CN106186730B - The size of FFU synthesis wooden sleeper alkali-free glass fibre yarn - Google Patents
The size of FFU synthesis wooden sleeper alkali-free glass fibre yarn Download PDFInfo
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- CN106186730B CN106186730B CN201610565882.5A CN201610565882A CN106186730B CN 106186730 B CN106186730 B CN 106186730B CN 201610565882 A CN201610565882 A CN 201610565882A CN 106186730 B CN106186730 B CN 106186730B
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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
Abstract
The present invention provides a kind of size and preparation method thereof of FFU synthesis wooden sleeper alkali-free glass fibre yarn, the size is formulated by coupling agent, lubricant, film forming agent, surfactant, pH adjusting agent, water, and pH value is 2~10；Gross mass based on nonaqueous component, the coupling agent, lubricant, film forming agent theoretical water removal after solid content part, surfactant, pH adjusting agent mass percent be respectively as follows: the solid content part 60%~85% after the theoretical water removal of coupling agent 1%~9%, lubricant 4%~18%, film forming agent, surfactant 1%~10%, pH adjusting agent 1%~5%；Compared with prior art, size of the present invention can make that the layer difference of glass fiber product keeps stablizing and wearability greatly improves, and with resin compatible is good, good penetrability, the mechanical performance of product is high, to meet market and application demand.
Description
(1) technical field
The present invention relates to a kind of sizes of glass fibre yarn, and in particular to a kind of FFU synthesis wooden sleeper alkali-free glass fibre yarn
Size.
(2) background technique
FFU (Fiber reinforced Foamed Urethane) is by the foaming body glass fibre of polyurethane resin
Light weight, the corrosion resistant composite material produced after being enhanced.FFU synthesis wooden sleeper is applied on track engineering with more
Advantage, is easy for construction and installation first, and the advantage light-weight, the laying time is short is particularly suited for bridge rail sleeper.Secondly,
FFU material is easy to make large size product, can be used for large-scale track switch etc..In addition, comparing conventional concrete sleeper, be free of in FFU
Reinforcing bar, it is not necessary to worry that short circuit accident occurs in construction.Meanwhile FFU composite material long service life, can reduce production life cycle at
This, to realize the reduction of totle drilling cost.
The FFU synthesis wooden sleeper highest attention by PU and railway circle at present is a heat of global PU material circle research
Point project.In the newly-built track of Japan, 80% or more engineering has used FFU synthesis wooden sleeper, in China Taiwan, FFU synthesis
Application of the sleeper on track engineering also starts the attention by owner.
It need to be calculated with 1800 or so sleepers by external experience 1km high-speed railway, 7000km high-speed railway FFU synthesis wooden sleeper
Market scale is up to 50,000,000,000 yuan.As the major matrix material of FFU synthesis wooden sleeper, the specific gravity of glass fibre is up to 80%, because
This, it may be said that the performance of glass fibre decides the performance of final product.For FFU synthesis wooden sleeper, glass fibre is required first
Yarn has excellent use smoothness, and such as filoplume low in pultrusion process, the requirement such as rub resistance followed by will be with polyurethane resin phase
Capacitive is good, is impregnated with quick and complete, it is most important that final fiberglass products have excellent mechanical performance.
General performance requires following (content of glass fiber is 75%, by taking 300tex as an example):
Tensile property (according to ASTMD2343 test method):
| Resin system | Polyurethane resin |
| Tensile strength | ≥2200MPa |
| Stretch modulus | ≥75GPa |
Cutting performance (according to ASTMD2344 test method):
| Resin system | Polyurethane resin |
| Shear strength | ≥60MPa |
Glass fiber yarn performance
| Layer difference test | ≤50mm |
| Wearability test | >=30 times |
2 meters of samples side-draw out of glass fiber yarn, by an alignment of yarn.Then the side of alignment is fixed, slowly
Ground will have loose part to flatten in glass fiber yarn inside.The other end of yarn alignment, measures longest and most in millimeters
The distance of shorter yarn, this is the test of layer difference.
