CN106751458A - Epoxy resin carbon nano tube compound material and preparation method thereof - Google Patents
Epoxy resin carbon nano tube compound material and preparation method thereof Download PDFInfo
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- CN106751458A CN106751458A CN201611009802.4A CN201611009802A CN106751458A CN 106751458 A CN106751458 A CN 106751458A CN 201611009802 A CN201611009802 A CN 201611009802A CN 106751458 A CN106751458 A CN 106751458A
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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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a kind of epoxy resin carbon nano tube compound material and preparation method thereof.Described preparation method includes：CNT is mixed in a solvent with oligomer of phenylamine and/or its derivative, obtain carbon nano tube dispersion liquid, carbon nano tube dispersion liquid and epoxy resin are uniformly mixed to form mixture, the solvent in the mixture is removed afterwards, obtain epoxy resin carbon mano-tube composite；And, epoxy resin carbon mano-tube composite is uniformly mixed with epoxy hardener.Epoxy resin carbon nano tube compound material of the invention has excellent mechanical performance, resistance to elevated temperatures and anti-wear performance, can be as excellent macromolecule self-lubricating materials'use, while its preparation process is simple, and raw material sources extensively, are implemented beneficial to scale.
Description
Technical field
Present invention relates particularly to a kind of epoxy resin carbon nano tube compound material and preparation method thereof, belong to high molecular nanometer
Field of compound material.
Background technology
Epoxy resin (EP) synthesizes so far from nineteen thirty, steady by its excellent physical and mechanical properties, electrical insulation capability, heat
Qualitative energy and resistance to chemical corrosion etc., have become a kind of resin being most widely used in thermosetting resin.However, due to
It is in three-dimensional net structure after epoxy resin cure, makes it while to there is crosslink density high, internal stress is big, and matter is crisp, toughness
The shortcomings of difference, so that its application also receives certain limitation.
It was discovered by researchers that preparing epoxy resin nano composites by adding Nano filling can significantly improve epoxy
The combination property of resin, this also becomes the focus of current research.Wherein, CNT (CNTs) has excellent mechanical property
Energy, thermal property, electric property and anti-wear performance etc., are the preferable modified fillers of polymer.Some researchers guess, will
CNT is combined with epoxy resin, can lift the performance of epoxy resin, extends its range of application.But, due to carbon nanometer
There is π-π interactions between pipe, and CNT has surface energy high, causes CNT to be prone to aggregation, causes
It is difficult to simple realization CNT in the epoxy dispersed, so as to be difficult to effectively be lifted the performance of epoxy resin.
The content of the invention
It is a primary object of the present invention to provide a kind of epoxy resin carbon nano tube compound material and preparation method thereof, with gram
Take deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of epoxy resin carbon nano tube compound material is the embodiment of the invention provides, it includes CNT, asphalt mixtures modified by epoxy resin
Fat, epoxy hardener and oligomer of phenylamine and/or oligomer of phenylamine derivative；Wherein, at least part of oligomer of phenylamine and/or benzene
Amine oligomer derivative combines to form compound with CNT by physics mode.
The embodiment of the present invention additionally provides a kind of preparation method of epoxy resin carbon nano tube compound material, and it includes：
CNT is mixed in a solvent with oligomer of phenylamine and/or oligomer of phenylamine derivative, CNT is obtained
Dispersion liquid,
The dispersion liquid of CNT and epoxy resin are uniformly mixed to form mixture, in removing the mixture afterwards
Solvent, obtains epoxy resin carbon mano-tube composite；
And, epoxy resin carbon mano-tube composite is uniformly mixed with epoxy hardener.
In some embodiments, described preparation method includes：CNT is low with oligomer of phenylamine and/or aniline
Polymers derivative mixes in a solvent, and carries out ultrasonically treated, the dispersion liquid of acquisition CNT.
In some embodiments, described preparation method is comprised the following steps：
(1) carbon nano tube dispersion liquid is prepared by dispersant of aniline quasi-oligomer and/or its derivative；
(2) in carbon nano tube dispersion liquid being evenly spread into epoxy resin by modes such as mechanical agitations or ultrasonic disperse,
Obtain epoxy resin carbon mano-tube composite；
(3) epoxy hardener is added in above-mentioned epoxy resin carbon mano-tube composite, solidification obtains CNT increasing
Strong epoxy resin composite material, i.e. epoxy resin carbon nano tube compound material.
