CN105646945B - A method of it preparing nano silicon dioxide using sulfydryl-alkene click-reaction and is grafted carbon fiber reinforcement - Google Patents
A method of it preparing nano silicon dioxide using sulfydryl-alkene click-reaction and is grafted carbon fiber reinforcement Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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Abstract
The method that nano silicon dioxide is grafted carbon fiber reinforcement is prepared using sulfydryl alkene click-reaction the present invention relates to a kind of, and specific step is：1）The processing of nano silicon dioxide sulfhydrylation；2）The acidification of carbon fiber；3）Carbon fiber surface amination processing；4）Allyl glycidyl ether is grafted the preparation of carbon fiber；5）Nano silicon dioxide, which is prepared, using sulfydryl alkene click-reaction is grafted carbon fiber reinforcement.After carbon fiber surface engrafted nanometer silica, surface roughness improves, with the wellability of resin be improved significantly, be conducive to improve the interface binding power between carbon fiber and resin matrix, and then improve the mechanical property of carbon fibre reinforced composite.In addition, after carbon fiber surface engrafted nanometer silica, thermal stability is significantly improved.Inventive method reaction time is short, yield is high, and by-product is harmless, is conducive to large-scale production.
Description
Technical field
The side that nano silicon dioxide is grafted carbon fiber reinforcement is prepared using sulfydryl-alkene click-reaction the present invention relates to a kind of
Method.
Background technology
Carbon fiber be it is a kind of have many advantages, such as low-density, high specific strength, high ratio modulus, endurance, heat conduction, conduction it is novel
Material has been widely used for the fields such as Aeronautics and Astronautics, stationery sports goods and textile machine.But due to carbon fiber self structure
Feature so that it is poor with the caking property of resin matrix, and not secured enough with resin matrix compound tense interface, composite material is very
More excellent properties cannot be brought into play well.Therefore, it is carbon fiber in polymer matrix composite to carbon fiber surface modification
The critical issue faced in.
Traditional surface treatment of carbon fibers technology is more demanding to equipment and technique, and treatment effect is bad.Utilize mercapto
It is when the new method of modifying of former that base-alkene click-reaction, which is modified inorganic material surface, and this method has application range
Extensively, the advantages that yield is high, by-product is harmless, the reaction time is short.The method avoids traditional method of modifying process time is long, mistake
Journey is toxic, it is difficult to the problems such as industrialized mass production.Nano silicon dioxide is grafted to carbon fiber by sulfydryl-alkene click-reaction
Behind dimension table face, the interface binding power between carbon fiber and resin matrix can be significantly improved, while improving the thermal stability of carbon fiber
Energy.
Invention content
The purpose of the present invention is to provide it is a kind of it is simple, quickly prepare nano silicon dioxide and be grafted carbon fiber reinforcement
The principle of method, this method is mainly based upon sulfydryl-alkene click-reaction, the nanometer two that the reaction time is short, yield is high, prepared
Silica grafting carbon fiber reinforcement have many advantages, such as surface roughness greatly, with resin infiltration is good, thermal stability is good.