1 meter of sample side-draw out of glass fiber yarn is the counterweight of 0.5kg at one.It in diameter is 10 millimeters by sample
It rubs on copper pipe, whether visual confirmation filoplume generates.Record Rubbing number when filoplume generates, as wearability test.
Thus under the premise of constant using E glass ingredient, energy and target need to be wanted by developing a kind of novel size
Resin has excellent compatibility, improves the effect of interface cohesion, to meet the index request of mechanical performance, while wanting to improve
Yam surface state improves convergence and wearability, reduces the generation of filoplume, is required with meeting doff and producing and using.
(3) summary of the invention:
It is an object of the present invention to provide a kind of sizes of FFU synthesis wooden sleeper alkali-free glass fibre yarn, using the size
The glass fiber yarn of production, not only with target resin compatible it is good, be impregnated with, and the mechanical performance of resulting product is high, uses
Smoothness is good, meets the requirement of standard.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of size of FFU synthesis wooden sleeper alkali-free glass fibre yarn, it is living by coupling agent, lubricant, film forming agent, surface
Property agent, pH adjusting agent, water be formulated, pH value is 2~10 (preferably 3~7)；
Wherein, the coupling agent uses silane coupling agent；
The lubricant uses water-soluble organic compounds, specific such as silicone oil or PEG series lubricant agent；
The film forming agent is the blend of epoxy emulsion, polyaminoester emulsion；
The surfactant is cationic surfactant；
The pH adjusting agent is acid；
In the size, the quality of nonaqueous component accounts for the 3%~10% of size gross mass, and surplus is water；It is described
Nonaqueous component are as follows: coupling agent, lubricant, film forming agent theoretical water removal after solid content part, surfactant, pH value adjust
Agent；Solid content part after the theoretical water removal of the film forming agent by after the theoretical water removal of epoxy emulsion solid content part and poly- ammonia
Solid content part composition after the theoretical water removal of ester lotion, and solid content part and polyurethane after the theoretical water removal of epoxy emulsion
The mass ratio of solid content part after the theoretical water removal of lotion is 1:0.18~0.75；
Gross mass based on nonaqueous component, the coupling agent, lubricant, film forming agent theoretical water removal after solid content portion
Divide, the mass percent of surfactant, pH adjusting agent is respectively as follows:
Preferably, based on the gross mass of nonaqueous component, the coupling agent, lubricant, film forming agent theoretical water removal after contain
Gu amount part, surfactant, pH adjusting agent mass percent be respectively as follows:
It is more preferred, the gross mass based on nonaqueous component, the coupling agent, lubricant, film forming agent theoretical water removal after
Solid content part, surfactant, pH adjusting agent mass percent be respectively as follows:
Most preferably, based on the gross mass of nonaqueous component, the coupling agent, lubricant, film forming agent theoretical water removal after
Solid content part, surfactant, pH adjusting agent mass percent be respectively as follows:
In the present invention, the preferred deionized water of the water.
The coupling agent generally uses the silane based coupling agents with epoxy group, vinyl or amino, what the present invention was applicable in
The available product grade of silane coupling agent has A-172, A-174, A-1100, A-187 etc..The use of coupling agent can protect fibre
Dimension avoids being damaged in drawing production, and plays the role of " bridge joint " between glass fibre and matrix resin, therefore is to influence
The key of glass fiber strength and glass fiber reinforced plastics product intensity.Suitable coupling agent selection, can make the glass fibers produced
Tieing up yarn product has better mechanical performance.The mass percent of coupling agent of the present invention is 1%~9%, preferably 2%~8%, more
It is preferred that 3%~7%, most preferably 4%~6%.
Water-soluble organic compound can be used in the lubricant, such as silicone oil or PEG series lubricant agent, specific such as polyethers
Modified silicon oil, PEG-400, PEG-600 etc..The use of lubricant predominantly meet glass fibre in wire drawing, post-process, used
The lubricant effect of journey, but excessive lubricant will affect the convergence of glass fiber yarn, and will affect final glass fiber reinforced plastics product
Mechanical performance.The mass percent of lubricant of the present invention is 4%~18%, preferably 5%~16%, more preferable 7%~14%,
Most preferably 9%~11%.