Further, foregoing oligomer of phenylamine and/or oligomer of phenylamine derivative include that aniline tripolymer, aniline four gather
Any one of body, aniline pentamer and the aggressiveness of aniline six or the derivative of any one.
Preferably, foregoing oligomer of phenylamine derivative includes organic molecule or macromolecule containing oligomer of phenylamine grafting.
Further, aforementioned epoxy resins include bisphenol A type epoxy resin or phenolic aldehyde based epoxy resin.
Further, aforementioned epoxy curing agent includes polyamide-based curing agent, acid anhydride type curing agent or imidazole type curing agent.
The embodiment of the present invention additionally provides the epoxy resin carbon nano tube compound material prepared by any one foregoing method.
Than prior art, the present invention utilizes oligomer of phenylamine and/or the physics phase between its derivative and CNT
Interaction, it is not necessary to harsh chemical reaction, CNT can be prepared only by physics modes such as physical agitation or ultrasounds
Dispersion liquid, then carbon nano tube dispersion liquid is well mixed with epoxy resin, epoxy hardener, solidify afterwards, obtain comprising uniform
The epoxy resin carbon nano tube compound material of the CNT of distribution, the composite has excellent mechanical performance, heat-resisting quantity
Can, while also there is good abrasion resistance, such as with low-friction coefficient and wear rate, can be as excellent high molecular self-lubricating
Sliding materials'use.The preparation process is simple of the epoxy resin carbon nano tube compound material of present invention offer simultaneously, raw material sources are wide
It is general, implement beneficial to scale.
Brief description of the drawings
Fig. 1 a- Fig. 1 b are respectively that embodiment 1-4 obtains pure epoxy in epoxy resin carbon nano tube compound material and comparative example 1
The PVvalue testing figure and wear rate test chart of the coating that resin is formed.
Specific embodiment
A kind of epoxy resin carbon nano tube compound material provided in an embodiment of the present invention include CNT, epoxy resin,
Epoxy hardener and oligomer of phenylamine and/or oligomer of phenylamine derivative；Wherein, at least part of oligomer of phenylamine and/or aniline
Oligomer derivative combines to form compound with CNT by physics mode.
Further, the content of CNT is 0.1wt%~50wt%, preferably 0.1wt% in the composite
~20wt%.
In some preferred embodiments, the composite includes：0.1wt%~50wt% CNTs,
79.88wt%~20wt% epoxy resin, 19.97wt%~5wt% epoxy hardeners and 0.05wt%~25wt% aniline are low
Polymers and/or oligomer of phenylamine derivative.
It is further preferred that the composite includes：0.1wt%~20wt% CNTs, 78.8wt%~
56wt% epoxy resin, 19.7wt%~14wt% epoxy hardeners and 0.05wt%~10wt% oligomer of phenylamine and/or benzene
Amine oligomer derivative.
In some embodiments, the epoxy resin carbon nano tube compound material can be by CNT, asphalt mixtures modified by epoxy resin
Fat and epoxy hardener is blended, cast, deaeration, solidification are formed.
Further, can be by the CNT of oligomer of phenylamine or derivatives thereof functionalization and epoxy resin, epoxy
Curing agent is blended, deaeration, pours solidification and forms.
A kind of preparation method of epoxy resin carbon nano tube compound material provided in an embodiment of the present invention includes：
CNT is mixed in a solvent with oligomer of phenylamine and/or oligomer of phenylamine derivative, CNT is obtained
Dispersion liquid,
The dispersion liquid of CNT and epoxy resin are uniformly mixed to form mixture, in removing the mixture afterwards
Solvent, obtains epoxy resin carbon mano-tube composite；
And, epoxy resin carbon mano-tube composite is uniformly mixed with epoxy hardener.
In some embodiments, described preparation method includes：CNT is low with oligomer of phenylamine and/or aniline
Polymers derivative mixes in a solvent, and carries out ultrasonically treated, the dispersion liquid of acquisition CNT.
