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, 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, ensures that carbon fibre composite has higher overall performance.
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 purposes 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%
Carbonic acid ester: 1-20%
Water: 0-96.5%
Surfactant: 0.5-15%.
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 carbonic acid ester refers to carbonic acid (H
2cO
3) compound after hydrogen atom in molecule on two hydroxyls (OH) is partly or entirely replaced by alkyl (R, R '), its structure is suc as formula shown in I or formula II; The preferred dimethyl carbonate of described carbonic acid ester and/or diphenyl carbonate.
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:
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.
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, carbonic acid ester, under 500-1000r/min, stir 60-100min; Then under 5000-10000r/min, stir emulsification pretreatment 15-35min; Finally under 500-1000r/min, stir 15-25min, obtain emulsion type carbon fiber sizing agent;
Above operation is all to carry out at 40-80 DEG C.
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 optimization polycarbonate resin-based carbon fiber composite.
The present invention has following advantage and effect with respect to prior art:
With the carbon fiber after sizing agent starching of the present invention, making after carbon fiber Merlon (PC) based composites, owing to containing carbonic acid ester in sizing agent, these carbonic acid esters have similar or identical construction unit with the matrix resin Merlon 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 PC matrix resin, carbon fiber is combined with thermoplasticity PC matrix resin effectively by sizing agent transition articulamentum, form an organic whole, improve more than 20% with respect to its interlaminar shear strength of existing carbon fibre composite, ensure that carbon fibre composite has higher overall performance.
Detailed description of the invention
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 96.5g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 2g, the dimethyl carbonate of 1g, the rotating speed with 1000r/min at 40 DEG C stirs 100min again; Then at 40 DEG C with the rotating speed high speed shear emulsification 35min of 10000r/min; Finally at 40 DEG C, the rotating speed with 1000r/min 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 91g, and agitation as appropriate mixes it; Add the bisphenol f type epoxy resin of 5g, the diphenyl carbonate of 2.5g, the rotating speed with 750r/min at 60 DEG C stirs 80min again; Then at 60 DEG C with the rotating speed high speed shear emulsification 25min of 7500r/min; Finally at 60 DEG C, the rotating speed with 750r/min 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 81.5g, and agitation as appropriate mixes it; Add the novolac epoxy resin of 10g, the carbonic acid ester of 5g (2.5g dimethyl carbonate, 2.5g diphenyl carbonate), the rotating speed with 500r/min at 60 DEG C stirs 60min again; Then at 60 DEG C with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally at 60 DEG C, the rotating speed with 500r/min 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 62g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 20g, the diphenyl carbonate of 10g, the rotating speed with 500r/min at 80 DEG C stirs 60min again; Then at 80 DEG C with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally at 80 DEG C, the rotating speed with 500r/min 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 43g, and agitation as appropriate mixes it; Add the bisphenol f type epoxy resin of 30g, the diphenyl carbonate of 15g, the rotating speed with 750r/min at 40 DEG C stirs 100min again; Then at 40 DEG C with the rotating speed high speed shear emulsification 35min of 7500r/min; Finally at 40 DEG C, the rotating speed with 750r/min 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 25g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 40g, the diphenyl carbonate of 20g, the rotating speed with 1000r/min at 80 DEG C stirs 80min again; Then at 80 DEG C with the rotating speed high speed shear emulsification 25min of 10000r/min; Finally at 80 DEG C, the rotating speed with 1000r/min 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 96.5g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 2g, the rotating speed with 1000r/min at 40 DEG C stirs 100min again; Then at 40 DEG C with the rotating speed high speed shear emulsification 35min of 10000r/min; Finally at 40 DEG C, 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 91g, and agitation as appropriate mixes it; Add the bisphenol f type epoxy resin of 5g, the rotating speed with 750r/min at 60 DEG C stirs 80min again; Then at 60 DEG C with the rotating speed high speed shear emulsification 25min of 7500r/min; Finally at 60 DEG C, 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 81.5g, and agitation as appropriate mixes it; Add the novolac epoxy resin of 10g, the rotating speed with 500r/min at 60 DEG C stirs 60min again; Then at 60 DEG C with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally at 60 DEG C, 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 62g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 20g, the rotating speed with 500r/min at 80 DEG C stirs 60min again; Then at 80 DEG C with the rotating speed high speed shear emulsification 15min of 5000r/min; Finally at 80 DEG C, 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 43g, and agitation as appropriate mixes it; Add the bisphenol f type epoxy resin of 30g, the rotating speed with 750r/min at 40 DEG C stirs 100min again; Then at 40 DEG C with the rotating speed high speed shear emulsification 35min of 7500r/min; Finally at 40 DEG C, 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 25g, and agitation as appropriate mixes it; Add the bisphenol A type epoxy resin of 40g, the rotating speed with 1000r/min at 80 DEG C stirs 80min again; Then at 80 DEG C with the rotating speed high speed shear emulsification 25min of 10000r/min; Finally at 80 DEG C, the rotating speed with 1000r/min stirs 20min, obtains emulsion type carbon fiber sizing agent.
Use respectively the carbon fiber after the sizing agent starching of embodiment, comparative example to make Merlon base carbon fiber composite material, measure the interlaminar shear strength (ILSS) of gained carbon fibre composite, list in table 1.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.
Table 1 carbon fibre composite interlaminar shear strength
Embodiment sequence number |
1 |
2 |
3 |
4 |
5 |
6 |
Interlaminar shear strength/MPa |
88.35 |
87.63 |
87.85 |
88.92 |
88.61 |
88.55 |
Comparative example sequence number |
1 |
2 |
3 |
4 |
5 |
6 |
Interlaminar shear strength/MPa |
71.35 |
70.27 |
70.78 |
71.86 |
71.65 |
71.48 |
In all embodiment, all added carbonic acid ester, and all do not added in comparative example, all the other component ratios are identical.Can find out by table 1, add the sizing agent of carbonic acid ester, the Merlon 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.
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.