CN102926205B - Sizing agent for emulsion type carbon fiber, preparation method and application of sizing agent - Google Patents
Sizing agent for emulsion type carbon fiber, preparation method and application of sizing agent Download PDFInfo
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- CN102926205B CN102926205B CN201210465964.4A CN201210465964A CN102926205B CN 102926205 B CN102926205 B CN 102926205B CN 201210465964 A CN201210465964 A CN 201210465964A CN 102926205 B CN102926205 B CN 102926205B
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Abstract
The invention discloses a sizing agent for emulsion type carbon fiber, a preparation method and an application of the sizing agent. The sizing agent is prepared by the following raw materials in percentage by weight: 2-40% of epoxy resin, 1-20% of modifier, 0-96.5% of water, 0.5-15% of surfactant and 0.1-2.0% of inorganic ammonium salt. The sizing agent comprises modifiers with structural units similar or same to the matrix resin polyether-ether-ketone in the carbon fiber composite, therefore, strong interface bonding force is formed between the carbon fiber and the sizing agent layer and between the sizing agent layer and thermoplastic PEEK matrix resin; the carbon fiber is effectively combined with the thermoplastic PEEK matrix resin through a sizing agent transition connecting layer to form an organic whole, in addition, with a synergistic effect of a stabilizer ammonium chloride, compared with the existing carbon fiber composite, the interlaminar shear strength is improved by more than 30%, and higher whole performance of the carbon fiber composite is ensured. As the sizing agent comprises a stabilizer inorganic ammonium salt, the storage stability of the sizing agent is greatly improved; during the use process, layering and demulsification cannot occur.
Description
Technical field
The invention belongs to carbon fiber production field, be specifically related to a kind of emulsion type carbon fiber sizing agent and its preparation method and application.
Background technology
In carbon fibre reinforced composite, for using sizing agent as transition zone between the carbon fiber that strengthens and matrix resin, sizing agent can connect carbon fiber well, can connect well again matrix resin, make carbon fibre reinforced composite become as a whole, there is very strong overall performance.
Patent CN1318686C discloses a kind of carbon fiber sizing agent, this carbon fiber contains with sizing agent, (A) in molecule, at least there is the compound of an epoxy radicals, (B) have using ammonium ion as the anionic surfactant to ion, (C) nonionic surface active agent.
But, apply the thermoplas tic resin composite (CFRTP) that the carbon fiber after above-mentioned carbon fiber sizing agent starching is made, epoxy resin in sizing agent transition articulamentum and the Chemical bonding effect between carbon fiber are stronger, and and a little less than Chemical bonding effect between thermoplastic resin matrix, the connection function between carbon fiber and thermoplastic resin matrix is just not strong yet on the whole.Thereby made thermoplastic carbon fiber resin composite materials interlaminar shear strength is less, and the overall performance of carbon fibre composite has been caused to great adverse effect.And, storage and the stability in use of above-mentioned carbon fiber sizing agent are poor, in storage and use procedure, there will be creaming of emulsion, emulsion concentration skewness, there are even too early breakdown of emulsion, flocculation, reunion etc., there is the phenomenons such as layering, sinking, muddiness in sizing agent, cannot carry out carbon fiber starching, and can not stir comparatively fast in use and course of conveying, this produces and has brought great inconvenience carbon fiber, and the overall performance of carbon fiber and composite thereof is also brought to very large adverse effect.
Summary of the invention
In order to overcome the less defect of carbon fibre composite interlaminar shear strength made from existing carbon fiber sizing agent, and overcome existing carbon fiber sizing agent and store and the bad problem of stability in use, primary and foremost purpose of the present invention is to provide a kind of emulsion type carbon fiber sizing agent, sizing agent of the present invention can greatly improve the interlaminar shear strength of carbon fibre composite, guarantees that carbon fibre composite has higher overall performance; And sizing agent of the present invention there will not be creaming of emulsion, emulsion concentration skewness phenomenon in storage and use procedure, and can stir comparatively fast in use and course of conveying, easy to use.
Another object of the present invention is to the preparation method of the emulsion type carbon fiber sizing agent that provides above-mentioned.
A further object of the present invention is the application of the emulsion type carbon fiber sizing agent that provides above-mentioned.
Object of the present invention is achieved through the following technical solutions:
A kind of emulsion type carbon fiber sizing agent, its raw materials comprises the composition of following mass percent:
Epoxy resin: 2-40%
Modifier: 1-20%
Water: 0-96.5%
Surfactant: 0.5-15%
Inorganic ammonium salt: 0.1-2.0%.
