CN104358103A - Sizing agent for carbon fiber and production method of sizing agent - Google Patents
Sizing agent for carbon fiber and production method of sizing agent Download PDFInfo
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- CN104358103A CN104358103A CN201410619017.5A CN201410619017A CN104358103A CN 104358103 A CN104358103 A CN 104358103A CN 201410619017 A CN201410619017 A CN 201410619017A CN 104358103 A CN104358103 A CN 104358103A
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- epoxy resin
- sizing agent
- carbon fiber
- emulsion
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Abstract
The invention provides a sizing agent for a carbon fiber and a production method of the sizing agent. An epoxy resin emulsion, which is excellent in stability, and of which the mean grain size is smaller than 300nm can be obtained if mechanical shearing is combined with ultrasonic emulsification, and an efficient emulsifier is used cooperatively under the premise that the epoxy resin is not subjected to hydrophilic modification. The emulsion is taken as the sizing agent for the carbon fiber, and is even to starch; and the water absorption of the starched fiber is small.
Description
Technical field
The present invention relates to fabric manufacturing area, particularly relate to a kind of carbon fiber sizing agent and production method thereof.
Background technology
Carbon fiber is a kind of reinforcing material of good mechanical performance, has very high specific strength and specific modulus.But, carbon fiber itself is a kind of fragile material, prepares in the process of composite, when rubbing mutually between fiber and manufacturing equipment and fiber at fiber production process and use fiber, be very easy to produce fibre single thread rub, thus produce the problem of a large amount of lousiness.In addition, because carbon fiber is through the product of high-temperature process acquisition, its surface exhibits goes out obvious chemical inertness, thus when preparing composite, fiber and as matrix material resin between compatibility poor, thus cause the mechanical property of fiber not played completely in the composite.
In order to solve the problem of above-mentioned two aspects, the carbon fiber of industrial production, usually all starching process to be carried out to fiber surface.Starching process refer to by fiber by certain density slurry, the active ingredient in slurry is deposited on fiber surface, through oven dry after fiber surface formed diaphragm.The film that this layer of sizing agent is formed both can reduce the friction between fiber and equipment and fiber, reduce the generation of lousiness, again can when preparing composite, as the transition zone between fiber and matrix resin, according to the parents' character of himself, affinity between significant raising fiber and matrix material, thus the performance improving carbon fibre composite.
The main component of general carbon fiber sizing agent is epoxy resin, and this is because epoxy resin itself has good conjunctiva, can form tough and firm film at fiber surface, well plays the effect of protection fiber.And the most widely used matrix material is also epoxy resin in carbon fibre composite, be, between the sizing agent of main component and epoxy resin base material, there is good compatibility with epoxy resin.But, because epoxy resin viscosity is large, be solid under part resin normal temperature, it to be formed homogeneous film at carbon fiber surface, resin dispersion must be formed dispersion in media as well, fiber stops the regular hour in dispersion, and what resin just can be homogeneous is deposited on fiber surface, namely forms the film of solidification after oven dry.Common dispersion has solution and emulsion.Epoxy resin is directly dissolved in acetone and other organic solvent and obtains resin solution, can process fiber as sizing agent.But organic solvent is usually all volatile, inflammable, be present in a large number in workshop and propose very high requirement to the safety in workshop, safety cost is very high, and causes the concentration of sizing agent in continuous change, does not thus use solution-type sizing agent in actual production process.Normally used sizing agent is that epoxy resin is prepared into water serial emulsion.The concentration of aqueous emulsion easily controls, and has excellent security.
