| Dye penetrant test | min | GB/T 19519-2004 | ≥15 |
| Leakage current | μA | GB/T 19519-2004 | ≤100 |
| Dc breakdown voltage | kV | GB/T1408.1-2006 | ≥50 |
Therefore, it is the performance requirement for meeting extra-high voltage electric transmission and transformation composite insulator, a kind of novel size need to be developed,
So that have excellent compatibility by the glass fibre and target resin of its coating preparation, so that the effect of interface cohesion is improved,
To meet the index request of mechanical performance and electrical property.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of size of extra-high voltage combined insulator glass fibre,
Using the glass fiber yarn of size coating production, not only with target resin, that is, epoxy resin compatibility is good, is impregnated with, and
The mechanical performance of product can be made high, electrical insulation properties are good, meet the requirement of extra-high voltage electric transmission and transformation professional standard.
According to an aspect of the invention, there is provided a kind of extra-high voltage combined insulator glass fiber infiltration agent, described
The solid masses of size accounts for the 4~12% of the size gross mass, and surplus is water；The size includes following component,
The percentage that the solid masses of each component accounts for the size solid masses is expressed as follows:
Wherein, the film forming agent is made of the first film forming agent and the second film forming agent；First film forming agent selects bisphenol A-type
One of epoxy resin latex or bisphenol f type epoxy resin lotion, second film forming agent select novolac epoxy resin emulsion；
The mass ratio of first film forming agent and second film forming agent is 2.5:1~1:1.
Wherein, the percentage that the solid masses of each component accounts for the size solid masses is expressed as follows:
The mass ratio of first film forming agent and second film forming agent is 2.4:1~1.2:1.
Wherein, the molecular weight of first film forming agent is 500~1400, particle diameter of dispersing phase
0.2~2.0 μm；The molecular weight of second film forming agent is 300~700, particle diameter of dispersing phase
0.2~2.0 μm.
Wherein, the molecular weight of first film forming agent is 600~1200, the molecular weight of second film forming agent is 400~
600。
Wherein, the coupling agent is made of the first coupling agent and the second coupling agent；First coupling agent be band epoxy group,
One of amino or vinyl-based silane coupling agent, second coupling agent are the silane coupling agent with polyamino；
The mass ratio of first coupling agent and second coupling agent is 4:1~1:1.
Wherein, the size includes following component, and the solid masses of each component accounts for the percentage of size solid masses
It is expressed as follows:
Wherein, the surfactant is cationic surfactant, using in Fixanol, quaternary ammonium salt and amine salt
It is a kind of.
Size of the invention is by coupling agent, lubricant, film forming agent, surfactant, pH adjusting agent and deionized water
It is prepared, the solid masses of size accounts for the 4~12% of size gross mass.
Wherein, coupling agent is silane coupling agent, and silane coupling agent is in the molecule while containing there are two types of different chemical property
The organo-silicon compound of group, classical product can use general formula YSiX3It indicates.In formula, Y is non-hydrolytic group, including alkenyl
(predominantly vinyl) and end have Cl, NH2, SH, epoxy, N3, (methyl) acryloxy, the functions such as isocyanate group
The alkyl of group, i.e. carbon functional group；X is hydrolyzable groups, including Cl, OMe, OC2H4OCH3, OSiMe3And OAc etc..Due to silane
This special construction of coupling agent, having simultaneously in the molecule thereof can be with inanimate matter material (such as glass, silica sand, metal) chemistry
In conjunction with reactive group and with organic material (synthetic resin etc.) chemically combined reactive group, play and glass fibre and base
Coupled action between body resin is the key that influence glass fiber strength and glass fiber reinforced plastics product intensity and electric property, therefore,
The selection of coupling agent is one of emphasis of the invention.To achieve the purpose that glass fibre has multifrequency nature, what the present invention used
Coupling agent is the blend of the first coupling agent and the second coupling agent；Specifically, the first coupling agent selects band epoxy group, amino or second
One of alkenyl one type of silane coupling agent；Preferably, the coupling agent with amino is selected；Second coupling agent is the silane with polyamino
Coupling agent.Wherein, γ-aminopropyltrimethoxysilane coupling agent, γ-(2,3- can be selected in the first coupling agent that the present invention is applicable in
The third oxygen of epoxy) propyl trimethoxy silicane, vinyl three (b- methoxy ethoxy) silane etc.；The second applicable coupling agent is optional
With N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, 3- diethylenetriamine base propyl trimethoxy silicane etc..