In some embodiments, described preparation method may also comprise：By physics modes such as stirring, ultrasound, vibrations
(such as mechanical agitation, ultrasound (can also coordinate other suitable non-physical methods in some embodiments certainly) by carbon nanometer
Simple physical mixes pipe in a solvent with oligomer of phenylamine and/or oligomer of phenylamine derivative, so as to obtain dividing for CNT
Dispersion liquid.Certainly, in these embodiments, if CNT is excessive, the carbon that will exist with forms such as precipitums is also needed
Nanotube etc. is removed by modes such as point liquid, centrifugations, so as to obtain uniform carbon nano tube dispersion liquid.
In some preferred embodiments, described preparation method includes：The mixing is removed by vacuum distillation mode
Solvent in thing.
In some preferably specific embodiment, described preparation method also includes：Epoxy resin CNT is answered
Compound uniformly mixes with epoxy hardener, and vacuum defoamation is carried out afterwards, then carries out illumination curing and/or heat cure treatment.
Further, in aforementioned preparation process, the CNT derives with oligomer of phenylamine and/or oligomer of phenylamine
The mass ratio of thing is 1：10~1：0.1, preferably 2：1~3：1.
Further, in aforementioned preparation process, epoxy resin carbon mano-tube composite institute carbon nanotubes, aniline
Oligomer and/or oligomer of phenylamine derivative and the mass ratio of epoxy resin are 0.15：79.88~75：20, preferably 0.75：
79.4。
Further, in aforementioned preparation process, the epoxy resin is 3 with the mass ratio of epoxy hardener：1~5：1,
Preferably 4：1.
In some more specific case study on implementation, a kind of method for preparing epoxy resin carbon nano tube compound material includes
Following steps：
(1) oligomer of phenylamine (such as aniline tripolymer) is dissolved in solvent, and adds CNT, then through ultrasound etc.
Treatment, forms uniform carbon nano tube dispersion liquid.
(2) carbon nano tube dispersion liquid is added in epoxy resin, is mixed by modes such as stirring, vibration, ultrasounds, then pass through
Solvent is removed in vacuum distillation, obtains epoxy resin carbon mano-tube composite.
(3) epoxy hardener is added in a certain amount of epoxy resin carbon mano-tube composite, is stirred, be poured into
In mould, vacuum deaerator, solidification obtains the epoxy resin carbon nano tube compound material of different content.
Present invention also offers the epoxy resin carbon nano tube compound material prepared by foregoing any one method.
, with not plus compared with the epoxy resin of carbon pipe, stretch modulus at least can be with for aforementioned epoxy resins carbon nano tube compound material
4~20% are improved, wear rate can at least lower 5.5%~23.5%.
In the present invention, foregoing oligomer of phenylamine is also known as aniline oligomer, and the aniline conjugation segment that it is included is shorter than polyphenyl
Amine, it is electroactive similar to polyaniline, but do not exist defect in molecule, and with more preferable dissolubility.Suitable for benzene of the invention
Any one or more of amine oligomer preferably from aniline tripolymer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Combination, but not limited to this.
In the present invention, foregoing oligomer of phenylamine derivative is mainly based upon oligomer of phenylamine formation, and the aniline is low
The lexical or textual analysis of polymers is as mentioned before.
Preferably, foregoing oligomer of phenylamine derivative may be selected from aniline tripolymer, Tetraaniline, aniline pentamer, benzene
The combination of the derivative of any one or various derivatives in the aggressiveness of amine six, but not limited to this.
Further, foregoing oligomer of phenylamine derivative includes carboxylic acid-terminated oligomer of phenylamine derivative, connects functional
Change the oligomer of phenylamine or the micromolecular compound containing oligomer of phenylamine of group.Preferably, the functionalization group includes alkane
Any one in epoxide, carboxyl, sulfonic group, phosphate or two or more combinations, but not limited to this.
Preferably, the oligomer of phenylamine derivative is selected from the polymer containing oligomer of phenylamine grafting or block.
Preferably, the oligomer of phenylamine derivative has any one in following chemical formula：
Wherein M includes Na+、K+, potassium or quaternary ammonium salt cationic, but not limited to this.
Foregoing oligomer of phenylamine or oligomer of phenylamine derivative approach can be obtained commercially available from, it is also possible to bibliography (example
Such as,《CHEM.COMMUN.》, the 2768-2769 pages in 2003；《Synthetic Metals》, 2001, volume 122
237-242 pages；CN101811997A；CN 1369478A, CN 1204655A etc.) self-control.
