CN100500984C - Temperature tolerance type carbon fibre emulsion sizing agent and its preparation process and application - Google Patents
Temperature tolerance type carbon fibre emulsion sizing agent and its preparation process and application Download PDFInfo
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Abstract
The heat resisting emulsion sizing agent for carbon fiber consists of main sizing agent and assistant in 1-5 wt% of the main sizing agent. The main sizing agent is mixture of thermoplastic polyimide resin and glycidol ether type epoxy resin in the weight ratio of 50-90 to 10-50; and the assistant includes emulsifier, wetting agent and defoaming agent in the weight ratio of 10-80 to 10-80 to 10. The present invention has the advantages of low cost, stable performance, convenient use and no environmental pollution.
Description
Technical field
The invention belongs to a kind of emulsion type compound that is used to be coated with the charcoal fiber and close sizing agent and preparation method.Said composition can be improved the surface property of going up pulp fibres, can suppress charcoal fiber lousiness in process generation, improve the fiber ABRASION RESISTANCE, the interface that also can improve fiber and matrix resin simultaneously bonds.
Background of invention
Polyacrylonitrile charcoal fiber (PANCF) is a main reinforcing fiber materials of making high-performance composite materials.Because its high specific strength, high ratio modulus and good heat conduction, conduction, performance such as corrosion-resistant make it reinforced composite materials and are used widely in fields such as Aeronautics and Astronautics, industry, building, physical culture.In recent years, along with the development of aerospace industry, require the temperature of 250～350 ℃ of matrix resin abilities, and polyimides (PI) resin etc. can reach this requirement; Therefore resistant to elevated temperatures polymer matrix composites such as CF/PI resin composite materials become the focus of concern.
In production and process, the charcoal fiber is easy to generate lousiness and single wire fracture phenomenon through mechanical friction, and fibre strength is reduced.Because the existence of lousiness also makes matrix resin can not fully soak into the charcoal fiber, cause prepared composite to produce hole, influence the mechanical property of composite.Therefore, must carry out starching to the charcoal fiber handles.
Yan Zhi sizing agent mainly was at the charcoal fibre reinforced epoxy resin composite in the past, opened flat 5-132863 as the spy and made sizing agent with the mixture of epoxy resin-polyurethane resin; Using polyurethane resin and polyether resin among the Te Kaiping 10-266076 is necessary composition, is aided with high-grade aliphatic ester and makes sizing agent; The spy opens among the 2005-179826 to propose to mix by a certain percentage with fatty family polyepoxides and fragrant family polyepoxides and makes sizing agent etc., and all being used for epoxy resin coating is the charcoal fiber of the composite of matrix.And report is seldom arranged at the charcoal fiber sizing agent of polyimide resin composite material, introduced linear polyamidoamine-acid imide with end-blocking and end-blocking not among the U.S.5239046 as the main slurry of composite polyimide material with charcoal fiber sizing agent, but this polyamidoimide needs own polymerization, and operation is more loaded down with trivial details.Having introduced the polyamic acid of fluoridizing among the U.S.4923752 has good adhesive property as sizing agent coated charcoal fiber and polyimide resin, and cost is higher but this fluoridizes polyamic acid.
Summary of the invention
The purpose of this invention is to provide that a kind of cost is low, the temp, resisting type carbon fibre emulsion sizing agent of stable performance and preparation method.
Sizing agent of the present invention is made up of main slurry and auxiliary agent, has added mixed surfactant as auxiliary agent in sizing agent master slurry.In order to make the high-quality charcoal fiber starching emulsion of stable performance, in the mixed aid of the present invention, comprised a certain amount of emulsifying agent.Because carbon fiber surface functional group is hydrophobicity, sizing agent is difficult to timely wetting fiber surface in the starching process, cause slurry not form uniform film at fiber surface, and influence the performance of fiber, therefore also comprise a certain amount of wetting agent in the mixed aid of the present invention, with the effective wettability of improving emulsion and fiber.Because after adding emulsifying agent and wetting agent, emulsion is bubbled easily and caused sizing agent coated inhomogeneous at fiber surface, thereby influences composite property, mixed aid of the present invention also includes the defoamer of trace, to suppress the generation of foam.
