CN104087224B - A kind of carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement - Google Patents
A kind of carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement Download PDFInfo
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- CN104087224B CN104087224B CN201410329481.0A CN201410329481A CN104087224B CN 104087224 B CN104087224 B CN 104087224B CN 201410329481 A CN201410329481 A CN 201410329481A CN 104087224 B CN104087224 B CN 104087224B
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Abstract
The present invention relates to a kind of carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, be made up of epoxy resin-base and CNT, the quality of CNT is the 0.1%～15% of epoxy resin-base gross mass；CNT used can through surface treatment so that it is the amine groups can reacted with epoxy resin in grafting is to obtain good modified effect；During strengthening construction dispensing, 100 parts of carbon nano-tube modification epoxy resin adds the epoxy hardener of 20～50 parts。After the epoxy resin adhesive that the method for the present invention is modified solidifies, tensile strength, comprcssive strength, bending strength and stretching shearing strength are higher, there is the performance of higher mechanical property, good infiltration carbon fiber, it is more suitable for the reinforcement process of viscous carbon fiber, it is possible to play better consolidation effect。
Description
Technical field
The present invention relates to a kind of epoxy resin adhesive, be specifically related to a kind of carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement。
Background technology
It is the novel reinforced Strengthening Technology risen in developed countries such as Japan and the United States beginning of the nineties late 1980s that carbon fiber reinforcement repairs concrete structure technique, is widely used at present among the reinforcing and repairing engineering of bridge, buildings or structures xoncrete structure。Compared with traditional reinforcement technique, viscous carbon fiber reinforcement have high-strength efficient, splendid corrosion resistance, durability and preferably fatigue resistance, the deadweight not increasing component and volume, the advantage such as widely applicable。
Owing to carbon fiber itself has very excellent mechanical property, therefore in viscous carbon fiber reinforcement technique, adhesive often becomes the key factor determining viscous carbon fiber reinforcement technique quality。If the quality of the adhesive for gluing carbon fiber reinforcement is not good, the consolidation effect of viscous carbon fiber reinforcement can be affected。Therefore it is highly desirable to improve the performance of adhesive, thus improving the consolidation effect of viscous carbon fiber reinforcement。
Summary of the invention
In view of this, tensile strength, comprcssive strength, bending strength and stretch the higher carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement of shearing strength after it is an object of the invention to provide a kind of solidification。
The technical scheme is that and be achieved in that: a kind of carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, be made up of epoxy resin-base and CNT。
The above-mentioned carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, the quality of CNT is the 0.1%～15% of epoxy resin-base gross mass。
The above-mentioned carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, described CNT is a kind of or two kinds and the two or more mixture in SWCN, multi-walled carbon nano-tubes, modified SWCN and modified multiwalled carbon nanotube。
The above-mentioned carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, the preparation method of modified SWCN or modified multiwalled carbon nanotube comprises the steps: the carboxylated step of (1) SWCN or multi-walled carbon nano-tubes；(2) step of carboxylated SWCN or the chloride of functionalized multi-wall carbonnanotubes；(3) through the step of the carboxylated SWCN of chloride process or the amino functionalization graft modification of functionalized multi-wall carbonnanotubes。
The above-mentioned carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, in step (1): SWCN or multi-walled carbon nano-tubes are put into water bath sonicator in the reaction vessel filling carboxylated reagent and processes 5～8 hours, water bath heating temperature is 60～100 DEG C, ultrasonic power is 40-60W, carboxylated SWCN or carboxylated multi-walled carbon nano-tubes are washed to filtrate in neutrality, then drying for standby after terminating by reaction with deionized water。