The film forming agent plays the role of protecting fiber as the main component of size, meets the continuous life of fiber
It produces, and conclusive influence is played on the mechanical strength of glass fibre final product, therefore, the selection of film forming agent is the present invention
Emphasis.The film forming agent that the present invention uses is the combination of epoxy emulsion and polyaminoester emulsion, and the present invention uses different types of cream
Liquid collocation uses, and is on the one hand to that glass fibre is made to have good convergence and wearability, is on the other hand to make glass
The compatibility requirements of fiber product and resin are good, to meet the requirement of final product mechanical property.The quality of film forming agent of the present invention
Percentage is 60%~85%, preferably 65%~80%, more preferable 68%~78%, most preferably 72%~77%.
Epoxy emulsion in the film forming agent is water-soluble epoxy resin lotion or bisphenol a epoxy resin emulsion, molecule
Measuring is 200~1200 (preferably 300~800), 0.2~2.0 μm of particle diameter of dispersing phase.Epoxy emulsion can be according to existing in the present invention
There is document voluntarily to prepare or use commercial goods.
Polyaminoester emulsion in the film forming agent is polyester polyurethane lotion, relative molecular mass is 20000~
40000 (preferably 25000~35000), particle diameter of dispersing phase are 0.2~2.0 μm, 10~50mpa.s of range of viscosities.Polyurethane
Lotion very strong ammonia ester bond containing polarized makes glass fibre have good convergence, is better than it to glass fibre protective effect
The film forming agent of its kind.Polyaminoester emulsion can voluntarily prepare according to existing literature or use commercial goods in the present invention.
The surfactant is cationic surfactant, can be selected from Fixanol, quaternary ammonium salt, one in amine salt
Kind, specifically such as octadecyltrimethylammonium chloride (1831), N- alkyl Diethylenetriamine, polyethyleneimine quaternary ammonium salt.This hair
The mass percent of bright surfactant be 1%~10%, preferably 2%~9%, more preferable 3%~8%, most preferably 6%~
7.5%.
The pH adjusting agent is using acid, organic acid or inorganic acid, such as citric acid, acetic acid, formic acid, acetic acid.
The effect of pH adjusting agent is primarily used to ancillary coupling agent dispersion and adjusts the pH value of prepared size.PH tune of the present invention
Save agent mass percent be 1%~5%, preferably 1.5%~4.5%, more preferable 2%~4%, most preferably 2.5%~
3.5%.
The size of FFU synthesis wooden sleeper alkali-free glass fibre yarn of the present invention, preparation method are as follows:
According to formula, in a clean container, the water of total amount 40%~50% is added, adds pH adjusting agent,
3~5min is stirred, silane coupling agent is subsequently added into, stirs 40~50min；Lubricant, surfactant is each 4~6 times personal
After 40~50 DEG C of water agitation and dilutions of quality, container is added；Again by after the water dilution of 1~3 times of quality of film forming agent, it is added and holds
Device；The amount for supplying water in formula, stirs evenly to get finished product.Wherein, the preferred deionized water of the water.
Using size of the present invention, according to the glass fibre production technology of this field routine, it can be made described
FFU synthesis wooden sleeper alkali-free glass fibre yarn, (i.e. the coated amount on the glass fibers of size accounts for glass fibers to combustible content
Tie up the ratio of quality) for general control 0.2%~0.8%, specific value needs the performance according to raw material itself, it is needed from product
From the point of view of the performance indicator and experimental results that reach, product of the combustible content 0.3%~0.6%, mechanical strength and resistance to
Mill performance is enough met the requirements.
Compared with prior art, size of the present invention can make the layer difference of glass fiber product keep stable and resistance to
Mill property greatly improves, and with resin compatible is good, good penetrability, the mechanical performance of product is high, to meet market and using need
It asks.
(4) specific embodiment
The present invention is specifically described by the following examples, but protection scope of the present invention is not by following implementation
Any restriction of example.
