CN101858038B - Carbon fiber emulsion sizing agent and preparation method and application thereof - Google Patents
Carbon fiber emulsion sizing agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon fiber emulsion sizing agent. The sizing agent comprises a main sizing agent, an auxiliary agent, an organic solvent and de-ionized water, wherein the auxiliary agent accounts for 5 to 15 percent of the mass of the main sizing agent; the mass ratio of the organic solvent to the main sizing agent is 20-50 to 50-80; and the mass ratio of the de-ionized water to the main sizing agent is 50-90 to 10-50. The invention also discloses a preparation method and application of the sizing agent. The sizing agent has low cost and environment friendliness and can be applied to different types of resin matrixes by varying the ratio of the components in the sizing agent. The preparation method is simple to operate and easy to implement. The sizing agent can improve the processability of the carbon fiber and the mechanical property of carbon fiber-enhanced resin-based composite materials when used in carbon fiber.
Description
Technical field
The present invention relates to a kind of carbon fiber sizing agent and its production and application, compound sizing agent of particularly a kind of carbon fiber emulsion type and its production and application.
Background technology
Carbon fiber is the most important reinforcing material of advanced composite material, and the every field in military affairs and civilian industry obtains extensive use.But carbon fiber belongs to fragile material, causes lousiness and single wire fracture easily through mechanical friction in production and process, and the intensity of carbon fiber is reduced, and influences the mechanical property of composite.For intensity and the deep processing performance of improving fiber, all is furnished with quetsch before the rolling of carbon fiber production line.Starching is to be coated with one deck protection glue on carbon fiber surface; not only can improve the processing characteristics of carbon fiber, reduce lousiness and single wire fracture phenomenon, make the carbon fiber boundling; and can improve bonding between fiber and matrix, improve composite interlayer shear strength (ILSS).
At present, sizing agent has two kinds: solvent-borne type and emulsion-type.Solvent evaporates easily caused resin residue on deflector roll when the solvent-borne type sizing agent used, fiber by the time can cause damage, the contaminated environment of organic solvent volatilization simultaneously need not at present abroad.The emulsion-type sizing agent generally is difficult for cull on deflector roll, solvent-free again contaminated environment, and, can improve the wetted property of fiber surface greatly owing to contain surfactant, can also reach the purpose that improves the carbon fibre composite mechanical property by auxiliary agent.Therefore, each carbon fiber production firm uses the emulsion-type sizing agent more now.
Researcher has in the past developed many emulsion-types or water miscible carbon fiber sizing agent.Adopt novolac epoxy resin or aromatic amine based epoxy resin as main slurry as US4751258, with non-ionic surface active agent as emulsifying agent, the aliphatic unit price alcohol ester of adding oleic acid or the unit price fatty acid ester of oleyl alcohol are as lubricant, this sizing agent can improve the lubricity of fiber, but the rub resistance of fiber and dispersion stabilization are undesirable.According to US 4420512, it consists of epoxy resin, nonionic emulsifier, lubricant, softener, and this sizing agent has excellent stability of emulsion and heat endurance, but the interface performance of starching carbon fibre composite is general.US5688554 has reported the sizing agent of being made up of the polyester of Special Category and special epoxide, and this sizing agent can improve lubricity, rub resistance and the dispersion stabilization of fiber simultaneously.In the report in the past, patent at epoxy resin-base is in the majority, when the resin matrix of carbon fibre composite was the resin (as unsaturated polyester resin, vinylite) of unsaturated class, used sizing agent of its carbon fiber and epoxide resin type sizing agent structure were different.U.S. Pat 4981947 adopts unsaturated alcohols and isocyanate reaction to form the compound with urethane bonds, prepare carbon fiber sizing agent with this as main component, but this polyurethane needs own polymerization, and operation is more loaded down with trivial details, and reaction is not easy control.US 4880881 has reported a kind of deep processing performance that not only can improve carbon fiber, and can be by regulating the sizing agent that component adapts to epoxy matrix and unsaturated polyester (UP) matrix.This carbon fiber sizing agent key component is epoxy resin, contain the special copolymer of the alkoxyl derivatives fragment (B1) of a condensed ring phenol and one or two monoesters or polyester fragment (B2), the alkoxyl derivatives of fortified phenol.The performance that can obtain to envision by molecular weight, ratio, structure and the composition of B1 and B2 in the adjusting B component.But the preparation of B component is more loaded down with trivial details.