First coupling agent can be improved the hygrometric state and dry state tensile strength and modulus of composite material, improve glass fiber reinforcement
The transparency of composite material.Second coupling agent, which is applied to fiberglass surfacing processing, can improve the convergence of glass fibre, protection
Property and processing technology, easily hydrolysis dispersion in aqueous solution, and amino activity is high, and phase of the inorganic filler with epoxy resin can be improved
Capacitive improves the bonding force of product and substrate；In reinforced epoxy, the dry and wet state bending resistance of reinforced plastics can be increased substantially
The physical and mechanical properties such as intensity, compression strength, shear strength and dry and wet state electric property, and improve the profit of filler in the polymer
It is moist and dispersed.In technical solution of the present invention, in terms of solid masses, the content of coupling agent is 14~25%, preferably 15~
24%, still more preferably, the first coupling agent 10~16%；Second coupling agent 4~10%.It is found in research, it is even by first
When to join mass ratio relationship that agent and the collocation of the second coupling agent are used, and both controlled be 4:1~1:1, that produces is extra-high
Press power transmission and transformation that there is better mechanical performance and electric property with alkali-free glass fibre product；And the second coupling agent ratio is excessively high easily
Situations such as appearance glass fiber yarn hardens and yarn rolls into a ball xanthochromia.Preferably, the mass ratio of the first coupling agent and the second coupling agent
Relationship is 3.8:1~1.2:1.
Film forming agent can play the role of protecting fiber as the main component of size, meet the continuous production of fiber,
And conclusive influence is played on the mechanical strength of glass fibre final product and electric property.Therefore, the selection of film forming agent
It is another emphasis of the invention.The film forming agent that the present invention uses is the combination of the first film forming agent and the second film forming agent.Wherein,
One film forming agent can be selected one of bisphenol a epoxy resin emulsion or bisphenol f type epoxy resin lotion, and molecular weight is 500~
1400, preferably 600~1200,0.2~2.0 μm of particle diameter of dispersing phase；Second film forming agent selects novolac epoxy resin emulsion,
Molecular weight be 300~700, preferably 400~600,0.2~2.0 μm of particle diameter of dispersing phase.Select molecular weight relatively simultaneously
Small epoxy emulsion, corresponding glass fiber yarn is soft, and wetting-out rate is fast, but convergence is poor；And use molecular weight relatively
Big epoxy emulsion, corresponding glass fibre convergence is good, but yarn is harder, wetting-out rate is partially slow.The present invention is selected bisphenol-A
Type epoxy resin latex or bisphenol f type epoxy resin lotion and novolac epoxy resin emulsion compatibility, can not only take into account glass fibers
Situations such as convergence, the yarn matter for tieing up yarn can also meet the feasibility that fiber produces, avoid filoplume, lousiness generation；Improve with
The compatibility of target resin, to improve the mechanical strength and electric property of glass fiber reinforced plastics product.Compared to other epoxy resin cream
Liquid combination (such as aqueous epoxy resins and bisphenol A type epoxy resin combination), solidification post-crosslinking density is high, the heat resistance of product,
Solvent resistance, chemical corrosion resistance and water resistance are more preferably.
Film forming agent is as component most important in size, accounting highest.The content summation of film forming agent of the present invention
It is 60~78%, preferably 61~75%, further preferably the first film forming agent 30~50%；Second film forming agent 20~30%.
Epoxy emulsion can voluntarily prepare according to existing literature or use commercial goods in the present invention.It is found in research, if the first film forming
Agent dosage is excessive, will lead to that yarn is partially hard, influences wetting-out rate of the yarn in resin；If the second film forming agent ratio is excessively high,
Then yarn can it is excessively soft, fugitive, convergence is poor, influence client using craftsmanship.Therefore, in the present invention, the first film forming agent and second
The mass ratio of film forming agent is controlled in 2.5:1~1:1, preferably 2.4:1~1.2:1.
It is found through experiments that, using film forming agent selected by the present invention and coupling agent compatibility, in heat resistance, water resistance and electricity
Gas aspect of performance is substantially better than other kinds of film forming agent and coupling agent；In suitable film forming agent, coupling agent type and content
Under proportion, glass fibre convergence is good, yarn is neither too hard, nor too soft, is impregnated with, and has good compatibility and interface to tie with matrix resin
Conjunction property；Mechanical property, the electric property of glass fiber reinforced plastics product can be significantly improved.