As the epoxy resin latex of carbon fiber sizing agent, have much concrete requirement, such as, particle diameter preferably at below 300nm, maximum can not more than 500nm, emulsion intercalation method will be got well, and starching is even, and the fibrous absorbent after starching wants little etc.Because epoxy resin is a kind of material with strong hydrophobicity, in order to be prepared into aqueous emulsion, have the method that two kinds are common, the first by epoxy resin with emulsifying agent together with water, high-speed stirred shear effect emulsified.This method, can ensure epoxy resin film strength and heat resistance, and after starching, the water imbibition of fiber is also very little, but even if adopt the emulsifier special of special synthesis, be also difficult to the emulsion obtaining excellent in stability, and the particle diameter of emulsion is large, usually at micron order.Another kind method is in epoxy molecule, introduce hydrophilic group, namely carries out hydrophilic modifying to epoxy resin, prepares hydrophilic matrix tablets, then by emulsified for its situation about existing at emulsifying agent.This method can obtain and have good stability, and average mark shot footpath is in the emulsion of hundreds of nanometer level.But owing to introducing hydrophilic radical in epoxy molecule, cause the heat resistance of epoxy resin to decline, water imbibition strengthens, and the film strength of formation is also influenced.Therefore, solve the problem and just seem particularly important.
Summary of the invention
The object of this invention is to provide a kind of carbon fiber sizing agent and production method thereof, under the prerequisite of epoxy resin not being carried out to hydrophilic modifying, if mechanical shearing and ultrasonic emulsification two kinds of means are combined, and with the use of efficient emulsifying agent, excellent in stability can be obtained, epoxy resin latex that average grain diameter is less than 300nm.This emulsion is as carbon fiber sizing agent, and starching is even, and the fibrous absorbent amount after starching is little, thus the problems referred to above have been gone up in solution.
The invention provides a kind of carbon fiber sizing agent, the constituent mass of described sizing agent is than as follows: epoxy resin is 30 ~ 45; Ester is 3 ~ 5; Emulsifying agent is 7 ~ 10; Water is 40 ~ 60.
Further improvement is: described epoxy resin comprises liquid-state epoxy resin and solid epoxy resin, and described liquid-state epoxy resin is low-molecular-weight epoxy resin, and solid epoxy resin is high molecular expoxy resin.
Further improvement is: described Ester is liquid monobasic ester, and carbon atom number is wherein between 13 ~ 25.
Further improvement is: described emulsifying agent is the polyethers emulsifying agent obtained with ethyoxyl and propoxyl group copolymerization.
A production method for carbon fiber sizing agent, described production method is as follows:
Step one: solid epoxy resin is ground with ball mill in advance, and weigh up rear input agitator tank with liquid-state epoxy resin, tristerin, epoxy resin emulsifying agent according to mass ratio 15,20,5,5;
Step 2: open heating and temperature is increased to 70 DEG C, open and stir;
Step 3: simultaneously open high speed shear;
Step 4: the water adding 55 parts of quality, opens the valve bottom agitator tank, and the liquid level in groove to be emulsified exceedes half and starts supersonic generator and circulating pump later, and emulsion is circulated in the entire system;
Step 5: regulate circular flow to make the liquid level of emulsifying tank and agitator tank keep stable;
Step 6: circulate after one hour and stop, emulsion being discharged from discharge gate, preparation completes.
Further improvement is: described step 3 medium shear rate is 3000rpm.
High speed machine emulsification pretreatment equipment in the present invention is the tank body that an inside is equipped with agitator and cutting head.The maximum shear speed of cutting head, should be not less than 2500rpm, if stir speed (S.S.) is less than 2500rpm, very little to the shear action of dispersion, affects the minimum grain size that final emulsion can reach.
High speed machine emulsification pretreatment tank has charge door, the various compositions of sizing agent, comprising resin, emulsifying agent, ester class and water etc. can add from charge door.The bottom of agitator tank has pipeline to be connected to ultrasonic emulsator, and on pipeline, be also furnished with discharging opening, the emulsion after emulsification completes can be discharged from discharging opening simultaneously.Agitator tank position is spatially higher than ultrasonic emulsator, and thus emulsion spontaneously under gravity can flow to ultrasonic emulsator from agitator tank.