Described epoxy resin refers to the compound that contains at least one epoxy radicals in molecule, preferably the one in bisphenol A type epoxy resin, bisphenol f type epoxy resin or novolac epoxy resin.
Described modifier, its structure is suc as formula shown in I or formula II, wherein, R
1, R
2for hydrogen or alkyl, R
3, R
4for hydrogen, alkyl, alkoxyl, hydroxyl, carboxyl, aldehyde radical, ketone group, amino, halogen, amide groups, ester group or siloxy; The preferred hydroquinones of described modifier and/or benzophenone;
Surfactant is the effect of playing emulsification, and described surfactant is anion surfactant and/or non-ionic surface active agent;
Described anion surfactant is organic ammonium (ammonia) salt and/or aminated compounds, and it contains suc as formula 1, the hydrophobic grouping shown in formula 2, formula 3 or formula 4:
Formula 1
Formula 2
Formula 3
Formula 4
In formula 1, formula 2, formula 3 and formula 4, R
1, R
2, R
3for H or C
1-C
3chain alkyl; R
4for divalent aliphatic alkyl; M is 1～3 integer.
Described non-ionic surface active agent is the polyalkylene oxide Addition on ethylene thing of senior alcohol ether type, the polyalkylene oxide Addition on ethylene thing of higher fatty acids type, polyalkylene oxide Addition on ethylene thing or the PO/EO block type polyethers of alkyl phenyl ether type, preferably polyethylene oxide alkyl ethers, polyethylene glycol oxide alkyl phenylate, polyoxyethylene fatty acid esters, polyethylene glycol oxide aliphatic acid amino ethers, polyol fatty acid ester, polyethylene glycol oxide polyol fatty acid ester, sucrose fatty ester, alkylolamides or polyoxygenated alkyl block virtue polymers.
Described inorganic ammonium salt is ammonium chloride, ammonium sulfate or ammonium nitrate; This wherein, the stablizing effect of ammonium chloride is best, the therefore described preferred ammonium chloride of inorganic ammonium salt, this is because the hydrogen bond action between ammonium chloride molecule and epoxy resin molecule and hydrone, ionic bond effect are stronger, is conducive to the two also stable existences that combine.
The preparation method of sizing agent for above-mentioned emulsion type carbon fiber, comprises the following steps:
Get surfactant and be added to the water, stir evenly; Add again epoxy resin, modifier, under 500-1000r/min, stir 60-100min; Then under 5000-10000r/min, stir emulsification pretreatment 15-35min; Finally add inorganic ammonium salt, under 500-1000r/min, stir 15-25min, obtain emulsion type carbon fiber sizing agent;
Above operation is all to carry out at 40-80 ℃.
Above-mentioned emulsion type carbon fiber can be used in carbon fibre composite with sizing agent, connects carbon fiber and resin matrix as transition zone.
A kind of carbon fiber, contains above-mentioned emulsion type carbon fiber sizing agent, and emulsion type carbon fiber is the 0.1-5% of carbon fiber gross mass by the quality of sizing agent.
A kind of carbon fibre composite, contains above-mentioned carbon fiber;
Described carbon fibre composite preferred, polyethers ether ketone resin base carbon fiber composite material.
Surfactant in sizing agent is as organic ammonium salt etc., in sizing agent, be as emulsifying agent, for the organic emulsification combination of two-phase of epoxy resin and water, lipophilic group in surfactant molecule and epoxy resin molecule are combined closely, hydrophilic radical in surfactant molecule and water molecules, make epoxy resin molecule and hydrone form comparatively stable micro emulsion grain by the connection function of surfactant molecule, these micro emulsion grains are comparatively evenly distributed in water.In the time being subject to the active forces such as ambient temperature variation, mechanical force, micro emulsion grain is assembled agglomerating, finally can make that profit two phase stratification is separated out, breakdown of emulsion.In sizing agent, ammonium chloride is as stabilizing agent; chloride leach is in water; after dissolving, chlorion and ammonium ion are because intermolecular force and electric charge graviational interaction can closely be dispersed in the skin of epoxy resin and the micro emulsion grain of hydrone formation; form one deck protection dispersion layer; thereby avoid the micro emulsion grain in sizing agent because the variation of external condition is assembled agglomerating; therefore there will not be that layering is separated out, the phenomenon of breakdown of emulsion, storage stability and the stability in use of the sizing agent greatly strengthening.