The above-mentioned carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, in step (1): after SWCN or multi-walled carbon nano-tubes being put in the reaction vessel filling carboxylated reagent, adding vanadium oxytrichloride again in reaction vessel, the addition of vanadium oxytrichloride is the 0.5%-1% of carbon nanotube mass。
The above-mentioned carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, described carboxylated reagent is hydrochloric acid, sulphuric acid, nitric acid, H2O2/NH3·H2Two or more the mixture in any one or hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid and Fluohydric acid. in O, phosphoric acid and Fluohydric acid.。
The above-mentioned carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, in step (2): carboxylated SWCN or carboxylated multi-walled carbon nano-tubes are put in reaction vessel, then in reaction vessel, thionyl chloride is added or with DMF, pyridine or thionyl chloride that triethylamine is solvent or Phosphorous chloride. solution, then reflux under magnetic stirring, reaction temperature is 60～80 DEG C, reaction removes thionyl chloride or Phosphorous chloride. by the mode of distillation of reducing pressure after terminating, then product is poured into sonic oscillation 5-20min in chloroform, then filtration under diminished pressure, use chloroform drip washing again, last again by products therefrom at 60～80 DEG C after vacuum drying 20～28 hours the multi-walled carbon nano-tubes of the SWCN of chloride or chloride。
The above-mentioned carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, in step (3): will put in reaction vessel through the SWCN of chloride or the multi-walled carbon nano-tubes of chloride, it is subsequently adding solvent N, dinethylformamide DMF or dimethyl sulfoxide DMSO, add the aminated compounds containing two or more amidos, then supersound process 20～28 hours, ultrasonic power is 80-100W, reaction temperature is 100～140 DEG C, reaction terminates rear filtration under diminished pressure, and use absolute ethanol washing product, at 60～80 DEG C, vacuum drying must modifiy SWCN or modified multiwalled carbon nanotube after 20～28 hours。
The above-mentioned carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement, described aminated compounds is any one or two kinds and two or more mixture in hexamethylene diamine, diethylenetriamine, triethylene tetramine, pentamethyl-diethylenetriamine and 2 methyl pentamethylenediamine。
The invention has the beneficial effects as follows:
1. had through the mechanical property of the epoxy resin adhesive of carbon nano-tube modification and significantly improved, be more suitable for viscous carbon fiber reinforcement。
2. infiltrate the ability enhancing of carbon fiber through the epoxy resin adhesive of carbon nano-tube modification, improve the effect of carbon fiber reinforcement。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail。
Embodiment 1
The multi-walled carbon nano-tubes of 1g is joined in the epoxy resin-base of 100g, process 5 hours with ultrasonic dispersing machine, make multi-walled carbon nano-tubes be well dispersed in epoxy resin-base, obtain adhesive。
The adhesive of 100g adds during construction the hardener for epoxy resin of 30g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 48MPa；Comprcssive strength 80MPa；Bending strength 52MPa；Stretch shearing strength 15MPa。
Embodiment 2
The SWCN of 1g is joined in the 100mL nitration mixture being made up of sulphuric acid and nitric acid (wherein sulphuric acid is 3:1 with the volume ratio of nitric acid, the mass fraction of sulphuric acid is 65%, the mass fraction of nitric acid is 60%), supersound process 5 hours at 70 DEG C, ultrasonic power is 50W, removes the impurity in SWCN, and makes it aoxidize carboxylic group, then with deionized water, the SWCN cyclic washing after carboxylated is filtered to filtrate in neutrality, drying for standby。
0.5g SWCN after carboxylated is placed in 100mL flask, adds 50mL thionyl chloride (SOCl2), magnetic agitation after refluxing 24 hours at 70 DEG C, decompression is distilled off unnecessary SOCl2, product is poured in 100mL chloroform, ultrasonic 10min, filtration under diminished pressure, again with 200mL chloroform drip washing, 70 DEG C of vacuum dryings of products therefrom are after 24 hours, it is poured in 100mL flask, add 50mLN, dinethylformamide (DMF) and 5.0g1, 6-hexamethylene diamine, react 24 hours under the ultrasound condition that ultrasonic power is 80W, reaction temperature is 100 DEG C, reaction terminates rear filtration under diminished pressure, and with absolute ethanol washing product till washing liquid is clarified, then with membrane filtering vacuum drying, at 80 DEG C, vacuum drying obtaining after 24 hours modifiies SWCN。