Ultrasonic emulsator utilizes hyperacoustic effect to carry out the equipment of emulsification to dispersion.It mainly comprises the formations such as supersonic generator, ultrasonic wave vibration plate, emulsifying tank.Wherein ultrasonic wave vibration plate is arranged in emulsifying tank.Ultrasonic wave, under different frequencies and intensity, may show emulsification, also may show demulsification, therefore, and supersonic generator preferably intensity and frequency-adjustable.For taking epoxy resin as the emulsion system of main component, through test of many times, find that emulsifying effectiveness is best when frequency is 20kHz, is thus defined as 20kHz by hyperacoustic frequency in the present invention.
Ultrasonic emulsification groove, agitator tank should possess heating and heat insulation function, and the specific implementation of heating and insulation is not limit, and can be electrical heating, also can be jacket water (J.W.) heating or other mode of heating.The pipeline of system also should carry out isothermal holding.
Circulating pump in the present invention is membrane pump, and the stable consideration of collateral security emulsion had better not use centrifugal pump.In addition, in order to ensure emulsifying effectiveness, special emulsification pump can be adopted, while completing Matter Transfer function, further emulsification can also be carried out to emulsion, therefore recommendation.The liquid level of agitator tank should be able to be kept stable by the flow of pump.
High speed machine emulsification pretreatment tank in the present invention and the size of ultrasonic emulsification groove all do not do concrete restriction, can decide according to the demand of reality.
When utilizing the emulsifying systems in the present invention to carry out the production of emulsifying agent, after various component is dropped into agitator tank in proportion, temperature is increased to preset value, opens high speed shear and stirring.The ordering in launching of each component does not do concrete restriction, can decide in its sole discretion according to technological requirement.Open the valve bottom agitator tank, the liquid level in groove to be emulsified exceedes half and starts supersonic generator and circulating pump later, and emulsion is circulated in the entire system.Circular flow is regulated to make the liquid level of emulsifying tank and agitator tank keep stable.The circulating emulsion time at least more than 1 hour, otherwise is difficult to fully emulsified, can not obtain enough little emulsion particle diameter.
Sizing agent in the present invention take epoxy resin as principle active component.The epoxy resin used, mainly bisphenol A type epoxy resin, comprise low molecular weight and high molecular two class.Low-molecular-weight epoxy resin is liquid at normal temperatures, such as epoxy resin E51, E44 etc.High molecular expoxy resin is solid-state or gel at normal temperatures, as epoxy resin E20, E33 etc.
Ester in the present invention, mainly serves as lubricant, reduces the friction and wear between fiber and equipment after starching and fiber, can also give fiber certain flexibility simultaneously.Ester class used is mainly liquid monobasic ester, and carbon atom number is wherein between 13 ~ 25.Concrete as isobutyl palmitate, tristerin etc., not strict especially restriction.
Emulsifying agent in the present invention is nonionic emulsifier, is more specifically the polyethers emulsifying agent obtained with ethyoxyl and propoxyl group copolymerization.
The water used in the present invention is deionized water.
In the present invention, in sizing agent, the mass ratio of various component is as follows: epoxy resin comprises liquid-state epoxy resin and solid epoxy resin, and mass fraction is about 30 ~ 45; Ester is 3 ~ 5; Emulsifying agent 7 ~ 10; Water 40 ~ 60.
The invention has the beneficial effects as follows: by mechanical shearing and hyperacoustic acting in conjunction, can under the prerequisite of epoxy resin not being carried out to hydrophilic modifying, obtain the emulsion of high stability, small particle diameter, this emulsion is used for the sizing agent of carbon fiber, effectively can control the saturated water imbibition of fiber, ensure the performance of carbon fibre composite.
Detailed description of the invention
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and this embodiment only for explaining the present invention, does not form limiting the scope of the present invention.
Method of testing is as follows:
Dewatering ability: use equipment is generic centrifuge, a small amount of finish sample is placed in 15ml test tube under the rotating speed of 3000rpm centrifugal 15 minutes, emulsion is stable without significant change, if precipitation appears in emulsion, lamination is poor stability.
Emulsion particle diameter: use equipment is laser particle analyzer.Get samples of latex laser particle analyzer and measure its particle diameter.