Summary of the invention
The present invention is in order to overcome above-mentioned deficiency, provide that a kind of cost is low, the carbon fiber emulsion pasting agent of stable performance, this sizing agent not only is adapted to epoxy resin-base, also be adapted to the vinyl esters matrix, in addition, this sizing agent can also improve the surface property and the deep processing performance of fiber, can improve the interface bonding of fiber and matrix resin simultaneously.
The present invention also provides the preparation method of this carbon fiber emulsion pasting agent, and this method is simple to operate, and is easy to implement.
The present invention also provides the application process of this carbon fiber emulsion pasting agent on carbon fiber.
The present invention is achieved by the following measures:
A kind of carbon fiber emulsion pasting agent, comprise: main slurry, auxiliary agent, organic solvent and deionized water, wherein, the quality of auxiliary agent is 5%～15% of a main stock quality, the mass ratio of organic solvent and main slurry is 20～50: 50～80, and the mass ratio of deionized water and main slurry is 50～90: 10～50.
In the above-mentioned sizing agent, described main slurry is glycidol ether type epoxy and the polyolefinic mixture of epoxidation aliphatic, and glycidol ether type epoxy and the polyolefinic mass ratio of epoxidation aliphatic are 10～90: 10～90.Described glycidol ether type epoxy is E-55, E-51, E-44, and described epoxidation aliphatic poly alkene is epoxidized polybutadiene.The epoxidized polybutadiene molecular weight is about 2000, and epoxide number is about 0.44.
In the above-mentioned sizing agent, described auxiliary agent comprises emulsifying agent and bleeding agent, and the mass ratio of emulsifying agent and bleeding agent is 20～90: 10～80.
Because the hydrophobicity and the high viscosity of resin are scattered in comparison difficulty in the water with it, this sizing agent adopts blended emulsifier.Emulsifying agent is two kinds of surfactant mixtures of A, B, mass ratio A: B=10～90: 10～90.Emulsifying agent A is polyoxyethylene nonylphenol ether (NP-10) phosphate ammonium salt, polyoxyethylene nonylphenol ether (NP-10) ammonium sulfate, and this type of emulsifying agent not only has good emulsion dispersion property, and does not influence the heat resistance of carbon fibre reinforced composite after the starching.
NP-10 ammonium sulfate can have been bought on market, NP-10 phosphate ammonium salt makes by the following method: the NP-10 phosphate is added reactor, under agitation add the ammoniacal liquor of 25-28wt%, when the pH value stops to drip during to 7.5-8.5, stir 1-1.5h at 35-45 ℃, promptly get NP-10 phosphate ammonium salt.
Emulsifying agent B is OPEO (OP-10), polyoxyethylene nonylphenol ether (NP-10), farming breast 1601 or T-80 (being Tween-80), and wherein, the structural formula of farming breast 1601 is:
Wherein, E is C
2H
4O, P are C
3H
6O.
Carbon fiber is a hydrophobic fibre, and the air of fibre gap is unfavorable for that sizing agent soaks into the inside of fiber, and the adding of bleeding agent is in order to improve the wettability of carbon fiber and matrix resin, to improve the interface cohesiveness of carbon fiber and matrix resin.Described bleeding agent is secondary octanol polyoxyethylene ether (JFC-2) or OPEO (OP-7).
Organic solvent is used for reducing the viscosity of resin as diluent, improves operability.This organic solvent comprises acetone, MEK, n-butanol, also can be other organic solvents.