Modified for 0.5g SWCN is joined in the epoxy resin-base of 100g, process 4h with ultrasonic dispersing machine, make SWCN be well dispersed in epoxy resin-base, obtain adhesive。
The above-mentioned adhesive of 100g adds during construction the hardener for epoxy resin of 33g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 57MPa；Comprcssive strength 104MPa；Bending strength 62MPa；Stretch shearing strength 17MPa。
Embodiment 3
The SWCN of 2g is joined in the 100mL nitration mixture being made up of sulphuric acid and nitric acid (wherein sulphuric acid is 3:1 with the volume ratio of nitric acid, the mass fraction of sulphuric acid is 70%, the mass fraction of nitric acid is 50%), supersound process 5 hours at 70 DEG C, ultrasonic power is 50W, removes the impurity in SWCN, and makes it aoxidize carboxylic group, then with deionized water, the SWCN cyclic washing after carboxylated is filtered to filtrate in neutrality, drying for standby。
1g SWCN after carboxylated is placed in 500mL flask, adds 200mL thionyl chloride (SOCl2) and 8mLDMF, magnetic agitation after refluxing 24 hours at 70 DEG C, decompression is distilled off unnecessary SOCl2Product is poured in 200mL chloroform, ultrasonic 10min, filtration under diminished pressure, again with 300mL chloroform drip washing, 70 DEG C of vacuum dryings of products therefrom are after 24 hours, it is poured in 500mL flask, adding 240mL triethylene tetramine, react 24 hours under the ultrasound condition that hunting power is 80W, reaction temperature is 120 DEG C, reaction terminates rear filtration under diminished pressure, and with absolute ethanol washing product till washing liquid is clarified, then with membrane filtering vacuum drying, at 60 DEG C, vacuum drying obtaining after 24 hours modifiies SWCN。
Modified for 0.8g SWCN is joined in the epoxy resin-base of 100g, process 3h with ultrasonic dispersing machine, make modified SWCN be well dispersed in epoxy resin-base, obtain adhesive。
The above-mentioned adhesive of 100g adds during construction the hardener for epoxy resin of 35g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 64MPa；Comprcssive strength 112MPa；Bending strength 72MPa；Stretch shearing strength 20MPa。
Embodiment 4
The multi-walled carbon nano-tubes of 1g is joined in the 100mL nitration mixture being made up of sulphuric acid and nitric acid (wherein sulphuric acid is 3:1 with the volume ratio of nitric acid, the mass fraction of sulphuric acid is 70%, the mass fraction of nitric acid is 60%), supersound process 5 hours at 70 DEG C, ultrasonic power is 50W, removes the impurity in multi-walled carbon nano-tubes, and makes it aoxidize carboxylic group, with deionized water, the multi-walled carbon nano-tubes cyclic washing after carboxylated is filtered to filtrate in neutrality, drying for standby afterwards。
0.5g multi-walled carbon nano-tubes after carboxylated is placed in 100mL flask, adds 50mL thionyl chloride (SOCl2) and 20mLDMF, magnetic agitation after refluxing 24 hours at 70 DEG C, decompression is distilled off unnecessary SOCl2, product is poured in 100mL chloroform, ultrasonic 10min, filtration under diminished pressure, again with 200mL chloroform drip washing, 70 DEG C of vacuum dryings of products therefrom are after 24 hours, it is poured in 100mL flask, add 50mLN, dinethylformamide (DMF) and 5.0g1, 6-hexamethylene diamine, react 24 hours under the ultrasound condition that hunting power is 80W, reaction temperature is 100 DEG C, reaction terminates rear filtration under diminished pressure, and with absolute ethanol washing product till washing liquid is clarified, then with membrane filtering vacuum drying, at 70 DEG C, vacuum drying obtaining after 24 hours modifiies SWCN。
Modified for 0.5g SWCN is joined in the epoxy resin-base of 100g, process 4h with ultrasonic dispersing machine, make CNT be well dispersed in epoxy resin-base, obtain adhesive。
The above-mentioned adhesive of 100g adds during construction the hardener for epoxy resin of 33g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 59MPa；Comprcssive strength 108MPa；Bending strength 76MPa；Stretch shearing strength 18MPa。
Embodiment 5
The multi-walled carbon nano-tubes of 2g is joined in the 100mL nitration mixture being made up of sulphuric acid and nitric acid (wherein sulphuric acid is 3:1 with the volume ratio of nitric acid, the mass fraction of sulphuric acid is 68%, the mass fraction of nitric acid is 55%), supersound process 5 hours at 70 DEG C, ultrasonic power is 50W, remove the impurity in multi-walled carbon nano-tubes, and make it aoxidize carboxylic group。With deionized water, the multi-walled carbon nano-tubes cyclic washing after carboxylated is filtered to filtrate in neutrality, drying for standby afterwards。
