CN108330691A - A kind of insulator direct roving sizing agent and its preparation method and application - Google Patents
A kind of insulator direct roving sizing agent and its preparation method and application Download PDFInfo
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- CN108330691A CN108330691A CN201810145364.7A CN201810145364A CN108330691A CN 108330691 A CN108330691 A CN 108330691A CN 201810145364 A CN201810145364 A CN 201810145364A CN 108330691 A CN108330691 A CN 108330691A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract
The present invention provides a kind of direct roving sizing agent of insulator, and the percentage that the solid masses of each component accounts for size solid masses in size is：Coupling agent 10~20%；Lubricant 3~10%；Antistatic agent 2~9%；Film forming agent 55~78%；Surfactant 0.5~6%；PH adjusting agent 3~10%；Film forming agent is made of the first film forming agent and the second film forming agent；First film forming agent selects one kind in water-soluble epoxy resin lotion, bisphenol a epoxy resin emulsion or bisphenol f type epoxy resin lotion, the second film forming agent to select bisphenol f type epoxy resin lotion；The mass ratio of two kinds of film forming agents is 1：4~1：0.6.The direct yarn produced using the size and can make the mechanical performance of product high not only with target resin, that is, epoxy resin compatibility is good, is impregnated with, and electrical insulation properties are good, meet the requirement of standard.
Description
Technical field
The present invention relates to glass-fiber reinforced thermo-setting resin technical field, more particularly to a kind of insulator is soaked with direct yarn
Moisten agent and its preparation method and application.
Background technology
With the extension of national grid, high pressure, EHV transmission become the mainstream technology of current power Transmission, using glass
The demand of the transformer equipment hollow combined insulator of glass fiber production also increasingly increases therewith.Composite hollow insulator and porcelain
Hollow insulator is compared with light weight, explosion-proof performance is good, stable mechanical performance, anti-fouling flashover performance is excellent and installation and transportation are tieed up
Protect the advantages that facilitating.At present casing GIS fully closed combined electric units, vacuum circuit breaker and current transformer etc. is widely used to set
It is standby upper；Its operational effect is good, is to substitute porcelain hollow insulator and solve filthy area transformer equipment porcelain insulator pollution flashover, break
The new generation product for the problems such as splitting, exploding.
Hollow combined insulator mainly climbs three full skirt, connection flange main portions by fiberglass insulation tube, the increasing of silicon rubber chamber
Part forms.Epoxy glass fibre insulating pipe is the insulation internals of hollow combined insulator, is set by dedicated microcomputer control winding
It is standby to be process according to the winding of mechanics Lay up design with epoxy resin leaching alkali-free glass fibre, there is excellent mechanical strength and Jie
Electrical property.External insulation of the full skirt as hollow combined insulator is climbed in silicon rubber increasing, is undertaken necessary electric function, is such as protected and carry
For creepage distance.Connection flange is formed by aluminium die casting, using distinctive adhesive technology, mechanical load is transmitted, to support and being connected
Structure provide sealing.Hollow combined insulator is suitable for 40.5kV~1100kV electric system, as sF6 mutual inductors, sF6 are disconnected
The high-voltage electrical apparatus such as road device sleeve, high-voltage tap changer, arrester, transformer, bushing, sectional capacitance device, cable termination produce
Product.
The core of hollow combined insulator is the winding of glass fibre epoxy resin dipping high temperature, it bears machinery simultaneously and answers
The chemical action of power, electric stress, sulfur hexafluoride and its decomposition product.Moisture in air may be due to design defect, mass defect
It is internal Deng entering, so that glass fiber reinforced epoxy resin pipe is deteriorated.This epoxy insulation pipe need to by resistance to extra-high voltage and
A series of professional standard tests such as mechanical performance, therefore the quality to glass fiber product and stability requirement height.General performance
It is required that following (using epoxy resin, content of glass fiber 80%, by taking 1200tex as an example)：
Performance indicator：
| Performance project | Unit | Technical indicator | Test method |
| Filoplume | mg/kg | ≤100 | / |
| Axial tensile strength | % | ＞ 65 | ASTM D2105 |
| Dc breakdown | kv | ＞ 50 | GB/T 1408.1 |
Therefore, to meet the performance requirement of hollow combined insulator, a kind of novel size need to be developed：Want energy and target
Resin has excellent compatibility, improves the effect of interface cohesion, to meet the index request of mechanical performance and electrical property.