Key of the present invention is the selection of main slurry, emulsifying agent and the proportion relation between each composition, can be by regulating glycidol ether type epoxy in the main slurry and the polyolefinic composition of epoxidation, ratio, and adopt emulsifying agent and the emulsifying process that adapts, obtain to be suitable for the sizing agent of different matrix.For example, if the ratio of glycidol ether type epoxy increases, the affinity of this sizing agent and epoxy resin can improve, and this system is more suitable for epoxy resin.On the contrary, if the epoxidation of olefins mass ratio in the A component increases, the affinity of sizing agent and vinyl ester resin matrix improves, and this moment, this sizing agent was more suitable for the vinyl ester resin matrix.If the composition proportion in the main slurry changes, used emulsifying agent kind, addition and A and B compound proportion all will adjust accordingly.
The preparation method of carbon fiber emulsion pasting agent of the present invention adopts phase conversion emulsifying to realize, step is: main slurry is dissolved in the organic solvent, add auxiliary agent, mix at 40～80 ℃, under the rotating speed of 8000～13000r/min, dropwise add deionized water then, after water injection the back continues to stir 20～60min, obtains carbon fiber emulsion pasting agent.
The solid content of gained carbon fiber emulsion pasting agent is 10～50wt% in the said method.
The application of carbon fiber emulsion pasting agent of the present invention, method is: it is 0.5～3.0wt% that above-mentioned sizing agent is diluted to solid content, with infusion process sizing agent is attached on the carbon fiber, and the impregnation time is 20～40s, carbon fiber dry 10min under 100 ℃ after the starching.
In the above-mentioned application, the rate of sizing of sizing agent on carbon fiber is 0.5～3.0wt%.
The present invention has the following advantages:
1. this sizing agent is the emulsion-type sizing agent, and as medium, cost is low with water, and is free from environmental pollution.
2. make this sizing agent not be only applicable to epoxy resin by the component of regulating main slurry, also can be suitable for vinyl ester resin.Vinyl ester resin there is compatibility preferably, has solved vinyl ester resin and the bad problem of carbon fiber cohesiveness.
3. by the suitable proportioning of each constituent, the stability of sizing agent of the present invention increases.
4. after using this sizing agent starching, the ABRASION RESISTANCE of carbon fiber improves, the lousiness amount reduces, and the back processing characteristics of carbon fiber improves; And the interface cohesiveness of carbon fiber and matrix resin is better, and interlaminar shear strength increases, and performance of composites also is increased.
5. preparation method of the present invention is simple to operate, easy to implement.
Description of drawings
Fig. 1 is the wear-resistant device schematic diagram;
Fig. 2 is a stiffness experimental provision schematic diagram, and wherein Fig. 2 a is a front view, and Fig. 2 b is a left view;
Among the figure, 1. godet roller, 2. stainless steel rider, 3. carbon fiber bundle, 4. reciprocating engine, 5. stainless steel hook, 6. carbon fiber, 7. slide scale.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further set forth, if no special instructions, the following mass percent that is.
Used epoxidized polybutadiene can have been bought in market, the epoxidized polybutadiene of using among the embodiment for Wuhan Yuancheng Technology Development Co., Ltd.'s sale, and molecular weight is about 2000, and epoxide number is about 0.44.
Preparation NP-10 phosphate ammonium salt: the NP-10 phosphate is added reactor, under agitation add the ammoniacal liquor of 25-28%,, stir 1-1.5h, promptly get NP-10 phosphate ammonium salt at 35-45 ℃ when the pH value stops to drip during to 7.5-8.5.