The present invention has following advantage and effect with respect to prior art:
1, through the carbon fiber of sizing agent starching of the present invention, making after carbon fiber polyether-ether-ketone resin based composites, owing to containing modifier in sizing agent, these modifier have similar or identical construction unit with the matrix resin polyether-ether-ketone in carbon fibre composite, thereby all there is stronger interface binding power between carbon fiber and sizing agent layer and between sizing agent layer and thermoplasticity PEEK matrix resin, carbon fiber is combined with thermoplasticity PEEK matrix resin effectively by sizing agent transition articulamentum, form an organic whole, add in addition the synergy of stabilizing agent ammonium chloride, improve more than 30% with respect to its interlaminar shear strength of existing carbon fibre composite, guarantee that carbon fibre composite has higher overall performance.
2, owing to containing stabilizing agent inorganic ammonium salt, sizing agent storage stability of the present invention improves greatly, stores more than 3 years emulsion and still can keep stable performance under normal temperature, there will not be layering and CONCENTRATION DISTRIBUTION uneven phenomenon; In sizing agent use procedure of the present invention, rotating speed that can 200r/min stirs conveying, the dilution etc. of carrying out sizing agent, and sizing agent there will not be layering, demulsifying phenomenon; Use the carbon fiber after sizing agent starching of the present invention, under normal temperature, store 5 years after carbon fiber surface sizing agent quality percentage composition unchanged; The carbon fibre composite that uses carbon fiber after sizing agent starching of the present invention to manufacture, under its normal temperature, store 2 years after mechanical property without significant change.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 0.5g (Japanese emulsifying agent company/Nikon that 707-SF) is added in the deionized water of 96.4g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 2g, the hydroquinones of 1g, the rotating speed with 1000r/min at 40 ℃ stirs 100min again; Then at 40 ℃ with the rotating speed high speed shear emulsification 35min of 10000r/min; Finally add the ammonium chloride of 0.1g, the rotating speed with 1000r/min at 40 ℃ stirs 25min, obtains emulsion type carbon fiber sizing agent.
The structure of surfactant is as follows:
Emulsifying agent company of Japan/Nikon that 707-SF
Embodiment 2
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 1.5g (0.75g mitsubishi rayon/BPEO20SON, 0.75g mitsubishi rayon/SPEO120SON) is added in the deionized water of 90.7g, and agitation as appropriate mixes it; Add the bisphenol f type epoxy resin of 5g, the benzophenone of 2.5g, the rotating speed with 750r/min at 60 ℃ stirs 80min again; Then at 60 ℃ with the rotating speed high speed shear emulsification 25min of 7500r/min; Finally add the ammonium chloride of 0.3g, the rotating speed with 750r/min at 60 ℃ stirs 20min, obtains emulsion type carbon fiber sizing agent.
The structure of surfactant is as follows:
Mitsubishi rayon/BPEO20SON
Mitsubishi rayon/SPEO120SON
Embodiment 3
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 3.5g (1.5g polyethylene oxide alkyl ethers, 2.0g polyethylene glycol oxide alkyl phenylate) is added in the deionized water of 80.9g, and agitation as appropriate mixes it; Add the novolac epoxy resin of 10g, the modifier of 5g (2.5g hydroquinones, 2.5g benzophenone), the rotating speed with 500r/min at 60 ℃ stirs 60min again; Then at 60 ℃ with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally add the ammonium chloride of 0.6g, the rotating speed with 500r/min at 60 ℃ stirs 15min, obtains emulsion type carbon fiber sizing agent.
Embodiment 4
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 8.0g (4g polyoxyethylene fatty acid esters, 4g polyethylene glycol oxide aliphatic acid amino ethers) is added in the deionized water of 60.8g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 20g, the hydroquinones of 10g, the rotating speed with 500r/min at 80 ℃ stirs 60min again; Then at 80 ℃ with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally add the ammonium chloride of 1.2g, the rotating speed with 500r/min at 80 ℃ stirs 15min, obtains emulsion type carbon fiber sizing agent.
Embodiment 5
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 12g (6g Mitsui NPES3030P, 6g polyol fatty acid ester) is added in the deionized water of 41.4g, and agitation as appropriate mixes it; Add the bisphenol f type epoxy resin of 30g, the benzophenone of 15g, the rotating speed with 750r/min at 40 ℃ stirs 100min again; Then at 40 ℃ with the rotating speed high speed shear emulsification 35min of 7500r/min; Finally add the ammonium chloride of 1.6g, the rotating speed with 750r/min at 40 ℃ stirs 25min, obtains emulsion type carbon fiber sizing agent.