1g multi-walled carbon nano-tubes after carboxylated is placed in 500mL flask, adds 200mL thionyl chloride (SOCl2) and 80mLDMF, magnetic agitation after refluxing 24 hours at 70 DEG C, decompression is distilled off unnecessary SOCl2Product is poured in 100mL chloroform, ultrasonic 10min, filtration under diminished pressure, again with 200mL chloroform drip washing, 70 DEG C of vacuum dryings of products therefrom are after 24 hours, it is poured in 500mL flask, adding 240mL triethylene tetramine, react 24 hours under the ultrasound condition that hunting power is 80W, reaction temperature is 120 DEG C, reaction terminates rear filtration under diminished pressure, and with absolute ethanol washing product till washing liquid is clarified, then with membrane filtering vacuum drying, at 60 DEG C, vacuum drying obtained modified multiwalled carbon nanotube after 24 hours。
0.8g modified multiwalled carbon nanotube is joined in the epoxy resin-base of 100g, process 3h with ultrasonic dispersing machine, make multi-walled carbon nano-tubes be well dispersed in epoxy resin-base, obtain adhesive。
The above-mentioned adhesive of 100g adds during construction the hardener for epoxy resin of 35g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 68MPa；Comprcssive strength 113MPa；Bending strength 73MPa；Stretch shearing strength 21MPa。
Embodiment 6
The SWCN of 4g is joined in the 150mL nitration mixture being made up of sulphuric acid and nitric acid (wherein sulphuric acid is 3:1 with the volume ratio of nitric acid, the mass fraction of sulphuric acid is 69%, the mass fraction of nitric acid is 53%), supersound process 5 hours at 70 DEG C, ultrasonic power is 50W, remove the impurity in SWCN, and make it aoxidize carboxylic group。With deionized water, the SWCN cyclic washing after carboxylated is filtered to filtrate in neutrality, drying for standby afterwards。
2.5g SWCN after carboxylated is placed in 500mL flask, add 70.5g Phosphorous chloride. and 300mLDMF, magnetic agitation after refluxing 24 hours at 70 DEG C, decompression is distilled off DMF and unnecessary Phosphorous chloride., product is poured in 200mL chloroform, ultrasonic 10min, filtration under diminished pressure, again with 200mL chloroform drip washing, 70 DEG C of vacuum dryings of products therefrom are after 24 hours, it is poured in 500mL flask, add 300mL diethylenetriamine, react 24 hours under the ultrasound condition that hunting power is 80W, reaction temperature is 120 DEG C, reaction terminates rear filtration under diminished pressure, and with absolute ethanol washing product till washing liquid is clarified, then with membrane filtering vacuum drying, at 60 DEG C, vacuum drying obtaining after 24 hours modifiies SWCN。
Modified for 1g SWCN is joined in the epoxy resin-base of 100g, process 3h with ultrasonic dispersing machine, make modified SWCN be well dispersed in epoxy resin-base, obtain adhesive。
The above-mentioned adhesive of 100g adds during construction the hardener for epoxy resin of 35g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 69MPa；Comprcssive strength 115Pa；Bending strength 84MPa；Stretch shearing strength 22MPa。
Embodiment 7
The multi-walled carbon nano-tubes of 4g is joined in the 150mL nitration mixture being made up of sulphuric acid and nitric acid (wherein sulphuric acid is 3:1 with the volume ratio of nitric acid, the mass fraction of sulphuric acid is 62%, the mass fraction of nitric acid is 57%), supersound process 5 hours at 70 DEG C, ultrasonic power is 50W, remove the impurity in multi-walled carbon nano-tubes, and make it aoxidize carboxylic group。With deionized water, the multi-walled carbon nano-tubes cyclic washing after carboxylated is filtered to filtrate in neutrality, drying for standby afterwards。
2.5g multi-walled carbon nano-tubes after carboxylated is placed in 500mL flask, add 70.5g Phosphorous chloride. and 300mLDMF, magnetic agitation after refluxing 24 hours at 70 DEG C, decompression is distilled off DMF and unnecessary Phosphorous chloride., product is poured in 200mL chloroform, ultrasonic 10min, filtration under diminished pressure, again with 200mL chloroform drip washing, 70 DEG C of vacuum dryings of products therefrom are after 24 hours, it is poured in 500mL flask, add 300mL pentamethyl-diethylenetriamine, react 24 hours under the ultrasound condition that hunting power is 80W, reaction temperature is 120 DEG C, reaction terminates rear filtration under diminished pressure, and with absolute ethanol washing product till washing liquid is clarified, then with membrane filtering vacuum drying, at 60 DEG C, vacuum drying obtained modified multiwalled carbon nanotube after 24 hours。
