CN101982602A - Sizing agent for carbon fiber - Google Patents
Sizing agent for carbon fiber Download PDFInfo
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- CN101982602A CN101982602A CN201010522312.0A CN201010522312A CN101982602A CN 101982602 A CN101982602 A CN 101982602A CN 201010522312 A CN201010522312 A CN 201010522312A CN 101982602 A CN101982602 A CN 101982602A
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- curing agent
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Abstract
The invention discloses a sizing agent for a carbon fiber, belonging to the fields of organic chemistry and fiber materials. The sizing agent is an epoxy water emulsion added with an aqueous curing agent, wherein the aqueous curing agent is modified epoxy amine curing agent, namely an amidated amine curing agent obtained by a reaction between a mono-fatty acid and an epoxy amine curing agent, a polyamide curing agent obtained by a reaction between a dimer acid and an epoxy amine curing agent and a curing agent obtained by a reaction between an epoxy amine curing agent and epoxy resin; the epoxy emulsion uses bisphenol A epoxy resin as the main body, and the epoxy equivalent is 200-500; the amount of the aqueous curing agent is 10% to 40% of theoretical one, and the theoretical amount should be calculated as follows: W=(Namine/NEP)*100, wherein Namine is the amine hydrogen equivalent of the curing agent, NEP is the epoxy equivalent of the epoxy resin, and W is the theoretical amount of the curing agent required by 100 grams of epoxy resin. The sizing agent is safe and healthy, the stability and the bundling performance are further improved, and the interface bonding strength of the composite material is enhanced.
Description
Technical field
The present invention relates to a kind of cementing agent, relate in particular to the cementing agent on the carbon fiber that a kind of 1000--3000 of being used for ℃ heat treatment obtains, belong to organic chemistry and fibrous material field.
Technical background
Carbon fiber is a kind of reinforcing material that grows up after the 1950's, it has a series of excellent properties such as high specific strength, high ratio modulus, high temperature resistant, corrosion-resistant, conduction and thermal coefficient of expansion be little, therefore is widely used in fields such as Aero-Space, sports equipment.Because the carbon fiber percentage elongation is low, belong to fragile material, in production and back process, rupture easily through the mechanical friction monofilament, produce lousiness, fiber and performance of composites thereof are descended.Therefore, carbon fiber surface will be coated with last layer protection glue usually, and promptly cementing agent makes the collection of filaments, reduces friction relatively, avoids producing lousiness in the process of back.Carbon fiber need use with the compound form with composite of resin matrix usually, and the mechanical property of excellences such as the high specific strength of carbon fiber, high ratio modulus will be fully played, and needs between carbon fiber and resin matrix bonding good.Carbon fiber is through after the high-temperature heat treatment, and surface-activity point is few, and inertia is big, and is relatively poor with the adhesive property of matrix resin.The cementing agent of carbon fiber surface is introduced suitable boundary layer between fiber and resin matrix, can increase the wettability with matrix resin, and carbon fiber is combined well with resin matrix, improves the adhesive strength at interface.Because under the more situation of matrix resin of carbon fibre reinforced composite is epoxy resin, therefore carbon fiber with cementing agent based on epoxy resin latex, though this aqueous emulsion type cementing agent has overcome problems such as the safety, health of early stage solvent-borne type cementing agent, but added emulsifying agent during owing to the preparation emulsion, cause its convergence to carbon fibre tow to descend, also there is negative effect the while to the interface of composite.
Summary of the invention
The purpose of this invention is to provide the cementing agent on the carbon fiber that a kind of 1000--3000 of being used for ℃ heat treatment obtains, on advantage bases such as assurance emulsion-type cementing agent safety and sanitation, further improve its stability and convergence, and can improve the interfacial adhesion strength of epoxy resin base carbon fiber composite material.
For achieving the above object, the technical scheme that cementing agent on the carbon fiber that a kind of 1000--3000 of being used for ℃ of heat treatment of the present invention obtains is taked is the epoxy resin aqueous emulsion that is added with waterborne curing agent, described waterborne curing agent is the epoxy resin amine curing agent of modification, it is the amidatioon amine curing agent that mono fatty acid and epoxy resin amine curing agent obtain according to the routine techniques reaction, the polyamide-based curing agent that dimeric dibasic acid and epoxy resin amine curing agent obtain according to the routine techniques reaction, the curing agent that epoxy resin amine curing agent and epoxy resin addition obtain, the curing agent after the above-mentioned three class modifications all can reach technique effect of the present invention; Epoxy resin latex is for being matrix resin with the bisphenol A epoxide resin, and epoxide equivalent is 200-500; The consumption of waterborne curing agent is the 10-40% of theoretical consumption.The computational methods of theoretical consumption are as follows:
W=(N
Amine/ N
EP) * 100
N wherein
AmineAmine hydrogen equivalent for curing agent; N
EPEpoxide equivalent for epoxy resin; W is the theoretical consumption of the curing agent of 100 gram epoxy resin needs, and unit is gram.