The water imbibition of tow after starching: take predrying (40 ± 5 DEG C) that about 1g fiber carries out 1h, then puts into standard atmosphere condition (or exposing and air) 3 days.Weigh, be designated as W0, then by sample over dry, weigh, be designated as Wd, be calculated as follows water absorption:
We(%)=（W0-Wd）/Wd×100
Embodiment 1
Epoxy resin E51, E20(are ground with ball mill in advance), tristerin, epoxy resin emulsifying agent weigh up rear input agitator tank according to mass ratio 20,15,5,5, open heating and temperature be increased to 70 DEG C, open and stir.Open high speed shear, shear rate is 3000rpm simultaneously, adds the water of 55 parts of quality, opens the valve bottom agitator tank, and the liquid level in groove to be emulsified exceedes half and starts supersonic generator and circulating pump later, and emulsion is circulated in the entire system.Circular flow is regulated to make the liquid level of emulsifying tank and agitator tank keep stable.Circulate after one hour and stop, from discharge gate, emulsion being discharged.
The particle diameter obtaining sizing agent is 303nm, good stability.
Acquisition sizing agent is diluted to 4.5%, uses general device for sizing to carry out starching to carbon fiber, starching amount is 0.82%, and water imbibition is 0.02%.
Embodiment 2
Epoxy resin E51, E20(are ground with ball mill in advance), tristerin, epoxy resin emulsifying agent weigh up rear input agitator tank according to mass ratio 20,15,5,5, open heating and temperature be increased to 80 DEG C, open and stir.Open high speed shear, shear rate is 3000rpm simultaneously, adds the water of 55 parts of quality, opens the valve bottom agitator tank, and the liquid level in groove to be emulsified exceedes half and starts supersonic generator and circulating pump later, and emulsion is circulated in the entire system.Circular flow is regulated to make the liquid level of emulsifying tank and agitator tank keep stable.Circulate after one hour and stop, from discharge gate, emulsion being discharged.
Obtain that the particle diameter of sizing agent is 267, good stability.
Acquisition sizing agent is diluted to 4.5%, uses general device for sizing to carry out starching to carbon fiber, starching amount is 0.80%, and water imbibition is 0.03%.
Embodiment 3
Epoxy resin E51, E20(are ground with ball mill in advance), tristerin, epoxy resin emulsifying agent weigh up rear input agitator tank according to mass ratio 20,15,5,5, open heating and temperature be increased to 70 DEG C, open and stir.Open high speed shear, shear rate is 2500rpm simultaneously, adds the water of 55 parts of quality, opens the valve bottom agitator tank, and the liquid level in groove to be emulsified exceedes half and starts supersonic generator and circulating pump later, and emulsion is circulated in the entire system.Circular flow is regulated to make the liquid level of emulsifying tank and agitator tank keep stable.Circulate after one hour and stop, from discharge gate, emulsion being discharged.
Obtain that the particle diameter of sizing agent is 318, good stability.
Acquisition sizing agent is diluted to 4.5%, uses general device for sizing to carry out starching to carbon fiber, starching amount is 0.81%, and water imbibition is 0.01%.
Embodiment 4
Epoxy resin E51, E20(are ground with ball mill in advance), tristerin, epoxy resin emulsifying agent weigh up rear input agitator tank according to mass ratio 20,15,5,5, open heating and temperature be increased to 70 DEG C, open and stir.Open high speed shear, shear rate is 3000rpm simultaneously, adds the water of 55 parts of quality, opens the valve bottom agitator tank, and the liquid level in groove to be emulsified exceedes half and starts supersonic generator and circulating pump later, and emulsion is circulated in the entire system.Circular flow is regulated to make the liquid level of emulsifying tank and agitator tank keep stable.Circulate after 2.5 hours and stop, from discharge gate, emulsion being discharged.
Obtain that the particle diameter of sizing agent is 318, good stability.
Acquisition sizing agent is diluted to 4.5%, uses general device for sizing to carry out starching to carbon fiber, starching amount is 0.83%, and water imbibition is 0.01%.