Sizing agent of the present invention is made up of main slurry and auxiliary agent, the auxiliary agent quality is 1%～5% of a main stock quality, main slurry by thermoplastic polyimide resin and glycidol ether type epoxy by weight being thermoplastic polyimide resin: the blend of glycidol ether type epoxy=50～90:10～50 is formed, auxiliary agent by emulsifying agent, wetting agent and defoamer by emulsifying agent: wetting agent: the mass ratio of defoamer is that 10～80:10～80:10 forms.
Described thermoplastic polyimide resin is GCPI
TM-L1 (below be abbreviated as GCPI) thermoplastic polyimide resin, the glycidol ether type epoxy is E-55, E-51, E-44, E-42, E-35 or E-31 glycidol ether type epoxy.
Described emulsifying agent is sorbitan monostearate polyoxyethylene ether (T-60), alkylphenol polyoxyethylene (OP-7), castor oil polyoxyethylene ether (EL), aliphatic acid and oxirane addition polymers (SE-10) or fatty alcohol-polyoxyethylene ether (O-10); Wetting agent is the mixture (1108) of fatty alcohol-polyoxyethylene ether (JFC), secondary octanol polyoxyethylene ether (JFC-2) or polyoxyethylene and polyethenoxy ether, and defoamer is a silicone defoaming agent.
Preparation method of the present invention is as follows:
At first main slurry is dissolved in the organic solvent, adds auxiliary agent again, be controlled to be at rotating speed under the stirring of 10000～20000rpm, dropwise add a certain amount of deionized water, continue afterwards to stir 30～60min, make white emulsion by main slurry composition.
The mass ratio of described organic solvent and main slurry is 0.5～5:1, and the mass ratio of deionized water and organic solvent is 0.04～0.2:1.
Described organic solvent is dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO).
The sizing agent that makes is diluted to 0.1～5wt%, is preferably in 0.5～3wt%.It is poor to be lower than the 0.1wt% starch finishing effect, and the charcoal fiber easily produces lousiness, and it is really up to the mark to surpass the 5wt% fiber, influences processing characteristics.To dilute good sizing agent with infusion process and be attached on the charcoal fiber, dip time is 5～30s, with the fiber after the soaking paste in 100～250 ℃ of following dried 30～200s.100 ℃ of water evaporations of less than are slower, and sizing agent is difficult for dry, are heated apt to deteriorate otherwise surpass 250 ℃ of sizing agents.
Advantage of the present invention is as follows
1, this sizing agent is the emulsion-type sizing agent, and is easy to use, free from environmental pollution;
2, this sizing agent itself can bear higher temperature, and its heat decomposition temperature is about 300 ℃.Be applicable to and the compound preparation composite of fire resistant resins such as polyimides or bimaleimide resin with the coated charcoal fiber of this sizing agent.
3, more starching charcoal fiber lousiness is not few, ABRASION RESISTANCE good with the coated charcoal fiber of this sizing agent, and does not more improve a lot during starching with the interface binding intensity of resin.
The specific embodiment
Embodiment 1
Sorbitan monostearate polyoxyethylene ether (T-60), fatty alcohol-polyoxyethylene ether (JFC), silicone defoaming agent are mixed by mass ratio 20:70:10, obtain mixed aid, place standby.Is that 80:20 mixes with GCPI and E-55 by mass ratio, stirring obtains sizing agent master slurry, and it is dissolved in the dimethyl formamide, and the mass ratio of main slurry and organic solvent is 1:1, add the mixed aid for preparing in advance then, the quality of mixed aid is 1% of a main stock quality.Stir with high-shearing dispersion emulsifying machine, rotating speed is 10000rpm.Under high degree of agitation, dropwise add deionized water, the mass ratio of deionized water and organic solvent is 0.04:1, continues afterwards to stir 30min, makes the starching emulsion.The emulsion that makes is diluted to 3wt%, is attached on the polyacrylonitrile charcoal fiber, soaking paste time 5s, dry 30S under 160 ℃ with the sizing agent of infusion process with this concentration.Measure the sizing agent emulsion stability, lousiness amount, ABRASION RESISTANCE to the wettability of fiber, starching charcoal fiber and with the interface shear strength (IFSS) of bimaleimide resin QY8911, method of testing is as described below, the results are shown in table 1.
Stability: get emulsion 10ml and put into glass system centrifugal sedimentation pipe.With centrifugal separator with 4000rpm centrifugation 10 minutes.Separate the back and remove supernatant liquid with gradient method, the precipitum dissolution with solvents with centrifugal sedimentation pipe bottom moves to it on glass dish, and evaporation is done solid.Measuring the quality of doing solid on the glass dish of solid back on the analytical balance.If the quality of solid thinks just that below 50mg the aqueous dispersion stability of sizing agent is no problem.