The size each component that the embodiment of the present invention uses is as follows:
The coupling agent uses aminopropyltriethoxywerene werene coupling agent, and product grade is A-1100 (manufacturer: beauty
Mai Tu company, state)；
The lubricant polyether modified silicon oil, product type are zbh-207 (manufacturer: precious chemical industry organosilicon in Qingdao
Co., Ltd)；
The film forming agent epoxy resin latex, product grade are DSM JS129 (manufacturer: Dutch DSM N. V.)；
The film forming agent polyaminoester emulsion, product grade are PU400S (manufacturer: Bayer Material Science Co., Ltd)；
The cationic surfactant octadecyltrimethylammonium chloride, product type are 1831 (manufacturers: Shanghai
Kingsoft longitude and latitude Chemical Co., Ltd.)；
The pH adjusting agent uses acetic acid.
What following table was produced by specific formulation examples (table 1) and according to the glass fibre production technology of this field routine
The specific test result (table 2) of 300tex spinning cake yarn.In each specific example of the present invention, the content of water accounts for size gross mass
94%, what is embodied in the following table 1 is the percentage that each nonaqueous component accounts for nonaqueous component total amount in size.
1 example 1~6 of table formula
| Component | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Coupling agent | 2 | 3 | 4 | 5 | 6 | 7 |
| Lubricant | 5 | 7 | 9 | 11 | 14 | 16 |
| Epoxy emulsion | 67 | 62 | 57 | 53 | 48 | 44 |
| Polyaminoester emulsion | 15 | 18 | 20 | 22 | 24 | 26 |
| Surfactant | 9.5 | 8 | 7.5 | 6 | 4.5 | 3 |
| PH adjusting agent | 1.5 | 2 | 2.5 | 3 | 3.5 | 4 |
| It is total to be formulated nonaqueous component ratio | 100 | 100 | 100 | 100 | 100 | 100 |
The example 1~6 of table 2 is formulated the test result of the spinning cake yarn of the size production of preparation
The embodiment of the present invention passes through size raw material according to the technical characterstic of polyurethane pultrusion molding process and FFU yarn
Selection, the optimization of formula, using the conventional suitable glass fibre production technology in this field, the FFU for producing meet demand is closed
At sleeper yarn product.
According to above formula test case, we can therefrom find out, by the design to component and constituent content, I
The available size to meet the requirements, wherein especially with example 3,4 better effects.The above is only preferred implementation sides of the invention
Formula, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvements and modifications, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (10)
1. a kind of size of FFU synthesis wooden sleeper alkali-free glass fibre yarn, which is characterized in that the size is by being coupled
Agent, lubricant, film forming agent, surfactant, pH adjusting agent, water are formulated, and pH value is 2~10；
Wherein, the coupling agent uses silane coupling agent；
The lubricant uses water-soluble silicone oil or PEG series lubricant agent；
The film forming agent is the blend of epoxy emulsion, polyaminoester emulsion, and the polyaminoester emulsion is polyester polyurethane cream
Liquid, relative molecular mass are 20000~40000；
The surfactant is cationic surfactant；
The pH adjusting agent is acid；
In the size, the quality of nonaqueous component accounts for the 3%~10% of size gross mass, and surplus is water；Described is non-
Water component are as follows: coupling agent, lubricant, film forming agent theoretical water removal after solid content part, surfactant, pH adjusting agent；
Solid content part after the theoretical water removal of the film forming agent by after the theoretical water removal of epoxy emulsion solid content part and polyurethane
Solid content part composition after the theoretical water removal of lotion, and solid content part and polyurethane cream after the theoretical water removal of epoxy emulsion
The mass ratio of solid content part after the theoretical water removal of liquid is 1:0.18~0.75；
Gross mass based on nonaqueous component, the coupling agent, lubricant, film forming agent theoretical water removal after solid content part, table
Face activating agent, pH adjusting agent mass percent be respectively as follows:
2. the size of FFU synthesis wooden sleeper alkali-free glass fibre yarn as described in claim 1, which is characterized in that based on non-
The gross mass of water component, the coupling agent, lubricant, film forming agent theoretical water removal after solid content part, surfactant, pH
The mass percent of value regulator is respectively as follows:
3. the size of FFU synthesis wooden sleeper alkali-free glass fibre yarn as described in claim 1, which is characterized in that based on non-
The gross mass of water component, the coupling agent, lubricant, film forming agent theoretical water removal after solid content part, surfactant, pH
The mass percent of value regulator is respectively as follows:
4. the size of FFU synthesis wooden sleeper alkali-free glass fibre yarn as described in claim 1, which is characterized in that described
Coupling agent is silane coupling A -172, A-174, A-1100 or A-187.