For example, a certain amount of p-phenylenediamine sulfate and aniline can be added in hydrochloric acid solution, and it is placed on -5
DEG C ice salt bath in, formed the first mixture.Separately weigh a certain amount of persulfate to be dissolved in hydrochloric acid solution, stirring makes its molten
Solution, then be slowly dropped in above-mentioned first mixture with the speed of per second one drop, treat after completion of dropping, continue stirring reaction two
Individual hour, reaction terminates, and product is cleaned with ammoniacal liquor, is cleaned twice with deionized water afterwards, obtains aniline tripolymer, dries standby
With.
In the present invention, aforementioned epoxy resins may be selected from all kinds of suitable epoxies known to industry, for example, can be selected from
Bisphenol A type epoxy resin, phenolic aldehyde based epoxy resin etc., and not limited to this.
Accordingly, aforementioned epoxy curing agent may be selected from polyamide-based curing agent, acid anhydride type curing agent or imidazole type curing agent
Deng, and not limited to this.
Aforementioned solvents can be particularly preferably organic from low boiling point solvent and/or high boiling point polar selected from water, organic solvent etc.
Solvent, such as preferably from ethanol, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide (DMSO), chloroform and 1-METHYLPYRROLIDONE
Any one or more, and not limited to this.
In foregoing embodiment, by between oligomer of phenylamine and/or oligomer of phenylamine derivative and CNT
Physics weak interaction, it is possible to achieve oligomer of phenylamine and/or oligomer of phenylamine derivative are compound with CNT, that is, obtain
The CNT of oligomer of phenylamine and its derivative functionalization is obtained, and then makes CNT in decentralized media such as water, organic solvents
Middle fine dispersion, obtains uniform and stable carbon nano tube dispersion liquid.And then, using the carbon nano tube dispersion liquid and epoxy resin etc.
Coordinate, you can described epoxy resin carbon nano tube compound material is obtained, and makes CNT multiple in epoxy resin CNT
Dispersed state is presented in condensation material.
Present invention also offers the purposes of aforementioned epoxy resins carbon nano tube compound material, for example, preparing with excellent power
Learn the purposes in protective coating, safeguard structure of performance and high-wear resistance (such as low-friction coefficient and low wear rate) etc. etc..
For example, can by the uncured epoxy resin carbon nano tube compound material by spraying, spin coating, print, scrape
Apply etc. mode and put on substrate surface, heat cure afterwards or photocuring form protective coating.
Again for example, also can by after solidification in the form of sheets, the epoxy resin carbon nano tube compound material of the form such as bulk makees
For protective materials is used.
Technical scheme will be described in further detail with reference to some embodiments as follows.
Oligomer of phenylamine in following examples or derivatives thereof can be produced or from commercially available way using mode known to industry
Footpath is bought.
The present embodiment of embodiment 1 is related to a kind of 0.25wt% epoxy resin carbon nano tube compound material (in the composite
Content of carbon nanotubes be 0.25wt%) preparation technology, including：
By p-phenylenediamine sulfate (8.87g), aniline (5.56g) is added to three mouthfuls of burnings of the hydrochloric acid solution (500mL) of 1M
In bottle, -5 DEG C are cooled to.Again by hydrochloric acid (1M) solution of 150mL ammonium persulfates (13.62g) by dropping funel be slowly added dropwise to
In above-mentioned reaction bulb, treat after completion of dropping, continue stirring reaction 1h, product is carried out into suction filtration, use a large amount of deionized waters
Cleaning, obtains blackish green solid product.Then with 10% ammonia spirit wash products, then cleaned twice with deionized water,
Product (aniline tripolymer) is finally placed in dried for standby in 40 DEG C of vacuum drying chamber.
Weighing aniline tripolymer (50mg), CNT (100mg) and tetrahydrofuran (20mL), a ultrasonic hour, to
Above-mentioned mixed solution adds epoxy resin E44 (32g), and tetrahydrofuran is removed in vacuum distillation, backward system addition curable epoxide
Agent polyetheramine D230 (8.0g), stirs, de-bubbled 15 minutes in 50 DEG C of vacuum drying oven, mixed liquor is imported pre-
In the Teflon mold of heat, solidification in baking oven is put into, condition of cure is 80 DEG C, 6 hours, finally gives 0.25wt% asphalt mixtures modified by epoxy resin
Fat carbon nano tube compound material.