Wettability: characterize with contact angle, it is generally acknowledged that contact angle is more little, wettability is good more.With JY-82 contact angle instrument (Chengde, Hebei province testing machine Co., Ltd).Adopt insertion, the ultimate angle (θ) when measuring fiber and liquid unsticking, calculate contact angle (90 °-θ).
The lousiness amount: the charcoal fibre bundle is wiped at two polyurethane sponges under (size 40mm * 5mm * 5mm, heavily about 0.35g) clamping, and whole polyurethane sponge is wiped load 200g.The charcoal fibre bundle passes through with 3m/min speed, surveys the weight that is attached to lousiness on the sponge after 10 minutes, is the friction lousiness amount of charcoal fibre bundle.
ABRASION RESISTANCE: the charcoal fiber strand silk with 120 ° angle and each autoparallel every 50mm at interval, zigzag 3 stainless steel bars that arrange, smooth surface, diameter 10mm contact and pass through.Fiber is hung on the stainless steel bar load-carrying 20g.With the speed reciprocating motion of 104 times/min, the number of times when writing down fiber and rubbing.
Interface shear strength (IFSS): adopt the composite material interface evaluating apparatus to measure, test process is earlier the charcoal fiber to be fixed on the iron plate, then with uncured aqueous resin point on fiber, in the process of being heating and curing, because surface tension effects, resin can form circular bead.With blade resin is clamped, and give the fiber imposed load, from resin, dial the load F that is born when taking off by measuring fiber, the diameter d of fiber, the diameter 2r of institute's assize fat bead calculates composite material interface shear strength τ.
Computing formula:
Embodiment 2
Alkylphenol polyoxyethylene (OP-7), secondary octanol polyoxyethylene ether (JFC-2), silicone defoaming agent are mixed by mass ratio 40:50:10, obtain mixed aid, place standby.Is that 80:20 mixes with GCPI and E-51 by mass ratio, stirring obtains sizing agent master slurry, and it is dissolved in the dimethylacetylamide, and the mass ratio of main slurry and organic solvent is 1.5:1, add the mixed aid for preparing in advance then, the quality of mixed aid is 2% of a main stock quality.Stir with high-shearing dispersion emulsifying machine, rotating speed is 13000rpm.Under high degree of agitation, dropwise add deionized water, the mass ratio of deionized water and organic solvent is 0.08:1, continues afterwards to stir 40min, makes the starching emulsion.The emulsion that makes is diluted to 1.0wt%, is attached on the polyacrylonitrile charcoal fiber, soaking paste time 10s, dry 60s under 180 ℃ with the sizing agent of infusion process with this concentration.Test result is as shown in table 1.
Embodiment 3
Mixture (1108), the silicone defoaming agent of sorbitan monostearate polyoxyethylene ether (T-60), polyoxyethylene and polyethenoxy ether are mixed by mass ratio 60:30:10, obtain mixed aid, place standby.Is that 70:30 mixes with GCPI and E-44 by mass ratio, stirring obtains sizing agent master slurry, and it is dissolved in the dimethyl sulfoxide (DMSO), and the mass ratio of main slurry and organic solvent is 2:1, add the mixed aid for preparing in advance then, the quality of mixed aid is 3% of a main stock quality.Stir with high-shearing dispersion emulsifying machine, rotating speed is 15000rpm.Under high degree of agitation, dropwise add deionized water, the mass ratio of deionized water and organic solvent is 0.1:1, continues afterwards to stir 60min, makes the starching emulsion.The emulsion that makes is diluted to 1.5wt%, is attached on the polyacrylonitrile charcoal fiber, soaking paste time 20s, dry 120s under 200 ℃ with the sizing agent of infusion process with this concentration.Test result is as shown in table 1.
Embodiment 4
Castor oil polyoxyethylene ether (EL), fatty alcohol-polyoxyethylene ether (JFC), silicone defoaming agent are mixed by mass ratio 20:70:10, obtain mixed aid, place standby.Is that 70:30 mixes with GCPI and E-42 by mass ratio, stirring obtains sizing agent master slurry, and it is dissolved in the dimethyl sulfoxide (DMSO), and the mass ratio of main slurry and organic solvent is 4:1, add the mixed aid for preparing in advance then, the quality of mixed aid is 4% of a main stock quality.Stir with high-shearing dispersion emulsifying machine, rotating speed is 19000rpm.Under high degree of agitation, dropwise add deionized water, the mass ratio of deionized water and organic solvent is 0.15:1, continues afterwards to stir 50min, makes the starching emulsion.The emulsion that makes is diluted to 2.0wt%, is attached on the polyacrylonitrile charcoal fiber, soaking paste time 8s, dry 180s under 180 ℃ with the sizing agent of infusion process with this concentration.Test result is as shown in table 1.