With emulsifying agent NP-10 phosphate ammonium salt and OP-10 75: 25 in proportion, the secondary octanol polyoxyethylene ether of emulsifying agent and bleeding agent (JFC-2) was preheating to 50 ℃ in proportion and is positioned in the container after mixing at 80: 20, obtains mixed aid.Epoxy resin E-44 and POLYBUTADIENE EPOXY RESIN are mixed by mass ratio at 80: 20, obtain sizing agent master slurry, it is dissolved in the acetone, the mass ratio of acetone and main slurry is 40: 60, add above mixed aid then, the addition of mixed aid is 15% of a main slurry.This mixture heated to 50 ℃ is mixed, and high-speed stirred under the constant rate of speed of 10000r/min dropwise adds deionized water then, and the ratio of deionized water and main slurry is 80: 20, and after water injection the back continues to stir 20min, obtains the sizing agent emulsion.It is 0.5% that this emulsion is diluted to solid content, is attached on the polyacrylonitrile carbon fiber with the sizing agent of infusion process with this concentration, and impregnation time 30s places 100 ℃ of dry 10min of baking oven then.The interlaminar shear strength (ILSS) of the rate of sizing, stiffness, lousiness amount, abrasion resistance and the carbon-fibre reinforced epoxy resin of the stability of this sizing agent emulsion of mensuration, starching carbon fiber under the room temperature.Test and evaluation method are as follows:
1. sizing agent stability of emulsion
Adopt centrifuge at room temperature to measure the centrifugal stability of different sizing agent emulsions, centrifugal stable classification is as follows:
I level: in 1500r/min * 20min lower leaf;
II level: in 2000r/min * 20min lower leaf;
III level: not stratified under 2500r/min * 20min;
IV level: not stratified under 3000r/min * 20min;
V level: not stratified under 3500r/min * 20min;
VI level: not stratified under 3500r/min * 30min.
2. carbon fibre composite interlaminar shear strength (ILSS)
The interlaminar shear strength of carbon fibre composite is measured gained according to JC/T773-1996 (GB3357-82).
The unidirectional carbon fiber dimension reinforced epoxy of preparation or the parameter of vinyl ester resin sample are: sample size is thick 3mm * wide 6mm * long 25mm, and span is 5 with the thickness ratio, and loading velocity is 1mm/min.
3. lousiness amount
Carbon fiber bundle is wiped at two polyurethane sponges and is of a size of under the clamping of 40mm (length) * 10mm (wide) * 5mm (thick), and whole polyurethane sponge is wiped load-carrying 200g.Carbon fiber bundle passes through minor face with the speed of 1m/min, is attached to the weight of lousiness on the sponge behind the survey 10min, is the friction lousiness amount of carbon fiber bundle.
4. ABRASION RESISTANCE
Wear-resistant device as shown in Figure 1, godet roller diameter are 10mm, and the stainless steel roller diameter is 15mm, and the angle of two godet rollers and stainless steel rider is 120 degree.Load-carrying G is the 50g/3000 root, and carbon fiber bundle is with the at the uniform velocity reciprocating motion of speed of per minute 120 times, and with stainless steel rider repeated friction, the number of times when the record fiber rubs.
5. stiffness
Performance when the research carbon fiber is subjected to flecition is very important, because carbon fiber is in the process of braiding, be subjected to repeated bending stress, especially when braiding multidimensional fabric, the angle of bank of carbon fiber on loom is very big, the flecition that is subjected to is very big, can produce flexural deformation, therefore requires carbon fiber to have the pliability of appropriateness.The stiffness of carbon fiber can reflect the pliability of carbon fiber to a certain extent before and after the starching, and stiffness is big more, and pliability is low more.
The mensuration of stiffness adopts the fiber of fixed length to put suspension therein, the principle of certain angle of can dangling.At first to carry out unwinding to carbon fiber.Carbon fiber is passed the twizzle of unwinding device, and walk around three stainless steel wheels, be wrapped in rotating speed and be on the bobbins about 10mm/s, starter motor is reeled.
Fiber after the unwinding carries out the test of stiffness.Testing arrangement as shown in Figure 2, by radius be the stainless steel hook of 10mm as hitch point, there is a slide scale at the 60mm place under hitch point, the carbon fiber of measuring after the 500mm unwinding is suspended on the hook, the equal in length that sample is stretched out from both sides leaves standstill the distance of measuring two ends behind the 30s.