As can be seen from embodiment 1-4 data, the present invention is by mechanical shearing and hyperacoustic acting in conjunction, can under the prerequisite of epoxy resin not being carried out to hydrophilic modifying, obtain the emulsion of high stability, small particle diameter, this emulsion is used for the sizing agent of carbon fiber, effectively can control the saturated water imbibition of fiber, ensure the performance of carbon fibre composite.
Claims (6)
1. a carbon fiber sizing agent, is characterized in that: the constituent mass of described sizing agent is than as follows: epoxy resin is 30 ~ 45; Ester is 3 ~ 5; Emulsifying agent is 7 ~ 10; Water is 40 ~ 60.
2. carbon fiber sizing agent as claimed in claim 1, it is characterized in that: described epoxy resin comprises liquid-state epoxy resin and solid epoxy resin, described liquid-state epoxy resin is low-molecular-weight epoxy resin, and solid epoxy resin is high molecular expoxy resin.
3. carbon fiber sizing agent as claimed in claim 1, is characterized in that: described Ester is liquid monobasic ester, and carbon atom number is wherein between 13 ~ 25.
4. carbon fiber sizing agent as claimed in claim 1, is characterized in that: described emulsifying agent is the polyethers emulsifying agent obtained with ethyoxyl and propoxyl group copolymerization.
5. a production method for carbon fiber sizing agent as claimed in claim 1, is characterized in that: described production method is as follows:
Step one: solid epoxy resin is ground with ball mill in advance, and weigh up rear input agitator tank with liquid-state epoxy resin, tristerin, epoxy resin emulsifying agent according to mass ratio 15,20,5,5;
Step 2: open heating and temperature is increased to 70 DEG C, open and stir;
Step 3: simultaneously open high speed shear;
Step 4: the water adding 55 parts of quality, opens the valve bottom agitator tank, and the liquid level in groove to be emulsified exceedes half and starts supersonic generator and circulating pump later, and emulsion is circulated in the entire system;
Step 5: regulate circular flow to make the liquid level of emulsifying tank and agitator tank keep stable;
Step 6: circulate after one hour and stop, emulsion being discharged from discharge gate, preparation completes.
6. the production method of a kind of carbon fiber sizing agent as claimed in claim 5, is characterized in that: described step 3 medium shear rate is 3000rpm.
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| CN201410619017.5A CN104358103A (en) | 2014-11-06 | 2014-11-06 | Sizing agent for carbon fiber and production method of sizing agent |
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Cited By (4)
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| CN105862428A (en) * | 2016-05-05 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method and product of graphene-modified carbon fiber sizing agent |
| CN106217825A (en) * | 2016-07-21 | 2016-12-14 | 中国商用飞机有限责任公司 | Prepare the method that carbon fibre fabric strengthens polyphenylene sulfide thermoplastic composite |
| CN107759147A (en) * | 2017-09-07 | 2018-03-06 | 霍邱县红顺生态建材科技有限责任公司 | A kind of preparation method of water-permeable brick |
| CN108350645A (en) * | 2015-11-05 | 2018-07-31 | 三菱化学株式会社 | Its molding fibre reinforced composites of progress of continuous carbon fibre bundle, sheet molding compound and use |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108350645A (en) * | 2015-11-05 | 2018-07-31 | 三菱化学株式会社 | Its molding fibre reinforced composites of progress of continuous carbon fibre bundle, sheet molding compound and use |
| CN105862428A (en) * | 2016-05-05 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method and product of graphene-modified carbon fiber sizing agent |
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| CN106217825A (en) * | 2016-07-21 | 2016-12-14 | 中国商用飞机有限责任公司 | Prepare the method that carbon fibre fabric strengthens polyphenylene sulfide thermoplastic composite |
| CN107759147A (en) * | 2017-09-07 | 2018-03-06 | 霍邱县红顺生态建材科技有限责任公司 | A kind of preparation method of water-permeable brick |
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Application publication date: 20150218 |