Water-soluble PEG series lubricant agent or silicone oil series lubricant agent can be used in the lubricant that the present invention uses, as PEG400,
PEG600, PEG1000, PEGMO, dimethyl-silicon oil lubricant etc.；It is preferred that water solubility PEG series lubricant agent.The use of lubricant
Predominantly meet glass fibre wire drawing, post-processing, use process lubricant effect, but excessive lubricant will affect glass fibers
The convergence for tieing up yarn, and will affect the mechanical performance of final glass fiber reinforced plastics product, thus in the present invention content of lubricant be 5~
12%, preferably 6~11%, further preferred 6.5~10%.
Surfactant, which refers to, is added the substance that significant change occurs for the interface state that can make its solution system on a small quantity, tool
There is fixed hydrophilic lipophilic group, can be aligned on the surface of solution.The molecular structure of surfactant has amphipathic: one
End is hydrophilic radical, and the other end is hydrophobic grouping；Hydrophilic radical is often polar group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amine
Base and its salt, hydroxyl, amide groups, ehter bond etc. also can be used as polar hydrophilic group；And hydrophobic grouping is often nonpolar hydrocarbon chain, such as 8
A above hydrocarbon chain of carbon atom.Surfactant is divided into cationic surfactant, anionic surfactant, non-ionic surface
Activating agent, amphoteric surfactant, compound surfactant, other surfaces activating agent etc..Surfactant can make oil-hydrosphere
Tension decline in face improves the stability of infiltration agent solution to reduce interfacial free energy.The surfactant that the present invention uses is
Cationic surfactant, it is preferred to use one of Fixanol, quaternary ammonium salt and amine salt.Cationic surfactant molecule
It is dissolved in after water ionizes, the hydrophilic group being connected with lipophilic group is positively charged, has strong adsorption capacity, they can be in fiber surface shape
At hydrophobic oil film, low-fiber coefficient of friction drops, with soft, smooth effect.Preferably, it can be quaternary ammonium salt sun
Ionic surface active agent also has certain antistatic property in addition to above-mentioned characteristic.In the present invention, cationic surfactant
Content when being 0.5~4%, can achieve relatively good effect, preferably 0.6~3.5%, further preferred 0.8~3%.
PH adjusting agent of the invention uses organic acid, such as citric acid, acetic acid, formic acid can be used；Special case, it can make
With the citric acid with inoxidizability and yellowing-resistant.The effect of pH adjusting agent is primarily used to ancillary coupling agent dispersion and adjusts
The pH value of prepared size, the content range of the pH adjusting agent of size of the invention are 2~10%, it is preferred that pH
The content range for being worth regulator is 3~8%.
According to another aspect of the present invention, the preparation of aforementioned extra-high voltage combined insulator glass fiber infiltration agent is provided
Method includes the following steps:
1S: being added pH adjusting agent, coupling agent in a reservoir, and then plus water progress is pre-dispersed；
2S: the container is added after the lubricant and surfactant are carried out predissolve processing respectively；
3S: the container is added after first film forming agent and second film forming agent are diluted respectively.
Wherein, in the step 1S, the coupling agent includes the first coupling agent and the second coupling agent, to described
Coupling agent carries out that pH adjusting agent is added when pre-dispersion operation.
Further, the preparation method of the extra-high voltage combined insulator glass fiber infiltration agent, each step is specifically such as
Under:
1S: being added 40%~50% water of size total amount in a reservoir, then adds pH adjusting agent, stirring 3
~after five minutes, be slowly added to the first coupling agent, after stirring 20~30 minutes, be slowly added to the second coupling agent, continue stirring 20~
30 minutes, until first coupling agent, the second coupling agent are uniformly dispersed；
Wherein, being slowly added to coupling agent facilitates being uniformly dispersed for coupling agent, while coupling agent production when preventing from rapidly joining
It is raw to splash, generally it is continuously added to by the speed of 100-200 Grams Per Second.
2S: lubricant, surfactant are dissolved in 40~50 DEG C of 5~10 times of its amounts of water, after agitation and dilution
Container is added；
3S: it is added and holds after 1.5~2 times of the water that its amount is respectively adopted in the first film forming agent and the second film forming agent is diluted
Device；
According to the third aspect of the present invention, aforementioned extra-high voltage combined insulator glass fiber infiltration agent is provided and applies overgrowth
The glass fiber product of production.Further, the alkali-free of extra-high voltage combined insulator glass fiber infiltration agent coating production is provided
The direct yarn of glass fibre or folded yarn product.