With emulsifying agent NP-10 ammonium sulfate and NP-10 70: 30 in proportion, emulsifying agent and bleeding agent OP-7 were preheating to 60 ℃ in proportion and are positioned in the container after mixing at 85: 15, obtain mixed aid.Epoxy resin E-51 and POLYBUTADIENE EPOXY RESIN are mixed by mass ratio at 20: 80, obtain sizing agent master slurry, it is dissolved in the acetone, the mass ratio of acetone and main slurry is 50: 50, add above mixed aid then, the addition of mixed aid is 12% of a main slurry.This mixture heated to 60 ℃ is mixed, and high-speed stirred under the constant rate of speed of 11000r/min dropwise adds deionized water then, and the ratio of deionized water and main slurry is 70: 30, and after water injection the back continues to stir 20min, obtains the sizing agent emulsion.It is 1.0% that this emulsion is diluted to solid content, with infusion process with the sizing agent of this concentration adhere to polyacrylonitrile carbon fiber on, impregnation time 25s places 100 ℃ of dry 10min of baking oven then.The interlaminar shear strength (ILS S) of the rate of sizing of carbon fiber, stiffness, lousiness amount, abrasion resistance and carbon fiber enhancing vinyl ester resin after the stability of this sizing agent emulsion of mensuration, the starching under the room temperature.
With emulsifying agent NP-10 ammonium sulfate and farming breast 1,601 65: 35 in proportion, emulsifying agent and the bleeding agent octanol polyoxyethylene ether second month in a season (JFC-2) were preheating to 60 ℃ in proportion and are positioned in the container after mixing at 90: 10, obtain mixed aid.Epoxy resin E-55 and POLYBUTADIENE EPOXY RESIN are mixed by mass ratio at 25: 75, obtain sizing agent master slurry, it is dissolved in the acetone, the mass ratio of acetone and main slurry is 50: 50, add above mixed aid then, the addition of mixed aid is 10% of a main slurry.This mixture heated to 60 ℃ is mixed, and high-speed stirred under the constant rate of speed of 9000r/min dropwise adds deionized water then, and the ratio of deionized water and main slurry is 60: 40, and after water injection the back continues to stir 30min, obtains the sizing agent emulsion.It is 2.0% that this emulsion is diluted to solid content, with infusion process with the sizing agent of this concentration adhere to polyacrylonitrile carbon fiber on, impregnation time 30s places 100 ℃ of dry 10min of baking oven then.The interlaminar shear strength (ILSS) of the rate of sizing of carbon fiber, stiffness, lousiness amount, abrasion resistance and carbon fiber enhancing vinyl ester resin after the stability of this sizing agent emulsion of mensuration, the starching under the room temperature.
With emulsifying agent NP-10 phosphate ammonium salt and T-80 90: 10 in proportion, emulsifying agent and bleeding agent OPEO OP-7 were preheating to 50 ℃ in proportion and are positioned in the container after mixing at 80: 20, obtain mixed aid.Epoxy resin E-51 and POLYBUTADIENE EPOXY RESIN are mixed by mass ratio at 75: 25, obtain sizing agent master slurry, it is dissolved in the MEK, the mass ratio of MEK and main slurry is 40: 60, add above mixed aid then, the addition of mixed aid is 8% of a main slurry.This mixture heated to 50 ℃ is mixed, and high-speed stirred under the constant rate of speed of 12000r/min dropwise adds deionized water then, and the ratio of deionized water and main slurry is 80: 20, and after water injection the back continues to stir 40min, obtains the sizing agent emulsion.It is 0.8% that this emulsion is diluted to solid content, with infusion process with the sizing agent of this concentration adhere to polyacrylonitrile carbon fiber on, impregnation time 30s places 100 ℃ of dry 10min of baking oven then.The interlaminar shear strength (ILSS) of the rate of sizing, stiffness, lousiness amount, abrasion resistance and the carbon-fibre reinforced epoxy resin of carbon fiber after the stability of this sizing agent emulsion of mensuration, the starching under the room temperature.