The present invention is achieved like this, and nano silicon dioxide is grafted the preparation method of carbon fiber reinforcement, it is characterized in that
Method and step is：
The first step：1g nano silicon dioxides and 0.4g deionized waters are added in 30 ~ 60mL ethyl alcohol, ultrasonication 60
2 ~ 4g is added after ~ 120 minutes and contains mercaptosilane coupling agents, is put into oil bath pan in 60~75 DEG C of back flow reactions 4 ~ 6 hours, reaction
After cleaned 4 times with ethyl alcohol and removed and contain mercaptosilane coupling agents on non-grafted, be placed in 100 DEG C of vacuum drying chambers dry 24
Hour, you can obtain the silica of engrafted nanometer containing mercaptosilane coupling agents；
Second step：5g carbon fibers are immersed in 100 ~ 160mL nitration mixture, ultrasonication 60 ~ 120 minutes then moves into oil
It is reacted 2 ~ 4 hours for 80 ~ 100 DEG C in bath, is washed with deionized water after completion of the reaction to neutrality, is subsequently placed in 100 DEG C of vacuum drying
In case dry 24 hours to get to sour Treatment of Carbon；
Third walks：5g acid Treatment of Carbon is dispersed in 150 ~ 200mL in the mixed solvents, with second acid for adjusting pH value to 4 ~ 5,
Ultrasonication 30 ~ 10 ~ 30g is added after sixty minutes containing amino silicane coupling agent, 60 DEG C are reacted 2 ~ 4 hours, are used after reaction
The mixed solution of ethyl alcohol, acetone and deionized water cleans 4 times and removes contains amino silicane coupling agent on non-grafted, is placed in 100 DEG C
It is 24 hours dry in vacuum drying chamber, you can to obtain being grafted carbon fiber containing amino silicane coupling agent；
4th step：By 2g containing amino silicane coupling agent grafting carbon fiber be dispersed in 30~60mL ethyl alcohol, then be added 4 ~
8g allyl glycidyl ethers, room temperature magnetic agitation 48 ~ 72 hours are cleaned 4 times with ethyl alcohol, then in 40 DEG C of vacuum drying chambers
It is 24 hours dry, you can to obtain allyl glycidyl ether grafting carbon fiber；
5th step：0.4g engrafted nanometers containing mercaptosilane coupling agents silica and 1g allyl glycidyl ethers are grafted
Carbon fiber is dispersed in the dimethylformamide of 30 ~ 60mL, ultrasonication 60 ~ 120 minutes, and the light of 0.1g is then added
Initiator uses wavelength for the ultraviolet light 1 ~ 2 hour of 365 nm, is then cleaned 4 times with ethyl alcohol, is dried in vacuo at 80 DEG C
It is 24 hours dry in case, you can to obtain nano silicon dioxide grafting carbon fiber reinforcement.
Described is γ-mercaptopropyl trimethoxysilane, γ-mercapto hydroxypropyl methyl dimethoxy silicon containing mercaptosilane coupling agents
One kind in alkane or gamma-mercaptopropyltriethoxysilane.
The nitration mixture be 65% by mass percent concentration concentrated nitric acid and mass percent concentration be 96% dense sulphur
Acid is 3 by volume:1 ratio mixes.
It is 4 by volume that the mixed solvent, which is by absolute ethyl alcohol and deionized water,:1 ratio mixes.
Described is gamma-aminopropyl-triethoxy-silane, γ-aminopropyltriethoxy diethoxy silicon containing amino silicane coupling agent
One kind in alkane or γ-aminopropyltrimethoxysilane.
The photoinitiator is one kind in benzoin dimethylether or 2- hydroxy-2-methyl -1- phenyl -1- acetone.
The solution have the advantages that：Nano silicon dioxide grafting carbon fiber reinforcement provided by the invention has surface thick
The advantages that rugosity is big, and nano silicon dioxide grafting rate is high, good with resin matrix caking property, and thermal stability is good.
Specific implementation mode
Embodiment 1：
This example demonstrates that a kind of utilization sulfydryl-alkene click-reaction provided by the invention prepares nano silicon dioxide grafted carbon
The method of fibre reinforcement.