Invention content
Technical problem to be solved by the invention is to provide a kind of direct roving sizing agents of composite hollow insulator, using this
The direct yarn of size production and can make the machinery of product not only with target resin, that is, epoxy resin compatibility is good, is impregnated with
Performance is high, and electrical insulation properties are good, meet the requirement of standard.
According to an aspect of the invention, there is provided a kind of direct roving sizing agent of insulator, the solid of the size
Quality accounts for the 4~15% of the size gross mass, and surplus is water；The solid masses of each component accounts for size in the size
The percentage of solid masses indicates 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 is selected water-soluble
One kind in epoxy resin latex, bisphenol a epoxy resin emulsion or bisphenol f type epoxy resin lotion, second film forming agent
Select bisphenol f type epoxy resin lotion；
The mass ratio of first film forming agent and second film forming agent is 1：4~1：0.6.
Wherein, in the size solid masses of each component account for size solid masses percentage indicate it is as follows：
The mass ratio of first film forming agent and second film forming agent is 1：3~1：0.857.
Wherein, the molecular weight of first film forming agent is 200~800,0.2~2.0 μm of particle diameter of dispersing phase；Described
The molecular weight of two film forming agents is 800~1500,0.2~2.0 μm of particle diameter of dispersing phase.
Wherein, the molecular weight of first film forming agent is 400~600, the molecular weight of second film forming agent is 1000~
1200。
Wherein, the coupling agent is made of the first coupling agent and the second coupling agent；First coupling agent is band epoxy group
Silane based coupling agents, second coupling agent be in amino, acryloxy, vinyl-based silane based coupling agents
It is a kind of；
The mass ratio of first coupling agent and second coupling agent is 1：1~8：1.
Wherein, first coupling agent be 3- glycidyl ether oxypropyltrimethoxysilane coupling agents, described second
Coupling agent is γ-aminopropyltrimethoxysilane.
Wherein, the lubricant is water solubility PEG series lubricant agents or silicone oil series lubricant agent；
The antistatic agent is inorganic salts or organic salt antistatic agent, selected from lithium chloride, lithium nitrate, ammonium chloride, alkane
One kind in base sulfonate, Polyoxyethylene fatty quaternary ammonium salt, Methylsulfate salt or imidazoline metal salt；
The surfactant be nonionic surfactant, the nonionic surfactant be polyethenoxy ether class,
Crystallite wax emulsion or chemical modification mineral oil emulsion；
The pH adjusting agent is acid, and the acid is organic acid or inorganic acid.
Wherein, in the size solid masses of each component account for size solid masses percentage indicate it is as follows：
The present invention size by coupling agent, lubricant, antistatic agent, film forming agent, surfactant, pH adjusting agent and
Deionized water is prepared, and the solid masses of size accounts for the 4~15% of size gross mass.
Coupling agent typically contains inorganic and organic two kinds of groups, and inorganic group is hydrolyzed into the hydroxyl of silanol groups and glass surface
Base reacts, and the organic group of coupling agent reacts with enhanced resin group, therefore coupling agent plays and glass
Coupled action between fiber and matrix resin is the pass for influencing glass fiber strength and glass fiber reinforced plastics product intensity and electric property
Key；Therefore, the selection of coupling agent is one of the emphasis of the present invention.The coupling agent that the present invention uses is that the first coupling agent and second are even
Join the blend of agent.Specifically, the first coupling agent is the silane coupling agent with epoxy group, inorganic filler and epoxy resin can be improved
Compatibility, improve product and base material bonding force, to improve composite material physical mechanical strength, electric property, and improve
Convergence, protectiveness and the processing technology of glass fibre；Second coupling agent selects band amino, acryloxy or vinyl eka-silicon
One kind in alkyl coupling agent can improve the wetability and dispersibility of glass fibre in the epoxy, and enhance its bonding
Property, increase substantially physical and mechanical properties such as the dry and wet state bending strength, compression strength, shear strength of glass fiber reinforced plastics product and electrical
Performance, anti-aging property.