Embodiment 5
With emulsifying agent NP-10 ammonium sulfate and farming breast 1,601 70: 30 in proportion, emulsifying agent and bleeding agent OPEO OP-7 were preheating to 40 ℃ in proportion and are positioned in the container after mixing at 20: 80, obtain mixed aid.Epoxy resin E-44 and POLYBUTADIENE EPOXY RESIN are mixed by mass ratio at 10: 90, it is dissolved in the n-butanol, and the mass ratio of n-butanol and main slurry is 40: 60, obtains sizing agent master slurry, add above mixed aid then, the addition of mixed aid is 5% of a main slurry.This mixture heated to 40 ℃ is mixed, and high-speed stirred under the constant rate of speed of 8000r/min dropwise adds deionized water then, the ratio of deionized water and main slurry is 50: 50, after water injection the back continues to stir 30min, obtains the sizing agent emulsion, and solid content is 45-52%.It is 3% that this emulsion is diluted to solid content, with infusion process with the sizing agent of this concentration adhere to polyacrylonitrile carbon fiber on, impregnation time 40s places 100 ℃ of dry 10min of baking oven then.The interlaminar shear strength (ILSS) of the rate of sizing of carbon fiber, stiffness, lousiness amount, abrasion resistance and carbon fiber enhancing vinyl ester resin after the stability of this sizing agent emulsion of mensuration, the starching under the room temperature.
Embodiment 6
With emulsifying agent NP-10 phosphate ammonium salt and NP-10 10: 90 in proportion, the secondary octanol polyoxyethylene ether of emulsifying agent and bleeding agent (JFC-2) was preheating to 80 ℃ in proportion and is positioned in the container after mixing at 30: 70, obtains mixed aid.Epoxy resin E-51 and POLYBUTADIENE EPOXY RESIN are mixed by mass ratio at 90: 10, it is dissolved in the MEK, and the mass ratio of MEK and main slurry is 20: 80, obtains sizing agent master slurry, add above mixed aid then, the addition of mixed aid is 10% of a main slurry.This mixture heated to 80 ℃ is mixed, and high-speed stirred under the constant rate of speed of 13000r/min dropwise adds deionized water then, the ratio of deionized water and main slurry is 90: 10, after water injection the back continues to stir 60min, obtains the sizing agent emulsion, and solid content is 8-11%.It is 0.5% that this emulsion is diluted to solid content, with infusion process with the sizing agent of this concentration adhere to polyacrylonitrile carbon fiber on, impregnation time 40s places 100 ℃ of dry 10min of baking oven then.The interlaminar shear strength (ILSS) of the rate of sizing, stiffness, lousiness amount, abrasion resistance and the carbon-fibre reinforced epoxy resin of carbon fiber after the stability of this sizing agent emulsion of mensuration, the starching under the room temperature.
Comparative example 1
Do not add emulsifying agent and bleeding agent in the process of preparation sizing agent emulsion, other condition is identical with embodiment 2.The interlaminar shear strength (ILSS) of the rate of sizing of carbon fiber, stiffness, lousiness amount, abrasion resistance and carbon fiber enhancing vinyl ester resin after the stability of this sizing agent emulsion of mensuration, the starching under the room temperature.
Comparative example 2
Except that main slurry does not add the POLYBUTADIENE EPOXY RESIN, other are with embodiment 5.The interlaminar shear strength (ILSS) of the rate of sizing of carbon fiber, stiffness, lousiness amount, abrasion resistance and carbon fiber enhancing vinyl ester resin after the stability of this sizing agent emulsion of mensuration, the starching under the room temperature.
Comparative example 3
Measure the stiffness, lousiness amount, abrasion resistance of starching carbon fiber not and the interlaminar shear strength of starching carbon-fibre reinforced epoxy resin (ILSS) not under the room temperature, the results are shown in shown in the table 1.
Comparative example 4
Measure under the room temperature stiffness, lousiness amount, abrasion resistance of starching carbon fiber not and not the starching carbon fiber strengthen the interlaminar shear strength (ILSS) of vinyl ester resin, the results are shown in shown in the table 1.