1g modified multiwalled carbon nanotube is joined in the epoxy resin-base of 100g, process 3h with ultrasonic dispersing machine, make modified multiwalled carbon nanotube be well dispersed in epoxy resin-base, obtain adhesive。
The above-mentioned adhesive of 100g adds during construction the hardener for epoxy resin of 35g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 70MPa；Comprcssive strength 116MPa；Bending strength 100MPa；Stretch shearing strength 23MPa。
Embodiment 8
The multi-walled carbon nano-tubes of 4g is joined in the 150mL nitration mixture being made up of hydrochloric acid and nitric acid (wherein hydrochloric acid is 3:1 with the volume ratio of nitric acid, the mass fraction of hydrochloric acid is 37.5%, the mass fraction of nitric acid is 58%), then the vanadium oxytrichloride of 0.03g is added, supersound process 6h at 70 DEG C, ultrasonic power is 50W, removes the impurity in multi-walled carbon nano-tubes, and makes it aoxidize carboxylic group。With deionized water, the multi-walled carbon nano-tubes cyclic washing after carboxylated is filtered to filtrate in neutrality, drying for standby afterwards。
2.5g multi-walled carbon nano-tubes after carboxylated is placed in 500mL flask, add 70.5g Phosphorous chloride. and 300mLDMF, magnetic agitation after refluxing 24 hours at 70 DEG C, decompression is distilled off DMF and unnecessary Phosphorous chloride., product is poured in 200mL chloroform, ultrasonic 10min, filtration under diminished pressure, again with 200mL chloroform drip washing, 70 DEG C of vacuum dryings of products therefrom are after 24 hours, it is poured in 500mL flask, add 300mL pentamethyl-diethylenetriamine, react 24 hours under the ultrasound condition that hunting power is 80W, reaction temperature is 120 DEG C, reaction terminates rear filtration under diminished pressure, and with absolute ethanol washing product till washing liquid is clarified, then with membrane filtering vacuum drying, at 60 DEG C, vacuum drying obtained modified multiwalled carbon nanotube after 24 hours。
1g modified multiwalled carbon nanotube is joined in the epoxy resin-base of 100g, process 3h with ultrasonic dispersing machine, make modified multiwalled carbon nanotube be well dispersed in epoxy resin-base, obtain adhesive。
The above-mentioned adhesive of 100g adds during construction the hardener for epoxy resin of 35g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 76MPa；Comprcssive strength 149MPa；Bending strength 124MPa；Stretch shearing strength 26MPa。
Embodiment 9
The multi-walled carbon nano-tubes of 4g is joined in the 150mL nitration mixture being made up of hydrochloric acid and nitric acid (wherein hydrochloric acid is 3:1 with the volume ratio of nitric acid, the mass fraction of hydrochloric acid is 35%～37.5%, the mass fraction of nitric acid is 50%～60%), it is subsequently adding the vanadium oxytrichloride of 0.04g, supersound process 5 hours at 70 DEG C, ultrasonic power is 50W, and carboxylated multi-walled carbon nano-tubes is washed to filtrate in neutrality after terminating by reaction with deionized water, and then dry putting into afterwards fills H2O2/NH3·H2Continuing water bath sonicator in the reaction vessel of O solution to vibrate 3 hours, water bath heating temperature is 100 DEG C, and ultrasonic power is 60W, and carboxylated multi-walled carbon nano-tubes is washed to filtrate in neutrality, then drying for standby after terminating by reaction with deionized water。
2.5g multi-walled carbon nano-tubes after carboxylated is placed in 500mL flask, add 70.5g Phosphorous chloride. and 300mLDMF, magnetic agitation after refluxing 24 hours at 70 DEG C, decompression is distilled off DMF and unnecessary Phosphorous chloride., product is poured in 200mL chloroform, ultrasonic 10min, filtration under diminished pressure, again with 200mL chloroform drip washing, 70 DEG C of vacuum dryings of products therefrom are after 24 hours, it is poured in 500mL flask, add 150mL diethylenetriamine and 150mL pentamethyl-diethylenetriamine, react 24 hours under the ultrasound condition that hunting power is 80W, reaction temperature is 120 DEG C, reaction terminates rear filtration under diminished pressure, and with absolute ethanol washing product till washing liquid is clarified, then with membrane filtering vacuum drying, at 60 DEG C, vacuum drying obtained modified multiwalled carbon nanotube after 24 hours。