Wherein, the available product grade of the first coupling agent that the present invention is applicable in has A-187 etc.；The second applicable coupling agent
Available product grade has A-1100, A-172, A-174 etc..It is furthermore preferred that the first coupling agent is 3- glycidol ether oxygroups
Propyl trimethoxy silicane coupling agent, the second coupling agent select γ-aminopropyltrimethoxysilane.Coupling agent contains in the present invention
Amount 10~20%, preferably 11~18%, still more preferably, 3- glycidyl ether oxypropyltrimethoxysilane coupling agents
9~15%；γ-aminopropyltrimethoxysilane 3~7%.Wherein, the mass ratio relationship of the first coupling agent and the second coupling agent
It is 1：1~8：1.The present invention arranges in pairs or groups by using different types of coupling agent and uses, and is carried out to its content and proportion relation
Research so that the direct yarn product of enhancing composite hollow insulator alkali-free glass fibre produced has better mechanicalness
Energy and electric property.
Water-soluble PEG series lubricant agents 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 agents.The use of lubricant
Predominantly meet glass fibre in wire drawing, post-processing, using the lubricant effect of process, but excessive lubricant can influence glass fibers
The convergence for tieing up yarn, and can influence the mechanical performance of final glass fiber reinforced plastics product, thus in the present invention content of lubricant be 3~
10%, preferably 3~9%, further preferred 3.5~8%.
The antistatic agent that the present invention uses is inorganic salts or organic salt antistatic agent, such as lithium chloride, lithium nitrate, chlorination
Ammonium, alkylsulfonate, the dilute fatty quaternary ammonium salt of polyoxy second, Methylsulfate salt, imidazoline metal salt etc., preferably Polyoxyethylene fatty
Quaternary ammonium salt.Since hollow insulator is very high to electrical performance demands, production environment humidity is very low, insulate in Hollow Compound
Glass fibre is extremely easy to produce static electricity after rubbing with contact point in sub- production process, and glass fiber yarn is caused to be beated, and influences final
The molding of product and performance.The use of antistatic agent can reinforce the anlistatig effect of product in use, ensure winding
Smooth and end article performance the stabilization of process.It is determined that the content of antistatic agent is 2~9%, preferably 3 by experimental study
~9%, further preferred 4~8.5%.
The surfactant that the present invention uses is nonionic surfactant, specifically uses polyethenoxy ether class, microwax
One kind in lotion, chemical modification mineral oil emulsion.Effect of the surfactant in size mainly maintains size
Stability prevents the hydrophobic components such as the resin in size, silicone oil to be separated from water generation precipitated and separated.Nonionic table of the present invention
The content of face activating agent is 0.5~6%, preferably 1~6%, further preferred 2~5.5%.