According to the fourth aspect of the present invention, aforementioned extra-high voltage combined insulator glass fiber infiltration agent processing is provided
Application of the glass fibre in extra-high voltage electric transmission and transformation field.
The size of inventive formulation, using different types of silane coupling agent and different molecular weight, different types of
Epoxy emulsion collocation use, with target resin and epoxy resin compatibility it is good, be impregnated with, while product have better mechanicalness
Energy and electric property.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with of the invention specific
Technical solution of the present invention is clearly and completely described in embodiment, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.It should be noted that In
In the case where not conflicting, the features in the embodiments and the embodiments of the present application can mutual any combination.
Extra-high voltage combined insulator glass fiber infiltration agent of the invention, solid masses account for the 4 of size gross mass
~12%, surplus is water；The percentage that the solid masses of each component accounts for size solid masses in size is expressed as follows: coupling
Agent 14~25%；Lubricant 5~12%；Film forming agent 60~78%；Surfactant 0.5~4%；PH adjusting agent 2~10%；
Preferably, coupling agent 15~24%；Lubricant 6~11%；Film forming agent 61~75%；Surfactant 0.6~
3.5%；PH adjusting agent 3~8%.
Wherein, film forming agent is made of the first film forming agent and the second film forming agent；First film forming agent selects bisphenol A type epoxy resin
One of lotion or bisphenol f type epoxy resin lotion, the second film forming agent select novolac epoxy resin emulsion；First film forming agent with
The mass ratio of second film forming agent is 2.5:1~1:1；Preferably, 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, particle diameter of dispersing phase 0.2
~2.0 μm；The molecular weight of second film forming agent be 300~700, preferably 400~600,0.2~2.0 μm of particle diameter of dispersing phase.
Coupling agent is made of the first coupling agent and the second coupling agent；First coupling agent is band epoxy group, amino or vinyl
One of one type of silane coupling agent, the second coupling agent are the silane coupling agent with polyamino；Preferably, the first coupling agent can be selected
γ-aminopropyltrimethoxysilane coupling agent, γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, (the b- methoxy of vinyl three
Base oxethyl) silane etc.；N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, 3- divinyl three can be selected in second coupling agent
Aminocarbonyl propyl trimethoxy silane etc..The mass ratio of first coupling agent and the second coupling agent be 4:1~1:1, preferably 3.8:1~
1.2:1.
Lubricant is water solubility PEG series lubricant agent or silicone oil series lubricant agent；Surfactant is cationic surfactant,
Using one of Fixanol, quaternary ammonium salt and amine salt；PH adjusting agent is organic acid.
The preparation method of the size of the extra-high voltage combined insulator glass fibre, includes the following steps:
1S: being added 40%~50% water of size total amount in a reservoir, then adds pH adjusting agent, stirring 3
~after five minutes, the first coupling agent is added；After stirring 20~30 minutes, the second coupling agent is added；Continue stirring 20~30 minutes,
Until the first coupling agent, the second coupling agent are uniformly dispersed；
2S: lubricant, surfactant are dissolved in 40~50 DEG C of 5~10 times of its amounts of water, after agitation and dilution
Container is added；
3S: it is added and holds after 1.5~2 times of the water that its amount is respectively adopted in the first film forming agent and the second film forming agent is diluted
Device；
The some embodiments of the application extra-high voltage combined insulator glass fiber infiltration agent are listed below.
Embodiment
Size each component used in the embodiment of the present invention is as follows:
Coupling agent:
γ-aminopropyltrimethoxysilane coupling agent, product grade A-1100；
N- β (aminoethyl)-γ-aminopropyltrimethoxysilane coupling agent, product grade A-1120；
Lubricant: PEGMO；
Film forming agent:
Bisphenol a epoxy resin emulsion, product grade are Neoxil 965 (manufacturer: Dutch DSM N. V.)；
Bisphenol f type epoxy resin lotion, product grade are Neoxil 962/D (manufacturer: Dutch DSM N. V.)；
Novolac epoxy resin emulsion can voluntarily prepare according to existing literature or use commercial goods.(chemical modification can be used
Method selects multifunctional phenolic epoxy resin and p-aminobenzoic acid (PABA) to carry out quantitative addition reaction, then uses emulsifier
Lauryl sodium sulfate co-emulsifier adds water phase reversal and novolac epoxy resin emulsion, preparation is made with diethanol amine at salt
Method can refer to document [Lin Weichuan, Wen Xiufang, Pi Pihui, Cai Zhiqi, Cheng Jiang, Yang Zhuoru environment-friendly type novolac epoxy resin emulsion
Preparation and performance study (A) plating and cover with paint, lacquer, colour wash, etc., 12 phases in 2010])；
Surfactant: organic quaternary ammonium salt 1631；
PH adjusting agent: citric acid.