Above-mentioned waterborne curing agent is the curing agent that obtains of epoxy resin amine curing agent and epoxy resin addition more preferably, and is because this curing agent has the molecular structure of close epoxy resin, good with epoxy resin compatibility.
In the epoxy resin aqueous emulsion, add waterborne curing agent, make the epoxy resin in the cementing agent coating of carbon fiber surface partly solidified, increase the crosslinking points between the monofilament, improve convergence.Curing agent has been introduced active function groups simultaneously, can improve the interfacial adhesion strength of epoxy resin base carbon fiber composite material.
The curing agent that adds in epoxy resin latex among the present invention is water miscible, and non-water-soluble curing agent causes the decline of emulsion-stabilizing easily, and waterborne curing agent has parents' structure of similar emulsifying agent, can improve the stability of emulsion.
Hardener dose very little, the raising of convergence, bonding interface is not obvious, the consumption of curing agent is too many, the fibre bundle hardening, the resin wettability of fiber is poor.
The epoxy resin latex that uses among the present invention is for to be matrix resin with bisphenol A epoxide resin, and epoxide equivalent is 200-500, and epoxide equivalent is too high, and resin viscosity is big, fibre bundle hardening after the gluing, back poor processability.Emulsifying agent is selected nonionic emulsifier for use, avoids the adverse effect of ionic emulsifying agent intermediate ion to cementing agent.Advantage of the present invention
The carbon current fiber based on epoxy resin latex, has added emulsifying agent during owing to the preparation emulsion with cementing agent, causes its convergence to carbon fibre tow to descend, and also there is negative effect the while to the interface of composite.The present invention is directed to the problem that conventional emulsion type cementing agent convergence and cementability aspect exist, a certain amount of waterborne curing agent is added in proposition in epoxy resin latex, make the epoxy resin in the cementing agent coating of carbon fiber surface partly solidified, increase the crosslinking points between the monofilament, improve convergence.The active function groups that exists in the curing agent has very great help to the interfacial adhesion strength that improves epoxy resin base carbon fiber composite material simultaneously.
Stability, convergence and the carbon fiber of effect of the present invention by epoxy resin latex and the interlaminar shear strength evaluation of the unidirectional composite laminate of epoxy resin.Concrete evaluation method is as follows.
1. stability of emulsion evaluation method
Accurately about 20 grams of the epoxy resin latex of weighing mass percent concentration 5% are put in the 50ml beaker, at room temperature place 7 days, observe the variation of emulsion.After 7 days, pour out beaker clear liquid at the middle and upper levels, the sediment at the bottom of remaining in glass is dry under the temperature of 105 degree, weigh, be calculated as follows precipitation capacity.
W％＝(m
1/(m
0×5％))×100％
Wherein, W is a precipitation capacity, m
0Be the weight of emulsion before placing, unit is gram; m
1Be sedimentary quality at the bottom of the cup, unit is gram.
2. the evaluation method of convergence
Get a segment length and be the carbon fibre tow after the gluing about 10 centimetres, tear along the fiber axis direction from the middle part of this section fibre bundle, observe the connection situation between the monofilament in the tow, the tie point between the monofilament is many, form network-like structure for well, the then convergence that tie point is few is poor.
3. the evaluation method of interlaminar shear strength (ILSS)
The evaluation method of interlaminar shear strength is measured by GB GB3357-82 method.Resin matrix adopts phenolic aldehyde epoxy 648, and curing agent is the boron trifluoride mono aminoethane.
Description of drawings
Fig. 1 uses the convergence contrast of carbon fibre tow after the different cementing agent gluings.
A embodiment 1, b embodiment 2, c Comparative Examples 1, d Comparative Examples 2, e Comparative Examples 3, f Comparative Examples 4
The specific embodiment
Embodiment 1
The polyethylene glycol of 80 gram bisphenol A type epoxy resin E-31,10 gram fatty alcohol-polyoxyethylene ether AE07 and 10 gram-molecular weights 400 is stirred with homogenizer under 55 ℃, slowly add entry in the whipping process, by the emulsification of phase reversal method, final acquisition solid content is the emulsion of mass percent about 40%, and this emulsion is designated as A.
A is diluted to mass percent 5%, add 20% of the theoretical consumption of 7k type waterborne curing agent (addition product of epoxy resin amine curing agent and epoxy resin, the production of the special beautiful intrinsic limit in Beijing company), obtain cementing agent B, carry out the emulsion-stabilizing property testing, the results are shown in Table 1.Carry out gluing, test then, method is as follows.
The 3K that 2500 ℃ of heat treatments are obtained, PAN base carbon fibre with cementing agent B gluing, carry out the test of convergence, ILSS with the original cementing agent of acetone flush away then, the results are shown in Table 1 and Fig. 1 in embodiment 1.
Embodiment 2
Epoxy resin latex A is diluted to mass percent 5%, adds the 7K type waterborne curing agent of theoretical consumption 30%, obtain cementing agent C, other is with embodiment 1.Test result see Table 1 and Fig. 1 in embodiment 2.
Comparative Examples 1
Epoxy resin latex A is diluted to mass percent 5%, adds the 7K type waterborne curing agent of theoretical consumption 50%, obtain cementing agent D, other is with embodiment 1.Test result see Table 1 and Fig. 1 in Comparative Examples 1.