Film forming agent plays the role of protecting fiber as the main component of size, meets the continuous production of fiber, and
Conclusive influence is played on the mechanical strength of glass fibre end article and electric property.Therefore, the selection of film forming agent is this
Another emphasis of invention.The film forming agent that the present invention uses is the combination of the first film forming agent, the second film forming agent.What the present invention used
First film forming agent can be selected in water-soluble epoxy resin lotion, bisphenol a epoxy resin emulsion or bisphenol f type epoxy resin lotion
One kind, molecular weight be 200~800, preferably 400~600,0.2~2.0 μm of particle diameter of dispersing phase；Second film forming agent selects
With bisphenol f type epoxy resin lotion, molecular weight is 800~1500, preferably 1000~1200, particle diameter of dispersing phase 0.2~
2.0μm。
The present invention is used using the epoxy emulsion collocation of different molecular weight, is mainly in view of bisphenol f type epoxy resin or double
Epoxy resin, which is blended, in phenol F types and bisphenol A-type has good heat resistance, water resistance and electric property, and is remarkably improved glass
The mechanical property of steel part.The relatively small epoxy emulsion of molecular weight is selected simultaneously, and corresponding glass fiber yarn is soft, is impregnated with
Speed is fast, but convergence is poor；And the relatively large epoxy emulsion of molecular weight is used, corresponding glass fibre convergence is good, but yarn
Line is harder, wetting-out rate is partially slow.The two collocation uses, so that it may which so that glass meets simultaneously, convergence is good, and yarn is neither too hard, nor too soft, leaching
It is thoroughly good, there are good compatibility and interfacial bonding property again with matrix resin.Epoxy emulsion can be according to existing literature certainly in the present invention
Row prepares or uses commercial goods.Wherein, the ratio of the first film forming agent and the second film forming agent is 1：4~1：0.6, preferably 1：3
~1：0.857.
The present invention is used using the collocation of two kinds of epoxy emulsions, in addition to taking into account the convergence of glass fiber yarn, yarn matter, also to be expired
The feasibility of sufficient fiber production, situations such as avoiding filoplume, lousiness, generate, while being also contemplated that the compatibility with resin, to carry
The mechanical strength and electric property of high glass fiber reinforced plastics product.Therefore, film forming agent is as most important component in size, and accounting is most
It is high.The content summation of film forming agent of the present invention is 55~78%, preferably 56~76%, further preferably bisphenol-A type ring
Oxygen resin emulsion 18~32%；Bisphenol f type epoxy resin lotion 34~42%.
It is found through experiments that, using the film forming agent and coupling agent compatibility selected by the present invention, in heat resistance, water resistance and electricity
Gas aspect of performance is substantially better than other kinds of film forming agent and coupling agent；Under suitable content proportioning, glass fibre can be made
Convergence is good, yarn is neither too hard, nor too soft, is impregnated with, and has good compatibility and interfacial bonding property with matrix resin；It can significantly carry
Mechanical property, the electric property of high glass fiber reinforced plastics product.
Citric acid, acetic acid, formic acid such as can be used using acid, organic acid or inorganic acid in the pH adjusting agent of the present invention
Deng.The effect of pH adjusting agent is primarily used to ancillary coupling agent dispersion and adjusts the pH value of prepared size, the present invention
Size pH value range be 3~8, it is preferred that pH value range be 4~7.
According to another aspect of the present invention, the preparation method of the direct roving sizing agent of aforementioned dielectric is provided, including such as
Lower step：
1S：40%~50% water of size total amount is added in a reservoir, then adds pH adjusting agent, stirring 3
~after five minutes, be slowly added to the first coupling agent, stirring 30~after forty minutes is slowly added to the second coupling agent, continue stirring 30~
40 minutes, until first coupling agent, the second coupling agent are uniformly dispersed；Being slowly added to coupling agent contributes to the dispersion of coupling agent
Uniformly, coupling agent generates splashing when while preventing from rapidly joining, and is generally continuously added to by the speed of 100-200 Grams Per Seconds.
2S：Lubricant, antistatic agent, surfactant are dissolved in 40~50 DEG C of 5~10 times of its amounts of water, stirred
Container is added after mixing dilution；
3S：Container is added after film forming agent is diluted using 1.5~2 times of water of its amount；
4S：PH adjusting agent is added again into container to be stirred, adjusts pH value range.
According to the third aspect of the present invention, it is direct in alkali-free glass fibre with direct roving sizing agent to provide a kind of insulator
Yarn enhances the application on composite hollow insulator.
The size of inventive formulation is taken using the epoxy emulsion of different types of silane coupling agent and different molecular weight
With use, with target resin and epoxy resin compatibility it is good, be impregnated with, while there is better mechanical performance and electric property.