Table 1
| Sample | Stability progression | The rate of sizing | Stiffness/mm | Lousiness amount/mg | Abrasion resistance/time | ILSS /MPa |
| Embodiment 1 | V | 0.56％ | 60 | 1.52 | 846 | 48.24 |
| Embodiment 2 | V | 1.26％ | 52 | 1.23 | 856 | 45.36 |
| |
VI | 1.84％ | 50 | 1.22 | 956 | 45.24 |
| |
VI | 1.39％ | 63 | 1.29 | 903 | 48.26 |
| Embodiment 5 | V | 2.67％ | 51 | 1.27 | 921 | 44.37 |
| Embodiment 6 | V | 1.36％ | 69 | 1.47 | 912 | 47.68 |
| Comparative example 1 | I | 1.01％ | 57 | 3.87 | 532 | 39.87 |
| Comparative example 2 | V | 1.22％ | 79 | 2.56 | 652 | 35.25 |
| Comparative example 3 | - | - | 60 | 26.80 | 302 | 41.84 |
| Comparative example 4 | - | - | 60 | 26.80 | 302 | 38.09 |
By the data in the table 1 as can be seen, sizing agent stability of the present invention is strong, ABRASION RESISTANCE raising, the lousiness amount of carbon fiber are reduced, the back processing characteristics of fiber improves, and the interface cohesiveness of carbon fiber after the starching and matrix resin is better, strengthens the interlaminar shear strength of vinyl ester resin and epoxy resin.
Claims (6)
1. carbon fiber emulsion pasting agent, it is characterized in that comprising: main slurry, auxiliary agent, organic solvent and deionized water, wherein, the quality of auxiliary agent is 5%～15% of a main stock quality, the mass ratio of organic solvent and main slurry is 20～50: 50～80, and the mass ratio of deionized water and main slurry is 50～90: 10～50;
Described main slurry is glycidol ether type epoxy and the polyolefinic mixture of epoxidation aliphatic, and glycidol ether type epoxy and the polyolefinic mass ratio of epoxidation aliphatic are 10～90: 10～90;
Described auxiliary agent comprises emulsifying agent and bleeding agent, and the mass ratio of emulsifying agent and bleeding agent is 20～90: 10～80;
Described emulsifying agent is a blended emulsifier, forms mass ratio A: B=10～90: 10～90 by A and two kinds of surfactants of B;
A is NP-10 phosphate ammonium salt, NP-10 ammonium sulfate; B is OP-10, NP-10, farming breast 1601 or T-80.
2. carbon fiber emulsion pasting agent according to claim 1 is characterized in that: described glycidol ether type epoxy is E-55, E-51, E-44, and described epoxidation aliphatic poly alkene is epoxidized polybutadiene.
3. carbon fiber emulsion pasting agent according to claim 1 is characterized in that: described bleeding agent is secondary octanol polyoxyethylene ether or OPEO OP-7.
4. according to each described carbon fiber emulsion pasting agent among the claim 1-3, it is characterized in that: described organic solvent is acetone, MEK or n-butanol.
5. the preparation method of each described carbon fiber emulsion pasting agent among the claim 1-3, it is characterized in that adopting phase conversion emulsifying to prepare described sizing agent, step is: main slurry is dissolved in the organic solvent, add auxiliary agent, mix at 40～80 ℃, dropwise add deionized water then under the rotating speed of 8000～13000r/min, after water injection the back continues to stir 20～60min, obtains carbon fiber emulsion pasting agent.
6. preparation method according to claim 5 is characterized in that: the solid content of described carbon fiber emulsion pasting agent is 10～50wt%.
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| CN104264484B (en) * | 2014-09-26 | 2016-10-26 | 济南大学 | Emulsion type carbon fiber sizing agent and its preparation method and application |
| CN106120345A (en) * | 2016-08-31 | 2016-11-16 | 郭迎庆 | A kind of preparation method of carbon fiber sizing agent |
| CN112878055B (en) * | 2020-12-25 | 2024-01-05 | 中复神鹰碳纤维股份有限公司 | Preparation method of carbon fiber for building reinforced carbon cloth |
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| CN1701148A (en) * | 2001-05-25 | 2005-11-23 | 三菱丽阳株式会社 | Sizing agent for carbon fiber, aqueous dispersion thereof, carbon fiber treated by sizing, sheet-form object comprising the carbon fiber, and carbon fiber-reinforced composite material |
| CN100999867A (en) * | 2006-12-20 | 2007-07-18 | 中国科学院山西煤炭化学研究所 | Temp, resisting type carbon fibre emulsion sizing agent and its preparation process and application |
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