The first step：1g nano silicon dioxides and 0.4g deionized waters are added in 30mL ethyl alcohol, ultrasonication 120 is divided
2g is added after clock and contains mercaptosilane coupling agents（γ-mercapto hydroxypropyl methyl dimethoxysilane）, it is put into oil bath pan and flows back at 70 DEG C
Reaction 5 hours, clean after reaction with ethyl alcohol remove for 4 times on non-grafted containing mercaptosilane coupling agents, be placed in 100 DEG C of vacuum
It is 24 hours dry in drying box, you can to obtain the silica of engrafted nanometer containing mercaptosilane coupling agents；
Second step：5g carbon fibers are immersed in 160mL nitration mixture, ultrasonication 60 minutes then moves into 80 in oil bath pan
DEG C reaction 4 hours, is washed with deionized water after completion of the reaction to neutrality, be subsequently placed in 100 DEG C of vacuum drying chambers it is 24 hours dry,
Obtain sour Treatment of Carbon；
Third walks：5g acid Treatment of Carbon is dispersed in 180mL in the mixed solvents, with second acid for adjusting pH value to 4, ultrasonic wave
Processing is added 10g after 45 minutes and contains amino silicane coupling agent（Gamma-aminopropyl-triethoxy-silane）, 60 DEG C are reacted 3 hours, reaction
After with the mixed solution of ethyl alcohol, acetone and deionized water clean 4 times remove it is non-grafted on contain amino silicane coupling agent, set
It is 24 hours dry in 100 DEG C of vacuum drying chambers, you can to obtain being grafted carbon fiber containing amino silicane coupling agent；
4th step：2g grafting carbon fibers containing amino silicane coupling agent are dispersed in 45mL ethyl alcohol, 4g allyls are then added
Base glycidol ether, room temperature magnetic agitation 48 hours are cleaned 4 times with ethyl alcohol, and then drying 24 is small in 40 DEG C of vacuum drying chambers
When, you can obtain allyl glycidyl ether grafting carbon fiber；
5th step：0.4g engrafted nanometers containing mercaptosilane coupling agents silica and 1g allyl glycidyl ethers are grafted
Carbon fiber is dispersed in the dimethylformamide of 30mL, ultrasonication 120 minutes, and the styrax that 0.1g is then added is double
Methyl ether uses wavelength for the ultraviolet light 1 hour of 365 nm, is then cleaned 4 times with ethyl alcohol, in 80 DEG C of vacuum drying chambers
It is 24 hours dry, you can to obtain nano silicon dioxide grafting carbon fiber reinforcement.
Embodiment 2：
This example demonstrates that a kind of utilization sulfydryl-alkene click-reaction provided by the invention prepares nano silicon dioxide grafted carbon
The method of fibre reinforcement.
The first step：1g nano silicon dioxides and 0.4g deionized waters are added in 60mL ethyl alcohol, ultrasonication 60 is divided
3g is added after clock and contains mercaptosilane coupling agents（Gamma-mercaptopropyltriethoxysilane）, it is put into oil bath pan in 75 DEG C of back flow reactions 6
Hour, clean after reaction with ethyl alcohol remove for 4 times on non-grafted containing mercaptosilane coupling agents, be placed in 100 DEG C of vacuum drying
It is 24 hours dry in case, you can to obtain the silica of engrafted nanometer containing mercaptosilane coupling agents；
Second step：5g carbon fibers are immersed in 120mL nitration mixture, ultrasonication 90 minutes then moves into 100 in oil bath pan
DEG C reaction 2 hours, is washed with deionized water after completion of the reaction to neutrality, be subsequently placed in 100 DEG C of vacuum drying chambers it is 24 hours dry,
Obtain sour Treatment of Carbon；
Third walks：5g acid Treatment of Carbon is dispersed in 150mL in the mixed solvents, with second acid for adjusting pH value to 5, ultrasonic wave
Processing is added 20g and contains amino silicane coupling agent after sixty minutes（γ-aminopropyltrimethoxysilane）, 60 DEG C are reacted 4 hours, reaction
After with the mixed solution of ethyl alcohol, acetone and deionized water clean 4 times remove it is non-grafted on contain amino silicane coupling agent, set
It is 24 hours dry in 100 DEG C of vacuum drying chambers, you can to obtain being grafted carbon fiber containing amino silicane coupling agent；
4th step：2g grafting carbon fibers containing amino silicane coupling agent are dispersed in 30mL ethyl alcohol, 6g allyls are then added
Base glycidol ether, room temperature magnetic agitation 72 hours are cleaned 4 times with ethyl alcohol, and then drying 24 is small in 40 DEG C of vacuum drying chambers
When, you can obtain allyl glycidyl ether grafting carbon fiber；
5th step：0.4g engrafted nanometers containing mercaptosilane coupling agents silica and 1g allyl glycidyl ethers are grafted
Carbon fiber is dispersed in the dimethylformamide of 60mL, ultrasonication 60 minutes, and the 2- hydroxyls -2- of 0.1g is then added
Methyl-1-phenyl-1- acetone uses wavelength for the ultraviolet light 2 hours of 365 nm, is then cleaned 4 times with ethyl alcohol, 80
It is 24 hours dry in DEG C vacuum drying chamber, you can to obtain nano silicon dioxide grafting carbon fiber reinforcement.