The size each component of the present invention and its selection of content, size the advantageous effect of preparation method will pass through reality
It applies example and provides specific experiment data and illustrate.
Being described below for embodiment is read with reference to the drawings, other property features of the invention and advantage will become clear
It is clear.
Description of the drawings
It is incorporated into specification and the attached drawing of a part for constitution instruction shows the embodiment of the present invention, and with
Principle for explaining the present invention together is described, in the drawings, similar reference numeral is used to indicate similar element, under
Attached drawing in the description of face is some embodiments of the present invention, rather than whole embodiments, and those of ordinary skill in the art are come
It says, it without creative efforts, can be obtain other attached drawings according to these attached drawings.
Fig. 1 shows a kind of preparation method flow chart of the direct roving sizing agent of insulator according to the present invention.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
The every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.It needs
Illustrate, in the absence of conflict, the features in the embodiments and the embodiments of the present application mutually can be combined arbitrarily.
The direct roving sizing agent of insulator of the present invention, solid masses account for the 4~15% of size gross mass, and surplus is
Water；In size the solid masses of each component account for size solid masses percentage indicate it is as follows：Coupling agent 10~20%；Profit
Lubrication prescription 3~10%；Antistatic agent 2~9%；Film forming agent 55~78%；Surfactant 0.5~6%；PH adjusting agent 3~
10%；
Preferably, coupling agent 11~18%；Lubricant 3~9%；Antistatic agent 3~9%；Film forming agent 56~76%；Surface
Activating agent 1~6%；PH adjusting agent 3.5~8.5%.
Wherein, film forming agent is made of the first film forming agent and the second film forming agent；First film forming agent selects water-soluble epoxy resin
One kind in lotion, bisphenol a epoxy resin emulsion or bisphenol f type epoxy resin lotion, the second film forming agent select Bisphenol F type ring
Oxygen resin emulsion；The mass ratio of first film forming agent and the second film forming agent is 1：4~1：0.6；Preferably, mass ratio 1：3~1：
0.857。
The molecular weight of first film forming agent is 200~800, preferably 400~600,0.2~2.0 μm of particle diameter of dispersing phase；
The molecular weight of second film forming agent is 800~1500, preferably 1000~1200,0.2~2.0 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 the silylation coupling with epoxy group
Agent, the second coupling agent are with one kind in amino, acryloxy, vinyl-based silane based coupling agents；Preferably, first
Coupling agent is 3- glycidyl ether oxypropyltrimethoxysilane coupling agents, and the second coupling agent is γ-aminopropyl trimethoxy
Silane.The mass ratio of first coupling agent and the second coupling agent is 1：1~8：1.
Lubricant is water solubility PEG series lubricant agents or silicone oil series lubricant agent.Antistatic agent is inorganic salts or organic salt
Antistatic agent, selected from lithium chloride, lithium nitrate, ammonium chloride, alkylsulfonate, Polyoxyethylene fatty quaternary ammonium salt, Methylsulfate salt or
One kind in imidazoline metal salt.Surfactant is polyethenoxy ether class, crystallite wax emulsion or chemical modification mineral oil emulsion.
PH adjusting agent is organic acid or inorganic acid.
The insulator preparation method of direct roving sizing agent, includes the following steps：
1S：40%~50% water of size total amount is added in a reservoir, then adds pH adjusting agent, stirring 3
~after five minutes, the first coupling agent is added；Stirring 30~after forty minutes, the second coupling agent is added；Continue stirring 30~40 minutes,
Until the first coupling agent, the second coupling agent are uniformly dispersed；
2S：Lubricant, antistatic agent, surfactant are dissolved in 40~50 DEG C of 5~10 times of its amounts of water, stirred
Container is added after mixing dilution；
3S：Container is added after film forming agent is diluted using 1.5~2 times of water of its amount；
4S：PH adjusting agent is added again into container to be stirred, adjusts pH value range.