Embodiment 5
Aliphatic acid and oxirane addition polymers (SE-10), secondary octanol polyoxyethylene ether (JFC-2), silicone defoaming agent are mixed by mass ratio 40:50:10, obtain mixed aid, place standby.Is that 60:40 mixes with GCPI and E-35 by mass ratio, stirring obtains sizing agent master slurry, and it is dissolved in the dimethyl sulfoxide (DMSO), and the mass ratio of main slurry and organic solvent is 1:1, add the mixed aid for preparing in advance then, the quality of mixed aid is 5% of a main stock quality.Stir with high-shearing dispersion emulsifying machine, rotating speed is 13000rpm.Under high degree of agitation, dropwise add deionized water, the mass ratio of deionized water and organic solvent is 0.2:1, continues afterwards to stir 60min, makes the starching emulsion.The emulsion that makes is diluted to 3.0wt%, is attached on the polyacrylonitrile charcoal fiber, soaking paste time 10s, dry 120s under 150 ℃ with the sizing agent of infusion process with this concentration.Test result is as shown in table 1.
Embodiment 6
Mixture (1108), the silicone defoaming agent of polyoxyethylene and polyethenoxy ether are mixed by mass ratio 60:30:10, obtain mixed aid, place standby.Is that 60:40 mixes with GCPI and E-31 by mass ratio, stirring obtains sizing agent master slurry, and it is dissolved in the dimethyl sulfoxide (DMSO), and the mass ratio of main slurry and organic solvent is 2:1, add the mixed aid for preparing in advance then, the quality of mixed aid is 3% of a main stock quality.Stir with high-shearing dispersion emulsifying machine, rotating speed is 15000rpm.Under high degree of agitation, dropwise add deionized water, the mass ratio of deionized water and organic solvent is 0.1:1, continues afterwards to stir 40min, makes the starching emulsion.The emulsion that makes is diluted to 3.0wt%, is attached on the polyacrylonitrile charcoal fiber, soaking paste time 10s, dry 180s under 180 ℃ with the sizing agent of infusion process with this concentration.Test result is as shown in table 1.
Comparative example 1
In preparation sizing agent process, do not add emulsifying agent.Fatty alcohol-polyoxyethylene ether (JFC) and silicone defoaming agent are mixed by mass ratio 80:10, obtain mixed aid, place standby.Is that 60:40 mixes with GCPI and E-44 by mass ratio, stirring obtains sizing agent master slurry, and it is dissolved in the dimethyl sulfoxide (DMSO), and the mass ratio of main slurry and organic solvent is 1:1, add the mixed aid for preparing in advance then, the quality of mixed aid is 3% of a main stock quality.Stir with high-shearing dispersion emulsifying machine, rotating speed is 10000rpm.Under high degree of agitation, dropwise add deionized water, the mass ratio of deionized water and organic solvent is 0.04:1, continues afterwards to stir 30min, makes the starching emulsion.The emulsion that makes is diluted to 1.0wt%, is attached on the polyacrylonitrile charcoal fiber, soaking paste time 30s, dry 120s under 180 ℃ with the sizing agent of infusion process with this concentration.Test result is as shown in table 1.
Comparative example 2
In preparation sizing agent process, do not add wetting agent.Sorbitan monostearate polyoxyethylene ether (T-60) and silicone defoaming agent are mixed by mass ratio 80:10, obtain mixed aid, place standby.Is that 70:30 mixes with GCPI and E-51 by mass ratio, stirring obtains sizing agent master slurry, and it is dissolved in the dimethyl sulfoxide (DMSO), and the mass ratio of main slurry and organic solvent is 3:1, add the mixed aid for preparing in advance then, the quality of mixed aid is 3% of a main stock quality.Stir with high-shearing dispersion emulsifying machine, rotating speed is 13000rpm.Under high degree of agitation, dropwise add deionized water, the mass ratio of deionized water and organic solvent is 0.2:1, continues afterwards to stir 40min, makes the starching emulsion.The emulsion that makes is diluted to 3.0wt%, is attached on the polyacrylonitrile charcoal fiber, soaking paste time 10s, dry 180s under 160 ℃ with the sizing agent of infusion process with this concentration.Test result is as shown in table 1.