Comparative Examples 2
In mass percent is 5% A, add the curing agent 3 ' of theoretical consumption 20%, 3-dimethyl 4 ', 4-diamino-dicyclohexyl methane (DMDC).DMDC can be dissolved in earlier in a spot of acetone soln, joins mass percent again and is among 5% the A, obtains cementing agent E, and other is with embodiment 1.Test result see Table 1 and Fig. 1 in Comparative Examples 2.
Comparative Examples 3
In mass percent was 5% A, the curing agent DMDC that adds theoretical consumption 50% obtained cementing agent F, and other is with embodiment 1.Test result see Table 1 and Fig. 1 in Comparative Examples 3
Comparative Examples 4
With mass percent be 5% A as cementing agent, other is with embodiment 1.Test result see Table 1 and Fig. 1 in Comparative Examples 4.
Table 1 stability of emulsion and ILSS test result
Claims (2)
1. cementing agent that is used on the carbon fiber that 1000--3000 ℃ of heat treatment obtains, it is characterized in that, described cementing agent is the epoxy resin aqueous emulsion that is added with waterborne curing agent, described waterborne curing agent is the epoxy resin amine curing agent of modification, it is the amidatioon amine curing agent that mono fatty acid and epoxy resin amine curing agent obtain according to the routine techniques reaction, the polyamide-based curing agent that dimeric dibasic acid and epoxy resin amine curing agent obtain according to the routine techniques reaction, the curing agent that epoxy resin amine curing agent and epoxy resin addition obtain, epoxy resin latex is for being matrix resin with the bisphenol A epoxide resin, and epoxide equivalent is 200-500; The consumption of waterborne curing agent is 1040% of a theoretical consumption, and the computational methods of theoretical consumption are as follows:
W=(N
Amine/ N
EP) * 100
N wherein
AmineAmine hydrogen equivalent for curing agent; N
EPEpoxide equivalent for epoxy resin; W is the theoretical consumption of the curing agent of 100 gram epoxy resin needs, and unit is gram.
2. according to the cementing agent of claim 1, it is characterized in that, also contain fatty alcohol-polyoxyethylene ether and PEG400 in the described epoxy resin aqueous emulsion.
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| CN201010522312A CN101982602B (en) | 2010-10-22 | 2010-10-22 | Sizing agent for carbon fiber |
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| CN201010522312A CN101982602B (en) | 2010-10-22 | 2010-10-22 | Sizing agent for carbon fiber |
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| CN101982602B CN101982602B (en) | 2011-11-30 |
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| CN201010522312A Expired - Fee Related CN101982602B (en) | 2010-10-22 | 2010-10-22 | Sizing agent for carbon fiber |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104141230A (en) * | 2014-07-24 | 2014-11-12 | 中复神鹰碳纤维有限责任公司 | Method for reducing friction coefficient of carbon fiber |
| CN105040444A (en) * | 2015-09-08 | 2015-11-11 | 湖州宏鑫绸厂 | Novel nano water-borne epoxy resin sizing agent for carbon fibers and preparation method thereof |
| CN105482081A (en) * | 2016-01-08 | 2016-04-13 | 中简科技股份有限公司 | Preparation method of emulsion type epoxy resin |
| CN108049183A (en) * | 2017-12-22 | 2018-05-18 | 北京化工大学 | It is a kind of for cementing agent of carbon fiber and preparation method thereof |
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| CN101858038A (en) * | 2010-06-18 | 2010-10-13 | 济南大学 | Carbon fiber emulsion sizing agent and preparation method and application thereof |
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2010
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| JP2855970B2 (en) * | 1992-06-16 | 1999-02-10 | 日東紡績株式会社 | Fixing agent for preventing fraying of glass fiber fabric and glass fiber fabric using the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104141230A (en) * | 2014-07-24 | 2014-11-12 | 中复神鹰碳纤维有限责任公司 | Method for reducing friction coefficient of carbon fiber |
| CN104141230B (en) * | 2014-07-24 | 2016-03-16 | 中复神鹰碳纤维有限责任公司 | A kind of method reducing carbon fiber friction coefficient |
| CN105040444A (en) * | 2015-09-08 | 2015-11-11 | 湖州宏鑫绸厂 | Novel nano water-borne epoxy resin sizing agent for carbon fibers and preparation method thereof |
| CN105040444B (en) * | 2015-09-08 | 2018-04-20 | 威海诺葳信和新材料有限公司 | A kind of preparation method of nanometer waterborne epoxy resin sizing agent for carbon fiber |
| CN105482081A (en) * | 2016-01-08 | 2016-04-13 | 中简科技股份有限公司 | Preparation method of emulsion type epoxy resin |
| CN108049183A (en) * | 2017-12-22 | 2018-05-18 | 北京化工大学 | It is a kind of for cementing agent of carbon fiber and preparation method thereof |
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| CN101982602B (en) | 2011-11-30 |
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Granted publication date: 20111130 Termination date: 20211022 |