Embodiment：
Size each component used in the embodiment of the present invention is as follows：
Coupling agent：3- glycidyl ether oxypropyltrimethoxysilane coupling agents, product grade A-187；γ-ammonia third
Base trimethoxy silane, product grade A-1100；
Lubricant uses PEGMO；
Antistatic agent uses Polyoxyethylene fatty quaternary ammonium salt；
Film forming agent：Bisphenol a epoxy resin emulsion, product grade are 965 (manufacturers of Neoxil：Dutch DSM is public
Department)；Bisphenol f type epoxy resin lotion, product grade are Neoxil 962/D (manufacturers：Dutch DSM N. V.)；
Nonionic surfactant uses alkyl phenol polyoxyethylene ether OP；
PH adjusting agent uses acetic acid.
Embodiment
Table 1 shows the section Example of the direct roving sizing agent of insulator according to the present invention.
1 size specific embodiment 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) for general control 0.4~1.2%, specific value needs the performance according to raw material itself, reach from product needs
Performance indicator and experimental results from the point of view of, in the product of 0.4~0.9% production, mechanical strength can expire combustible content
Foot requires.
Comparative example：
Comparative example 1：
Coupling agent：3- glycidyl ether oxypropyltrimethoxysilanes coupling agent 6%, product grade A-187；γ-
Aminopropyl trimethoxysilane 10%, product grade A-1100；
Lubricant：PEGMO 3%；
Antistatic agent：Polyoxyethylene fatty quaternary ammonium salt 8.5%；
Film forming agent：Bisphenol a epoxy resin emulsion 16.5%, (product grade is Neoxil 965, Dutch DSM N. V.)；
Polyester emulsion 45% (trade mark DSM Neoxil 958, Dutch DSM N. V., relative molecular mass 1800)；
Surfactant：Alkyl phenol polyoxyethylene ether OP 4.5%；
PH adjusting agent：Acetic acid 6.5%.
Comparative example 2：
Coupling agent：γ-methacryloxypropyl front three oxosilane 8%, the production of EVONIC companies, model
MEMO；Cationic benzylamino silane 12%, the production of EVONIC companies, model 1161；
Lubricant：Alkyl imidazoline derivatives 3%；
Antistatic agent：Polyoxyethylene fatty quaternary ammonium salt 8.5%；
Film forming agent：Bisphenol A-type unsaturated polyester emulsion is from JS-111 21.5% (product grade JS-111, Italy
COIM companies), bisphenol f type epoxy resin lotion 35% (product grade is Neoxil 962/D, Dutch DSM N. V.)；
Surfactant：Alkyl phenol polyoxyethylene ether OP 5%；
PH adjusting agent：Acetic acid 7%.
Experiment test example
Here is to apply to produce work in certain glass fibre according to the size of the Example formulations data production in table 1
The specific test result for the direct yarns of 1200tex that skill is produced.
The performance test results of 2 different glass fiber reinforced epoxy resin of table winding
From above formula test case, we can therefrom find out, by the design to component and constituent content, we
The size that can be meeted the requirements, properties are superior to comparative example data；It is wherein especially better with embodiment 3,4.
In conclusion the direct yarn that the direct roving sizing agent of insulator using the present invention produces, not only with target resin
Compatibility is good, is impregnated with, and the mechanical performance of product can be made high, and good electric property meets the requirement of 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, it will be understood by those of ordinary skill in the art that：It still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features；
And these modifications or replacements, various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of direct roving sizing agent of insulator, which is characterized in that it is total that the solid masses of the size accounts for the size
The 4~15% of quality, surplus are water；The solid masses of each component accounts for the percentage table of size solid masses in the size
Show 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 soluble epoxide
One kind in resin emulsion, bisphenol a epoxy resin emulsion or bisphenol f type epoxy resin lotion, second film forming agent are selected
Bisphenol f type epoxy resin lotion；
The mass ratio of first film forming agent and second film forming agent is 1：4~1：0.6.