The present embodiment of embodiment 2 is related to a kind of 0.5wt% epoxy resin carbon nano tube compound material (in the composite
Content of carbon nanotubes is 0.5wt%) preparation technology, including：
Weighing aniline tripolymer (100mg), CNT (200mg) and tetrahydrofuran (40mL), a ultrasonic hour, to
Above-mentioned mixed solution adds epoxy resin E44 (32g), and tetrahydrofuran is removed in vacuum distillation, backward system addition curable epoxide
Agent polyetheramine D230 (8.0g), stirs, de-bubbled 15 minutes in 50 DEG C of vacuum drying oven, mixed liquor is imported pre-
In the Teflon mold of heat, solidification in baking oven is put into, condition of cure is 80 DEG C, 6 hours, finally gives 0.5wt% asphalt mixtures modified by epoxy resin
Fat carbon nano tube compound material.
The present embodiment of embodiment 3 is related to a kind of 1.0wt% epoxy resin carbon nano tube compound material (in the composite
Content of carbon nanotubes is 1.0wt%) preparation technology, including：
Weighing aniline tripolymer (200mg), CNT (400mg) and tetrahydrofuran (80mL), a ultrasonic hour, to
Above-mentioned mixed solution adds epoxy resin E44 (32g), rotates excessive tetrahydrofuran, backward system addition curable epoxide
Agent polyetheramine D230 (8.0g), stirs, de-bubbled 15 minutes in 50 DEG C of vacuum drying oven, mixed liquor is imported pre-
In the Teflon mold of heat, solidification in baking oven is put into, condition of cure is 80 DEG C, 6 hours, finally gives 1.0wt% asphalt mixtures modified by epoxy resin
Fat carbon nano tube compound material.
The present embodiment of embodiment 4 is related to a kind of 2.0wt% epoxy resin carbon nano tube compound material (in the composite
Content of carbon nanotubes is 2.0wt%) preparation technology, including：
Weighing aniline tripolymer (400mg), CNT (800mg) and tetrahydrofuran (160mL), a ultrasonic hour,
Add epoxy resin E44 (32g) to above-mentioned mixed solution, rotate excessive tetrahydrofuran, backward system add epoxy solid
Agent polyetheramine D230 (8.0g), is stirred, de-bubbled 15 minutes in 50 DEG C of vacuum drying oven, and mixed liquor is imported
In the Teflon mold of preheating, solidification in baking oven is put into, condition of cure is 80 DEG C, 6 hours, finally gives 2.0wt% epoxies
Resin carbon nano tube compound material.
A kind of preparation technology of pure epoxy resin that 1 comparative example of comparative example is related to includes：
Epoxy resin E44 (27g) is weighed, tetrahydrofuran (10mL) is added, the system one hour of ultrasound rotated
Many solvents, add epoxy hardener polyetheramine D230 (8g) after vacuum distillation, 10~15 points of de-bubbled is vacuumized at 50 DEG C
Clock, mixed liquor is imported in the Teflon mold having been warmed up, and is put into solidification in baking oven, and condition of cure is 80 DEG C, 6 hours,
Finally give pure epoxy resin.
A kind of preparation technology of epoxy composite material that 2 comparative examples of comparative example are related to includes：
Weigh aniline tripolymer (50mg), CNT (100mg), tetrahydrofuran (20mL) and epoxy resin E44 (32g)
After mixing, ultrasound 1 hour, then vacuum distillation removes the tetrahydrofuran in mixture, backward system add epoxy hardener poly-
Ether amines D230 (8.0g), is stirred, de-bubbled 15 minutes in 50 DEG C of vacuum drying oven, and mixed liquor is imported into what is had been warmed up
In Teflon mold, solidification in baking oven is put into, condition of cure is 80 DEG C, 6 hours, finally gives epoxy resin CNT and answer
Condensation material.