5. the size of FFU synthesis wooden sleeper alkali-free glass fibre yarn as described in claim 1, which is characterized in that described
Lubricant is polyether modified silicon oil, PEG-400 or PEG-600.
6. the size of FFU synthesis wooden sleeper alkali-free glass fibre yarn as described in claim 1, which is characterized in that it is described at
Epoxy emulsion in film is water-soluble epoxy resin lotion or bisphenol a epoxy resin emulsion, and molecular weight is 200~1200,
0.2~2.0 μm of particle diameter of dispersing phase.
7. the size of FFU synthesis wooden sleeper alkali-free glass fibre yarn as described in claim 1, which is characterized in that it is described at
Polyaminoester emulsion in film is polyester polyurethane lotion, and relative molecular mass is 20000~40000, disperses phase average
Partial size is 0.2~2.0 μm, 10~50mpa.s of range of viscosities.
8. the size of FFU synthesis wooden sleeper alkali-free glass fibre yarn as described in claim 1, which is characterized in that described
Surfactant is octadecyltrimethylammonium chloride, N- alkyl Diethylenetriamine or polyethyleneimine quaternary ammonium salt.
9. the size of FFU synthesis wooden sleeper alkali-free glass fibre yarn as described in claim 1, which is characterized in that described
PH adjusting agent is citric acid, acetic acid, formic acid or acetic acid.
10. a kind of preparation method of the size of FFU synthesis wooden sleeper alkali-free glass fibre yarn as described in claim 1,
It is characterized in that, the preparation method are as follows:
According to formula, in a clean container, the water of total amount 40%~50% is added, adds pH adjusting agent, stirring 3
~5min is subsequently added into silane coupling agent, stirs 40~50min；By each personal 4~6 times of quality of lubricant, surfactant
After 40~50 DEG C of water agitation and dilutions, container is added；Again by after the water dilution of 1~3 times of quality of film forming agent, container is added；It supplies
The amount of water, stirs evenly to get finished product in formula.
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| CN108863109A (en) * | 2017-05-12 | 2018-11-23 | 巨石集团有限公司 | A kind of glass fiber infiltration agent and its application in the preparation direct yarn of continuous fiber reinforcement polyamide alkali-free |
| CN107935411A (en) * | 2017-11-30 | 2018-04-20 | 巨石集团有限公司 | A kind of glass fiber infiltration agent and preparation method thereof |
| CN110511573B (en) * | 2019-08-06 | 2021-06-15 | 青岛中集创赢复合材料科技有限公司 | Wetting dispersion reinforcing agent, prepreg and glass fiber reinforced thermoplastic prepreg tape |
| CN112209637A (en) * | 2020-10-13 | 2021-01-12 | 巨石集团有限公司 | Glass fiber direct roving impregnating compound and preparation method and application thereof |
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| US3655353A (en) * | 1969-05-21 | 1972-04-11 | Ppg Industries Inc | Glass fiber size |
| CN103771732B (en) * | 2014-01-10 | 2015-12-30 | 巨石集团有限公司 | The treating compound of the direct yarn of a kind of epoxy pressure piping alkali free glass fibre |
| CN103880300B (en) * | 2014-01-29 | 2016-08-17 | 巨石集团有限公司 | A kind of size of thermoplastic glass's direct yarn of steel conduit alkali-free glass fibre |
| CN105174750B (en) * | 2015-09-02 | 2018-03-02 | 巨石集团有限公司 | A kind of size for strengthening the direct yarn of winding-type medium-alkali glass fibre |
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