Comparative example 3
Test starching charcoal fiber not lousiness amount, ABRASION RESISTANCE and with the interface shear strength of bimaleimide resin QY8911, the results are shown in table 1.
Table 1
| Sample | Stability/mg | Contact angle/° | Lousiness amount/g | Abrasion resistance/time | IFSS/MPa |
| Embodiment 1 | 28 | 27 | 0.00132 | 698 | 68.21 |
| Embodiment 2 | 23 | 29 | 0.00147 | 534 | 71.27 |
| Embodiment 3 | 17 | 35 | 0.00220 | 942 | 69.56 |
| Embodiment 4 | 32 | 29 | 0.00165 | 892 | 66.24 |
| Embodiment 5 | 22 | 32 | 0.00179 | 983 | 59.50 |
| Embodiment 6 | 15 | 41 | 0.00298 | 1081 | 61.24 |
| Comparative example 1 | 55 | 25 | 0.00248 | 853 | 63.21 |
| Comparative example 2 | 15 | 60 | 0.00187 | 870 | 67.10 |
| Comparative example 3 | — | — | 0.03912 | 213 | 36.31 |
Claims (9)
1, a kind of temp, resisting type carbon fibre emulsion sizing agent, it is characterized in that sizing agent is by main slurry, auxiliary agent, organic solvent and deionized water are formed, the auxiliary agent quality is 1%～5% of a main stock quality, main slurry is thermoplastic polyimide resin by weight by thermoplastic polyimide resin and glycidol ether type epoxy: the blend of glycidol ether type epoxy=50～90:10～50 is formed, auxiliary agent is by emulsifying agent, wetting agent and defoamer are by emulsifying agent: wetting agent: the mass ratio of defoamer is that 10～80:10～80:10 forms, the mass ratio of organic solvent and main slurry is 0.5～5:1, and the mass ratio of deionized water and organic solvent is 0.04～0.2:1.
2, a kind of temp, resisting type carbon fibre emulsion sizing agent as claimed in claim 1 is characterized in that the glycidol ether type epoxy is E-55, E-51, E-44, E-42, E-35 or E-31 glycidol ether type epoxy.
3, a kind of temp, resisting type carbon fibre emulsion sizing agent as claimed in claim 1 is characterized in that described emulsifying agent is sorbitan monostearate polyoxyethylene ether, alkylphenol polyoxyethylene, castor oil polyoxyethylene ether or aliphatic acid and oxirane addition polymers.
4, a kind of temp, resisting type carbon fibre emulsion sizing agent as claimed in claim 1 is characterized in that described wetting agent is a fatty alcohol-polyoxyethylene ether, or the mixture of polyoxyethylene and polyethenoxy ether.
5, a kind of temp, resisting type carbon fibre emulsion sizing agent as claimed in claim 1 is characterized in that described defoamer is a silicone defoaming agent.
6,, it is characterized in that comprising the steps: as the preparation method of each described a kind of temp, resisting type carbon fibre emulsion sizing agent of claim 1-5
At first main slurry is dissolved in the organic solvent, adds auxiliary agent again, be controlled to be at rotating speed under the stirring of 10000～20000rpm, dropwise add a certain amount of deionized water, continue afterwards to stir 30～60min, make white emulsion by main slurry composition;
The mass ratio of described organic solvent and main slurry is 0.5～5:1, and the mass ratio of deionized water and organic solvent is 0.04～0.2:1.
7, the preparation method of a kind of temp, resisting type carbon fibre emulsion sizing agent as claimed in claim 6 is characterized in that described organic solvent is dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO).
8, as the application process of each described a kind of temp, resisting type carbon fibre emulsion sizing agent of claim 1-5, it is characterized in that sizing agent is diluted to 0.1～5wt%, to dilute good sizing agent with infusion process is attached on the charcoal fiber, dip time is 5～30s, with the fiber after the soaking paste in 100～250 ℃ of following dried 30～200s.
9, the application process of a kind of temp, resisting type carbon fibre emulsion sizing agent as claimed in claim 8 is characterized in that described sizing agent is diluted to 0.5～3wt%.
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