It is noted that the specific type and content of the above selected each component are not to the protection scope structure of the application
At limitation.
Table 1 shows the section Example of extra-high voltage combined insulator glass fiber infiltration agent according to the present invention.
1 size some embodiments list of table
It should be noted that (i.e. the amount of size coating on the glass fibers accounts for glass fibre to the combustible content in table 1
The ratio of quality) 0.3~1.2%, specific value needs to be determined according to the performance of raw material itself general control；It is needed from product
From the point of view of the performance indicator and experimental results that reach, product of the combustible content in 0.4~0.9% production, mechanical strength energy
Enough meet the requirements.
Test case
Test case one
Select embodiment 3 infiltration agent prescription (in addition to film forming agent, the types of other components, content with 3 data of embodiment
It is identical), study the direct yarn enhancing diameter 18mm epoxy pultrusion core of 4800tex that the size of different film forming agent combinations is produced
The performance test results of stick.
Different film forming agent combination formulas are expressed as follows:
A: the first film forming agent is only selected
B: aqueous epoxy resin emulsion: bisphenol a epoxy resin emulsion=1:1
C: the first film forming agent: the second film forming agent=3:1
D: the first film forming agent: the second film forming agent=2.5:1
E: the first film forming agent: the second film forming agent=2:1
F: the first film forming agent: the second film forming agent=1:1
G: the first film forming agent: the second film forming agent=1:1.2；
Wherein, above first film forming agent selects bisphenol f type epoxy resin lotion.
The product properties test result of the different film forming agent combination sizes of table 2
By above data, it can be seen that, the infiltration agent prescription combined using film forming agent defined herein is answered
For extra-high voltage electric transmission and transformation industry, product has mechanical performance outstanding, electric property, excellent combination property.
Test case two
Beneficial effect in order to further illustrate the present invention, using different content proportion infiltration agent prescription as a comparison
Example, and test is compared to the product properties of embodiment and comparative example.
Comparative example 1:
Coupling agent:
Methyl-propyl acyloxy silane coupling agent, product grade A-174,13%；
γ-aminopropyltrimethoxysilane coupling agent, product grade A-1100,6%；
Lubricant: PEGMO 9%；
Film forming agent:
Bisphenol a epoxy resin emulsion, product grade be Neoxil 965, Dutch DSM N. V., 41%；
Polyester emulsion, trade mark DSM Neoxil 958, Dutch DSM N. V., 24%；
Surfactant: organic quaternary ammonium salt 1,631 2%；
PH adjusting agent: acetic acid 5%.
Comparative example 2:
Coupling agent:
γ-aminopropyltrimethoxysilane coupling agent, product grade A-1100,13%；
N- β (aminoethyl)-γ-aminopropyltrimethoxysilane coupling agent, product grade A-1120,6%；
Lubricant: PEGMO 9%；
Film forming agent:
Bisphenol f type epoxy resin lotion, product grade be Neoxil 962/D, Dutch DSM N. V., 41%；
Unsaturated polyester emulsion JS-111, product grade JS-111, Italian COIM company, 24%；
Surfactant: organic quaternary ammonium salt 1,631 2%；
PH adjusting agent: acetic acid 5%.
Comparative example 3:
Coupling agent:
γ-aminopropyltrimethoxysilane coupling agent, product grade A-1100,6%；
N- β (aminoethyl)-γ-aminopropyltrimethoxysilane coupling agent, product grade A-1120,11%；
Lubricant: PEGMO, 10%；
Film forming agent:
Bisphenol f type epoxy resin lotion, product grade are Neoxil 962/D (manufacturer: Dutch DSM N. V.),
40%；
Novolac epoxy resin emulsion, can voluntarily prepare according to existing literature or using commercial goods, and 25%；
Surfactant: organic quaternary ammonium salt 1631,4%；
PH adjusting agent: citric acid, 4%.