A kind of preparation technology of epoxy composite material that 3 comparative examples of comparative example are related to includes：Weigh polyaniline
(100mg), CNT (200mg) and tetrahydrofuran (40mL), a ultrasonic hour, asphalt mixtures modified by epoxy resin are added to above-mentioned mixed solution
Fat E44 (32g), tetrahydrofuran is removed in vacuum distillation, backward system add epoxy hardener polyetheramine D230 (8.0g), stirring
Uniformly, de-bubbled 15 minutes in 50 DEG C of vacuum drying oven, mixed liquor is imported in the Teflon mold having been warmed up, and is put into
Solidify in baking oven, condition of cure is 80 DEG C, 6 hours, finally gives epoxy resin carbon nano tube compound material.
Refer to table 1 below and list previous embodiment 1-4 and obtain epoxy resin carbon nano tube compound material and the institute of comparative example 1
Obtain the mechanical property of pure epoxy resin, it can be seen that a small amount of CNT of addition can significantly improve epoxy resin CNT
The modulus of composite.
Meanwhile, it is 5N in load using UMT-3 rubbing machines, under conditions of frequency 2Hz, 20 minutes bars of reciprocating sliding friction
Under part, the coating and previous embodiment 1-4 of pure epoxy resin composition is obtained to comparative example 1, and to obtain epoxy resin CNT compound
The polishing machine of the coating of material composition is characterized, and test result see Fig. 1 a and Fig. 1 b, it can be seen that these are combined
The coefficient of friction and wear rate of material are effectively improved, and are especially added with the composite coating of 0.5wt% CNTs
Coefficient of friction and wear rate it is minimum.
Additionally, inventor is also in the same way, the coating of composite formation is obtained to foregoing comparative example 2,3
Polishing machine be tested, test result shows, comparative example 2,3 obtains the coating of composite formation under dry state and water
Coefficient of friction and wear rate under environment have the reduction of certain amplitude than pure epoxy coating, but are significantly larger than previous embodiment
1-4 obtains the coating of epoxy boron nitride nm composite material formation.
Table 1
The present embodiment of embodiment 5 is related to a kind of 0.25wt% epoxy resin carbon nano tube compound material (in the composite
Content of carbon nanotubes be 0.25wt%, dispersant be Tetraaniline grafted maleic anhydride) preparation technology, including：
Weigh Tetraaniline grafted maleic anhydride (50mg), CNT (100mg) and tetrahydrofuran (20mL), ultrasound
One hour, to above-mentioned mixed solution add epoxy resin E44 (32g), tetrahydrofuran is removed in vacuum distillation, backward system add
Enter epoxy hardener polyetheramine D230 (8.0g), stir, de-bubbled 15 minutes in 50 DEG C of vacuum drying oven, by mixed liquor
In the Teflon mold that importing has been warmed up, solidification in baking oven is put into, condition of cure is 80 DEG C, 6 hours, is finally given
0.25wt% epoxy resin carbon nano tube compound materials.
The present embodiment of embodiment 6 is related to a kind of 0.5wt% epoxy resin carbon nano tube compound material (in the composite
Content of carbon nanotubes is 0.5wt%, and dispersant is aniline tripolymer grafted maleic anhydride) preparation technology, including：
Weigh aniline tripolymer-maleic anhydride (100mg), CNT (200mg) and tetrahydrofuran (40mL), ultrasound one
Individual hour, to above-mentioned mixed solution add epoxy resin E44 (32g), tetrahydrofuran is removed in vacuum distillation, backward system addition
Epoxy hardener polyetheramine D230 (8.0g), is stirred, and de-bubbled 15 minutes, mixed liquor is led in 50 DEG C of vacuum drying oven
Enter in the Teflon mold having been warmed up, be put into solidification in baking oven, condition of cure is 80 DEG C, 6 hours, is finally given
0.5wt% epoxy resin carbon nano tube compound materials.
The present embodiment of embodiment 7 is related to a kind of 1.0wt% epoxy resin carbon nano tube compound material (in the composite
Content of carbon nanotubes is 1.0wt%, and dispersant is Carboxylation Tetraaniline) preparation technology, including：
Weigh Carboxylation Tetraaniline (200mg), CNT (400mg) and tetrahydrofuran (80mL), ultrasound one
Individual hour, to above-mentioned mixed solution add epoxy resin E44 (32g), rotate excessive tetrahydrofuran, backward system addition
Epoxy hardener polyetheramine D230 (8.0g), is stirred, and de-bubbled 15 minutes, mixed liquor is led in 50 DEG C of vacuum drying oven
Enter in the Teflon mold having been warmed up, be put into solidification in baking oven, condition of cure is 80 DEG C, 6 hours, is finally given
1.0wt% epoxy resin carbon nano tube compound materials.