Embodiment 3：
This example demonstrates that a kind of utilization sulfydryl-alkene click-reaction provided by the invention prepares nano silicon dioxide grafted carbon
The method of fibre reinforcement.
The first step：1g nano silicon dioxides and 0.4g deionized waters are added in 45mL ethyl alcohol, ultrasonication 90 is divided
4g is added after clock and contains mercaptosilane coupling agents（γ-mercaptopropyl trimethoxysilane）, it is put into oil bath pan in 60 DEG C of back flow reactions 4
Hour, clean after reaction with ethyl alcohol remove for 4 times on non-grafted containing mercaptosilane coupling agents, be placed in 100 DEG C of vacuum drying
It is 24 hours dry in case, you can to obtain the silica of engrafted nanometer containing mercaptosilane coupling agents；
Second step：5g carbon fibers are immersed in 100mL nitration mixture, ultrasonication 120 minutes then moves into 90 in oil bath pan
DEG C reaction 3 hours, is washed with deionized water after completion of the reaction to neutrality, be subsequently placed in 100 DEG C of vacuum drying chambers it is 24 hours dry,
Obtain sour Treatment of Carbon；
Third walks：5g acid Treatment of Carbon is dispersed in 200mL in the mixed solvents, with second acid for adjusting pH value to 4, ultrasonic wave
Processing is added 30g after 30 minutes and contains amino silicane coupling agent（γ-aminopropyltriethoxy diethoxy silane）, 60 DEG C are reacted 2 hours,
4 times are cleaned with the mixed solution of ethyl alcohol, acetone and deionized water remove being coupled containing amino silane on non-grafted after reaction
Agent is placed in 100 DEG C of vacuum drying chambers 24 hours dry, you can obtains being grafted carbon fiber containing amino silicane coupling agent；
4th step：2g grafting carbon fibers containing amino silicane coupling agent are dispersed in 60mL ethyl alcohol, 8g allyls are then added
Base glycidol ether, room temperature magnetic agitation 60 hours are cleaned 4 times with ethyl alcohol, and then drying 24 is small in 40 DEG C of vacuum drying chambers
When, you can obtain allyl glycidyl ether grafting carbon fiber；
5th step：0.4g engrafted nanometers containing mercaptosilane coupling agents silica and 1g allyl glycidyl ethers are grafted
Carbon fiber is dispersed in the dimethylformamide of 45mL, ultrasonication 90 minutes, and the styrax that 0.1g is then added is double
Methyl ether uses wavelength for the ultraviolet light 1 hour of 365 nm, is then cleaned 4 times with ethyl alcohol, is done in 80 DEG C of vacuum drying chambers
Dry 24 hours, you can obtain nano silicon dioxide grafting carbon fiber reinforcement.