Here is that the size produced by each Example formulations and comparative example data is applied in certain glass fibre production
The specific test result of the direct yarn of the 4800tex that technique is produced.
The performance test results of 3 different glass fiber reinforcement diameter 18mm epoxy pultrusion plug of table
It can see from above formula test case, by the design to component and constituent content, the application's is extra-high
The properties of pressure used in composite insulator glass fiber infiltration agent are superior to comparative example data, the quality of glass fiber product and
Stability is high；It is far out of the line industry test mark using the electrical property of fiberglass products of the application size production, mechanical performance
It is quasi-.
In conclusion the glass fibre produced using extra-high voltage combined insulator of the invention with glass fiber infiltration agent,
Not only with target resin compatible it is good, be impregnated with, and the mechanical performance of product can be made high, good electric property meets extra-high voltage
The requirement of power transmission and transformation professional standard.
Descriptions above can combine implementation individually or in various ways, and these variants all exist
Within protection scope of the present invention.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations.Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of extra-high voltage combined insulator glass fiber infiltration agent, which is characterized in that the solid masses of the size accounts for
The 4~12% of the size gross mass, surplus is water；The size includes following component, and the solid masses of each component accounts for
The percentage of the size solid masses is expressed as follows:
Wherein, the film forming agent is made of the first film forming agent and the second film forming agent；First film forming agent selects bisphenol type epoxy
One of resin emulsion or bisphenol f type epoxy resin lotion, second film forming agent select novolac epoxy resin emulsion；
The mass ratio of first film forming agent and second film forming agent is 2.5:1~1:1.
2. extra-high voltage combined insulator glass fiber infiltration agent as described in claim 1, which is characterized in that each component is consolidated
The percentage that weight accounts for the size solid masses is expressed as follows:
The mass ratio of first film forming agent and second film forming agent is 2.4:1~1.2:1.
3. extra-high voltage combined insulator glass fiber infiltration agent as claimed in claim 1 or 2, which is characterized in that described
The molecular weight of one film forming agent be 500~1400,0.2~2.0 μm of particle diameter of dispersing phase；The molecular weight of second film forming agent is
300~700,0.2~2.0 μm of particle diameter of dispersing phase.
4. extra-high voltage combined insulator glass fiber infiltration agent as claimed in claim 3, which is characterized in that the first one-tenth described
The molecular weight of film is 600~1200, and the molecular weight of second film forming agent is 400~600.
5. extra-high voltage combined insulator glass fiber infiltration agent as claimed in claim 1 or 2, which is characterized in that the idol
Connection agent is made of the first coupling agent and the second coupling agent；First coupling agent is with epoxy group, amino or vinyl-based silicon
One of alkane coupling agent, second coupling agent are the silane coupling agent with polyamino；
The mass ratio of first coupling agent and second coupling agent is 4:1~1:1.
6. extra-high voltage combined insulator glass fiber infiltration agent as claimed in claim 5, which is characterized in that the size
Comprising following component, the percentage that the solid masses of each component accounts for size solid masses is expressed as follows:
7. extra-high voltage combined insulator glass fiber infiltration agent as claimed in claim 1 or 2, which is characterized in that the table
Face activating agent is cationic surfactant, using one of Fixanol, quaternary ammonium salt and amine salt.
8. a kind of preparation side of such as described in any item extra-high voltage combined insulator glass fiber infiltration agents of claim 1-7
Method includes the following steps:
1S: being added pH adjusting agent, coupling agent in a reservoir, and then plus water progress is pre-dispersed；
2S: the container is added after the lubricant and surfactant are carried out predissolve processing respectively；
3S: the container is added after first film forming agent and second film forming agent are diluted respectively.
9. a kind of as the described in any item extra-high voltage combined insulators of claim 1-7 coat production with glass fiber infiltration agent
Glass fiber product.
10. a kind of glass handled such as the described in any item extra-high voltage combined insulators of claim 1-7 with glass fiber infiltration agent
Application of the glass fiber in extra-high voltage electric transmission and transformation field.
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| CN110922069A (en) * | 2019-11-25 | 2020-03-27 | 巨石集团有限公司 | Glass fiber impregnating compound for wet weaving and puffing, and preparation method, product and application thereof |
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