2. the direct roving sizing agent of insulator as described in claim 1, which is characterized in that each component consolidates in the size
The percentage that weight accounts for size solid masses indicates as follows：
The mass ratio of first film forming agent and second film forming agent is 1：3~1：0.857.
3. the direct roving sizing agent of insulator as claimed in claim 1 or 2, which is characterized in that point of first film forming agent
Son amount is 200~800,0.2~2.0 μm of particle diameter of dispersing phase；The molecular weight of second film forming agent is 800~1500, point
0.2~2.0 μm of dephasing average grain diameter.
4. the direct roving sizing agent of insulator as claimed in claim 3, which is characterized in that the molecular weight of first film forming agent
It is 400~600, the molecular weight of second film forming agent is 1000~1200.
5. the direct roving sizing agent of insulator as claimed in claim 1 or 2, which is characterized in that the coupling agent is even by first
Join agent and the second coupling agent composition；First coupling agent is the silane based coupling agents with epoxy group, and second coupling agent is
With one kind in amino, acryloxy, vinyl-based silane based coupling agents；
The mass ratio of first coupling agent and second coupling agent is 1：1~8：1.
6. the direct roving sizing agent of insulator as claimed in claim 5, which is characterized in that first coupling agent shrinks for 3-
Glyceryl etheroxypropyltrimethoxysilane coupling agent, second coupling agent are γ-aminopropyltrimethoxysilane.
7. the direct roving sizing agent of insulator as claimed in claim 6, which is characterized in that
The lubricant is water solubility PEG series lubricant agents or silicone oil series lubricant agent；
The antistatic agent is inorganic salts or organic salt antistatic agent, selected from lithium chloride, lithium nitrate, ammonium chloride, alkyl sulphur
One kind in hydrochlorate, Polyoxyethylene fatty quaternary ammonium salt, Methylsulfate salt or imidazoline metal salt；
The surfactant is nonionic surfactant, and the nonionic surfactant is polyethenoxy ether class, crystallite
Wax emulsion or chemical modification mineral oil emulsion；
The pH adjusting agent is acid, and the acid is organic acid or inorganic acid.
8. the direct roving sizing agent of insulator as claimed in claim 7, which is characterized in that each component consolidates in the size
The percentage that weight accounts for size solid masses indicates as follows：
3- glycydoxies
9. a kind of insulator as described in any one of 5-8 claims preparation method of direct roving sizing agent, including walk as follows
Suddenly：
1S：40%~50% water of size total amount is added in a reservoir, then adds pH adjusting agent, stirs 3~5 points
The first coupling agent is added in Zhong Hou；Stirring 30~after forty minutes, the second coupling agent is added；Continue stirring 30~40 minutes, until institute
State the first coupling agent, the second coupling agent is uniformly dispersed；
2S：Lubricant, antistatic agent, surfactant are dissolved in 40~50 DEG C of 5~10 times of its amounts of water, stirring is dilute
The container is added after releasing；
3S：The container is added after film forming agent is diluted using 1.5~2 times of water of its amount；
4S：PH adjusting agent is added again into the container to be stirred, adjusts pH value range.
10. a kind of such as claim 1-8 any one of them insulator is with direct roving sizing agent in the direct yarn of alkali-free glass fibre
Enhance the application on composite hollow insulator.
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| CN112830689A (en) * | 2021-01-21 | 2021-05-25 | 河南光远新材料股份有限公司 | Impregnating compound for low-dielectric glass fiber direct roving and preparation method thereof |
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| CN111663332A (en) * | 2020-06-05 | 2020-09-15 | 巨石集团有限公司 | Direct yarn impregnating compound for glass fiber multi-axial fabric and preparation method and application thereof |
| 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 |
| CN112830689A (en) * | 2021-01-21 | 2021-05-25 | 河南光远新材料股份有限公司 | Impregnating compound for low-dielectric glass fiber direct roving and preparation method thereof |
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