Claims (6)
1. a kind of preparing the method that nano silicon dioxide is grafted carbon fiber reinforcement using sulfydryl-alkene click-reaction, feature exists
In the described method comprises the following steps：
The first step：1g nano silicon dioxides and 0.4g deionized waters are added in 30 ~ 60mL ethyl alcohol, ultrasonication 60 ~ 120
2 ~ 4g is added after minute and contains mercaptosilane coupling agents, is put into oil bath pan in 60~75 DEG C of back flow reactions 4 ~ 6 hours, reaction terminates
It is cleaned 4 times with ethyl alcohol afterwards and is removed and contain mercaptosilane coupling agents on non-grafted, it is small to be placed in 100 DEG C of vacuum drying chambers dry 24
When, you can obtain the silica of engrafted nanometer containing mercaptosilane coupling agents；
Second step：5g carbon fibers are immersed in 100 ~ 160mL nitration mixture, ultrasonication 60 ~ 120 minutes then moves into oil bath pan
In 80 ~ 100 DEG C react 2 ~ 4 hours, be washed with deionized water after completion of the reaction to neutrality, be subsequently placed in 100 DEG C of vacuum drying chambers
Dry 24 hours to get to sour Treatment of Carbon；
Third walks：5g acid Treatment of Carbon is dispersed in 150 ~ 200mL in the mixed solvents, with second acid for adjusting pH value to 4 ~ 5, ultrasound
Wave processing 30 ~ after sixty minutes be added 10 ~ 30g contain amino silicane coupling agent, 60 DEG C react 2 ~ 4 hours, after reaction use ethyl alcohol,
Acetone and the mixed solution of deionized water clean 4 times and remove contains amino silicane coupling agent on non-grafted, and it is dry to be placed in 100 DEG C of vacuum
It is 24 hours dry in dry case, you can to obtain being grafted carbon fiber containing amino silicane coupling agent；
4th step：2g grafting carbon fibers containing amino silicane coupling agent are dispersed in 30~60mL ethyl alcohol, 4 ~ 8g alkene is then added
Propyl glycidyl ether, room temperature magnetic agitation 48 ~ 72 hours are cleaned 4 times with ethyl alcohol, then dry in 40 DEG C of vacuum drying chambers
24 hours, you can obtain allyl glycidyl ether grafting carbon fiber；
5th step：0.4g engrafted nanometers containing mercaptosilane coupling agents silica and 1g allyl glycidyl ethers are grafted carbon fiber
Dimension is dispersed in the dimethylformamide of 30 ~ 60mL, ultrasonication 60 ~ 120 minutes, and the light-initiated of 0.1g is then added
Agent uses wavelength for the ultraviolet light 1 ~ 2 hour of 365 nm, is then cleaned 4 times with ethyl alcohol, in 80 DEG C of vacuum drying chambers
It is 24 hours dry, you can to obtain nano silicon dioxide grafting carbon fiber reinforcement.
2. a kind of as described in claim 1 prepare nano silicon dioxide grafting fibre reinforced using sulfydryl-alkene click-reaction
The method of body, it is characterised in that described is γ-mercaptopropyl trimethoxysilane, γ-mercapto propyl first containing mercaptosilane coupling agents
One kind in base dimethoxysilane or gamma-mercaptopropyltriethoxysilane.
3. a kind of as described in claim 1 prepare nano silicon dioxide grafting fibre reinforced using sulfydryl-alkene click-reaction
The method of body, it is characterised in that the nitration mixture be by mass percent concentration be 65% concentrated nitric acid and mass percent concentration
The concentrated sulfuric acid for 96% is 3 by volume:1 ratio mixes.
4. a kind of as described in claim 1 prepare nano silicon dioxide grafting fibre reinforced using sulfydryl-alkene click-reaction
The method of body, it is characterised in that it is 4 by volume that the mixed solvent, which is by absolute ethyl alcohol and deionized water,:1 ratio is mixed
It closes.
5. a kind of as described in claim 1 prepare nano silicon dioxide grafting fibre reinforced using sulfydryl-alkene click-reaction
The method of body, it is characterised in that described is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl first containing amino silicane coupling agent
One kind in base diethoxy silane or γ-aminopropyltrimethoxysilane.
6. a kind of as described in claim 1 prepare nano silicon dioxide grafting fibre reinforced using sulfydryl-alkene click-reaction
The method of body, it is characterised in that the photoinitiator is benzoin dimethylether or 2- hydroxy-2-methyl -1- phenyl -1- acetone
In one kind.
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