1g modified multiwalled carbon nanotube is joined in the epoxy resin-base of 100g, process 3h with ultrasonic dispersing machine, make modified multiwalled carbon nanotube be well dispersed in epoxy resin-base, obtain adhesive。
The above-mentioned adhesive of 100g adds during construction the hardener for epoxy resin of 35g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 82MPa；Comprcssive strength 160MPa；Bending strength 133MPa；Stretch shearing strength 28MPa。
Embodiment 10
Hydrochloric acid (mass fraction 35%～37.5%) and nitric acid (mass fraction 50%～60%) volume ratio that the multi-walled carbon nano-tubes of 4g joins 150mL are in the mixed acid of 3:1, it is subsequently adding the vanadium oxytrichloride of 0.04g, supersound process 5 hours at 70 DEG C, ultrasonic power is 50W, carboxylated multi-walled carbon nano-tubes is washed to filtrate in neutrality after terminating by reaction with deionized water, and then dry putting into afterwards fills H2O2/NH3·H2Continuing water bath sonicator in the reaction vessel of O solution to vibrate 3 hours, water bath heating temperature is 100 DEG C, and ultrasonic power is 60W, and carboxylated multi-walled carbon nano-tubes is washed to filtrate in neutrality, then drying for standby after terminating by reaction with deionized water。
2.5g multi-walled carbon nano-tubes after carboxylated is placed in 500mL flask, add 70.5g Phosphorous chloride. and 300mLDMF, magnetic agitation after refluxing 24 hours at 70 DEG C, decompression is distilled off DMF and unnecessary Phosphorous chloride., product is poured in 200mL chloroform, ultrasonic 10min, filtration under diminished pressure, again with 200mL chloroform drip washing, 70 DEG C of vacuum dryings of products therefrom are after 24 hours, it is poured in 500mL flask, add 200mL diethylenetriamine and 100mL pentamethyl-diethylenetriamine, react 24 hours under the ultrasound condition that hunting power is 80W, reaction temperature is 120 DEG C, reaction terminates rear filtration under diminished pressure, and with absolute ethanol washing product till washing liquid is clarified, then with membrane filtering vacuum drying, at 60 DEG C, vacuum drying obtained modified multiwalled carbon nanotube after 24 hours。
1g modified multiwalled carbon nanotube is joined in the epoxy resin-base of 100g, process 3h with ultrasonic dispersing machine, make modified multiwalled carbon nanotube be well dispersed in epoxy resin-base, obtain adhesive。
The above-mentioned adhesive of 100g adds during construction the hardener for epoxy resin of 35g, namely can be used for after mix homogeneously gluing carbon fiber reinforcement。
Some Mechanical Properties index after the solidification of this adhesive is as follows:
Tensile strength 86MPa；Comprcssive strength 168MPa；Bending strength 142MPa；Stretch shearing strength 34MPa。
Embodiment 1 to embodiment 10 is the epoxy resin adhesive that with the addition of CNT, i.e. carbon nano-tube modification epoxy resin adhesive, its mechanical property is compared with the mechanical property of pure epoxy resin adhesive, hot strength, comprcssive strength, bending strength and stretching shearing strength are all improved largely, and the mechanical property of the adhesive obtained after pure epoxy resin adhesive being modified with the CNT after amidine functional group graft modification is compared with the adhesive obtained after pure epoxy resin adhesive being modified with untreated CNT, better by the mechanical property of the adhesive obtained after pure epoxy resin adhesive is modified by modified CNT, the modified carbon nano-tube that the preparation method wherein adopted with embodiment 10 prepares to pure epoxy resin adhesive modified the mechanical property of acquisition adhesive best。
Above-described embodiment is only for clearly demonstrating the invention example, and is not the restriction to the invention detailed description of the invention。For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description。Here without also cannot all of embodiment be given exhaustive。All any apparent changes extended out within the spirit and principles in the present invention or variation are still among the invention scope of the claims。
Claims (3)