The structure of surfactant is as follows:
Mitsui NPES3030P
Embodiment 6
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 15g (5g Japan emulsifying agent company/Nikon you 723-SF, 5g produce chemical industrial company/FO180EO6SON, 5g polyethylene glycol oxide polyol fatty acid ester daily) is added in the deionized water of 23g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 40g, the hydroquinones of 20g, the rotating speed with 1000r/min at 80 ℃ stirs 80min again; Then at 80 ℃ with the rotating speed high speed shear emulsification 25min of 10000r/min; Finally add the ammonium chloride of 2.0g, the rotating speed with 1000r/min at 80 ℃ stirs 20min, obtains emulsion type carbon fiber sizing agent.
The structure of surfactant is as follows:
Emulsifying agent company of Japan/Nikon that 723-SF
Daily output chemical industrial company/FO180EO6SON
Comparative example 1
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 0.5g (Japanese emulsifying agent company/Nikon that 707-SF) is added in the deionized water of 96.4g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 2g, the rotating speed with 1000r/min at 40 ℃ stirs 100min again; Then at 40 ℃ with the rotating speed high speed shear emulsification 35min of 10000r/min; Finally at 40 ℃, the rotating speed with 1000r/min stirs 25min, obtains emulsion type carbon fiber sizing agent.
Comparative example 2
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 1.5g (0.75g mitsubishi rayon/BPEO20SON, 0.75g mitsubishi rayon/SPEO120SON) is added in the deionized water of 90.7g, and agitation as appropriate mixes it; Add the bisphenol f type epoxy resin of 5g, the rotating speed with 750r/min at 60 ℃ stirs 80min again; Then at 60 ℃ with the rotating speed high speed shear emulsification 25min of 7500r/min; Finally at 60 ℃, the rotating speed with 750r/min stirs 20min, obtains emulsion type carbon fiber sizing agent.
Comparative example 3
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 3.5g (1.5g polyethylene oxide alkyl ethers, 2.0g polyethylene glycol oxide alkyl phenylate) is added in the deionized water of 80.9g, and agitation as appropriate mixes it; Add the novolac epoxy resin of 10g, the rotating speed with 500r/min at 60 ℃ stirs 60min again; Then at 60 ℃ with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally at 60 ℃, the rotating speed with 500r/min stirs 15min, obtains emulsion type carbon fiber sizing agent.
Comparative example 4
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 8.0g (4g polyoxyethylene fatty acid esters, 4g polyethylene glycol oxide aliphatic acid amino ethers) is added in the deionized water of 60.8g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 20g, the rotating speed with 500r/min at 80 ℃ stirs 60min again; Then at 80 ℃ with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally at 80 ℃, the rotating speed with 500r/min stirs 15min, obtains emulsion type carbon fiber sizing agent.
Comparative example 5
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 12g (6g Mitsui NPES3030P, 6g polyol fatty acid ester) is added in the deionized water of 41.4g, and agitation as appropriate mixes it; Add the bisphenol f type epoxy resin of 30g, the rotating speed with 750r/min at 40 ℃ stirs 100min again; Then at 40 ℃ with the rotating speed high speed shear emulsification 35min of 7500r/min; Finally at 40 ℃, the rotating speed with 750r/min stirs 25min, obtains emulsion type carbon fiber sizing agent.
Comparative example 6
A kind of emulsion type carbon fiber sizing agent, is prepared by following steps:
The surfactant of 15g (5g Japan emulsifying agent company/Nikon you 723-SF, 5g produce chemical industrial company/FO180EO6SON, 5g polyethylene glycol oxide polyol fatty acid ester daily) is added in the deionized water of 23g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 40g, the rotating speed with 1000r/min at 80 ℃ stirs 80min again; Then at 80 ℃ with the rotating speed high speed shear emulsification 25min of 10000r/min; Finally at 80 ℃, the rotating speed with 1000r/min stirs 20min, obtains emulsion type carbon fiber sizing agent.
By its stability of visual observations after storing 3 years under the sizing agent normal temperature of embodiment, the rotating speed with 200r/min in use stirs its stability of visual observations, and performance is listed in table 1.
Use the sizing agent of embodiment to impregnated carbon fiber starching, sizing agent quality is 0.1% of carbon fiber gross mass, surveys its sizing agent mass percent after storing 5 years under normal temperature, lists in table 2.The detection method of sizing agent content is GB/T 26752-2011 polyacrylonitrile-based carbon fibre.
Use the carbon fiber after the starching of embodiment sizing agent to make polyether-ether-ketone resin base carbon fiber composite material, measure the interlaminar shear strength (ILSS) of gained carbon fibre composite; After storing 2 years under normal temperature, survey its interlaminar shear strength, list in table 3.The detection method of composite interlayer shear strength is that JC/T 773-2010 fibre reinforced plastics short beam method is measured interlaminar shear strength.
By its stability of visual observations after storing 15 months under the sizing agent normal temperature of comparative example, the rotating speed with 30r/min in use stirs its stability of visual observations, and performance is listed in table 1.
Use the sizing agent of comparative example to impregnated carbon fiber starching, sizing agent quality is 5% of carbon fiber gross mass, surveys its sizing agent mass percent after storing 5 years under normal temperature, lists in table 2.The detection method of sizing agent content is GB/T 26752-2011 polyacrylonitrile-based carbon fibre.
Use the carbon fiber after the starching of comparative example sizing agent to make polyether-ether-ketone resin base carbon fiber composite material, measure the interlaminar shear strength (ILSS) of gained carbon fibre composite; After storing 2 years under normal temperature, survey its interlaminar shear strength, list in table 3.The detection method of composite interlayer shear strength is that JC/T 773-2010 fibre reinforced plastics short beam method is measured interlaminar shear strength.
The stability of table 1 sizing agent
Table 2 carbon fiber sizing agent changes of contents
Table 3 carbon fibre composite interlaminar shear strength
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Interlaminar shear strength/MPa | 95.61 | 95.32 | 96.01 | 96.33 | 96.58 | 95.79 |
| Store interlaminar shear strength/MPa after 2 years | 95.01 | 94.80 | 95.53 | 95.62 | 95.66 | 95.11 |
| Comparative example | 1 | 2 | 3 | 4 | 5 | 6 |
| Interlaminar shear strength/MPa | 72.55 | 72.76 | 73.14 | 73.55 | 73.21 | 72.82 |
| Store interlaminar shear strength/MPa after 2 years | 61.02 | 60.98 | 61.79 | 62.05 | 61.87 | 61.11 |
In all embodiment, all added modifier and stabilizing agent ammonium chloride, and all do not added in comparative example, all the other component ratios are identical.
Can find out by table 1: added the storage stability of sizing agent after stabilizing agent ammonium chloride and greatly strengthened, and in use procedure, stability when agitation and dilution is also strengthened greatly, can stir and dilute with rotating speed more than 200r/min.
Can find out by table 2: added the sizing agent of stabilizing agent ammonium chloride, after using it to carbon fiber starching, the sizing agent storage stability of carbon fiber surface strengthens greatly.
Can find out by table 3: the sizing agent that has added modifier and stabilizing agent ammonium chloride, the polyether-ether-ketone resin base carbon fiber composite material that uses the carbon fiber after its starching to make, the mechanical properties such as its interlaminar shear strength have great increase, and after carbon fibre composite stores 2 years, interlaminar shear strength is substantially unchanged, and its storage stability strengthens greatly.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. an emulsion type carbon fiber sizing agent, is characterised in that: its raw materials comprises the composition of following mass percent:
Epoxy resin: 2-40%
Modifier: 1-20%
Water: 0-96.5%
Surfactant: 0.5-15%
Inorganic ammonium salt: 0.1-2.0%;
Described modifier is hydroquinones and/or benzophenone.
2. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: described epoxy resin is the one in bisphenol A type epoxy resin, bisphenol f type epoxy resin or novolac epoxy resin.
3. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: described inorganic ammonium salt is ammonium chloride, ammonium sulfate or ammonium nitrate.
4. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: described inorganic ammonium salt is ammonium chloride.
5. emulsion type carbon fiber sizing agent according to claim 1, is characterized in that: described surfactant is anion surfactant and/or non-ionic surface active agent.
6. the preparation method of sizing agent for the emulsion type carbon fiber described in claim 1-5 any one, is characterized in that comprising the following steps:
Get surfactant and be added to the water, stir evenly; Add again epoxy resin, modifier, under 500-1000r/min, stir 60-100min; Then under 5000-10000r/min, stir emulsification pretreatment 15-35min; Finally add inorganic ammonium salt, under 500-1000r/min, stir 15-25 min, obtain emulsion type carbon fiber sizing agent.
7. the application in carbon fibre composite with sizing agent of the emulsion type carbon fiber described in claim 1-5 any one.
8. a carbon fiber, is characterized in that: contain the emulsion type carbon fiber sizing agent described in claim 1-5 any one, emulsion type carbon fiber is the 0.1-5% of carbon fiber gross mass by the quality of sizing agent.
9. a carbon fibre composite, is characterized in that: contain carbon fiber claimed in claim 8.
10. carbon fibre composite according to claim 9, is characterized in that: described carbon fibre composite is polyether-ether-ketone resin base carbon fiber composite material.
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