1. the carbon nano-tube modification epoxy resin adhesive being used for gluing carbon fiber reinforcement, it is characterised in that be made up of epoxy resin-base and CNT；The quality of CNT is the 0.1%～1.0% of epoxy resin-base gross mass；Described CNT is a kind of in modified SWCN and modified multiwalled carbon nanotube or both mixture；The preparation method of described modified SWCN or modified multiwalled carbon nanotube comprises the steps: the carboxylated step of (1) SWCN or multi-walled carbon nano-tubes: SWCN or multi-walled carbon nano-tubes are put in the reaction vessel filling carboxylated reagent, vanadium oxytrichloride is added again in reaction vessel, the addition of vanadium oxytrichloride is the 0.5%-1% of carbon nanotube mass, water bath sonicator processes 5～8 hours, water bath heating temperature is 60～100 DEG C, ultrasonic power is 40-60W, carboxylated SWCN or carboxylated multi-walled carbon nano-tubes are washed to filtrate in neutrality after terminating by reaction with deionized water, then drying for standby；(2) step of carboxylated SWCN or the chloride of functionalized multi-wall carbonnanotubes: carboxylated SWCN or carboxylated multi-walled carbon nano-tubes are put in reaction vessel, then in reaction vessel, thionyl chloride is added or with DMF, pyridine or thionyl chloride that triethylamine is solvent or Phosphorous chloride. solution, then reflux under magnetic stirring, reaction temperature is 60～80 DEG C, reaction removes thionyl chloride or Phosphorous chloride. by the mode of distillation of reducing pressure after terminating, then product is poured into sonic oscillation 5-20min in chloroform, then filtration under diminished pressure, use chloroform drip washing again, last again by products therefrom at 60～80 DEG C after vacuum drying 20～28 hours the multi-walled carbon nano-tubes of the SWCN of chloride or chloride；(3) through the step of the carboxylated SWCN of chloride process or the amino functionalization graft modification of functionalized multi-wall carbonnanotubes: will put in reaction vessel through the SWCN of chloride or the multi-walled carbon nano-tubes of chloride, it is subsequently adding solvent N, dinethylformamide DMF or dimethyl sulfoxide DMSO, add the aminated compounds containing two or more amidos, then supersound process 20～28 hours, ultrasonic power is 80-100W, reaction temperature is 100～140 DEG C, reaction terminates rear filtration under diminished pressure, and use absolute ethanol washing product, at 60～80 DEG C, vacuum drying must modifiy SWCN or modified multiwalled carbon nanotube after 20～28 hours。
2. the carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement according to claim 1, it is characterised in that described carboxylated reagent is hydrochloric acid, sulphuric acid, nitric acid, H2O2/NH3·H2Two or more the mixture in any one or hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid and Fluohydric acid. in O, phosphoric acid and Fluohydric acid.。
3. the carbon nano-tube modification epoxy resin adhesive for gluing carbon fiber reinforcement according to claim 1, it is characterized in that, described aminated compounds is any one or two kinds and two or more mixture in hexamethylene diamine, diethylenetriamine, triethylene tetramine, pentamethyl-diethylenetriamine and 2 methyl pentamethylenediamine。
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| CN104830278B (en) * | 2015-05-20 | 2018-08-24 | 沈阳化工研究院有限公司 | A kind of improved silica shape-stabilized phase change energy storage and preparation method thereof |
| CN107022332A (en) * | 2017-03-29 | 2017-08-08 | 京东方科技集团股份有限公司 | sealant and preparation method thereof, display panel and display device |
| CN111171322B (en) * | 2020-03-12 | 2022-01-25 | 衢州学院 | Preparation method of carbon nano tube amidated grafted polysilsesquioxane flame retardant |
| CN111531976A (en) * | 2020-05-08 | 2020-08-14 | 風速汽車有限公司 | Carbon fiber wire cover plate layer piece and manufacturing method thereof |
| CN111925720A (en) * | 2020-08-24 | 2020-11-13 | 江苏华夏制漆科技有限公司 | Waterborne organic fluorine-silicon modified ship coating and preparation method thereof |
| CN112143427B (en) * | 2020-09-21 | 2022-05-03 | 沈阳航空航天大学 | Chopped composite carbon fiber reinforced adhesive and preparation method and application thereof |
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| CN100357346C (en) * | 2006-03-14 | 2007-12-26 | 同济大学 | Process for preparing multifunctional carbon nanotube for epoxy resin nano composites |
| CN100420714C (en) * | 2006-06-09 | 2008-09-24 | 中国科学院广州化学研究所 | Process for preparing carbon nano tube/epoxy resin composite material |
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| EP3666657A1 (en) * | 2018-12-16 | 2020-06-17 | Goodrich Corporation | Selectively meltable adhesives for bonding of deicers |
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