The present embodiment of embodiment 8 is related to a kind of 2.0wt% epoxy resin carbon nano tube compound material (in the composite
Content of carbon nanotubes is 2.0wt%, and dispersant is the aggressiveness of aniline six of ethylene glycol grafting) preparation technology, including：
Weigh six aggressiveness of aniline-ethylene glycol (400mg), CNT (800mg) and tetrahydrofuran (160mL), ultrasound one
Individual hour, to above-mentioned mixed solution add epoxy resin E44 (32g), rotate excessive tetrahydrofuran, backward system addition
Epoxy hardener polyetheramine D230 (8.0g), is stirred, and de-bubbled 15 minutes, mixed liquor is led in 50 DEG C of vacuum drying oven
Enter in the Teflon mold having been warmed up, be put into solidification in baking oven, condition of cure is 80 DEG C, 6 hours, is finally given
2.0wt% epoxy resin carbon nano tube compound materials.
Likewise, inventor also uses UMT-3 rubbing machines, it is 5N in load, under conditions of frequency 2Hz, to foregoing
The polishing machine that embodiment 5-8 obtains the coating of epoxy boron nitride nm composite material formation is tested, and as a result shows, by
The coefficient of friction and wear rate of the coating that these composites are formed are significantly reduced than pure epoxy resin coating.
Embodiment described above is only used for helping the core concept for understanding the method for the present invention, and its description is more specific and detailed
Carefully, but can not therefore and be interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for the common skill of this area
For art personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to this hair
In bright protection domain.To various modifications of these embodiments it is clear that institute herein for one of skill in the art
The General Principle of definition can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore,
Protection scope of the present invention should be determined by the appended claims, and without limitation on these shown in this article examples, but accord with
Close the scope consistent with principles disclosed herein and feature.
Claims (10)
1. a kind of epoxy resin carbon nano tube compound material, it is characterised in that including CNT, epoxy resin, epoxy hardener
With oligomer of phenylamine and/or oligomer of phenylamine derivative；Wherein, at least part of oligomer of phenylamine and/or oligomer of phenylamine derive
Thing combines to form compound with CNT by physics mode.
2. epoxy resin carbon nano tube compound material as claimed in claim 1, it is characterised in that：Carbon is received in the composite
The content of mitron is 0.1wt%~50wt%, preferably 0.1wt%~20wt%.
3. epoxy resin carbon nano tube compound material as claimed in claim 1, it is characterised in that the composite includes：
0.1wt%~50wt% CNTs, 79.88wt%~20wt% epoxy resin, 20wt%~5wt% epoxy hardeners and
0.05wt%~25wt% oligomer of phenylamine and/or oligomer of phenylamine derivative；Preferably, the composite includes：
1.0wt%~20wt% CNTs, 78.8wt%~56wt% epoxy resin, 19.7wt%~14wt% epoxy hardeners and
0.5wt%~10wt% oligomer of phenylamine and/or oligomer of phenylamine derivative.
4. the epoxy resin carbon nano tube compound material as any one of claim 1-3, it is characterised in that：The aniline
Oligomer and/or oligomer of phenylamine derivative are included in aniline tripolymer, Tetraaniline, aniline pentamer and the aggressiveness of aniline six
Any one or any one derivative；Preferably, the oligomer of phenylamine derivative includes having containing oligomer of phenylamine grafting
Machine small molecule or macromolecule；And/or, the epoxy resin includes bisphenol A type epoxy resin or phenolic aldehyde based epoxy resin；And/or,
The epoxy hardener includes polyamide-based curing agent, acid anhydride type curing agent or imidazole type curing agent.
5. a kind of preparation method of epoxy resin carbon nano tube compound material, it is characterised in that including：
CNT is mixed in a solvent with oligomer of phenylamine and/or oligomer of phenylamine derivative, dividing for CNT is obtained
Dispersion liquid,
The dispersion liquid of CNT and epoxy resin are uniformly mixed to form mixture, are removed afterwards molten in the mixture
Agent, obtains epoxy resin carbon mano-tube composite；
And, epoxy resin carbon mano-tube composite is uniformly mixed with epoxy hardener.
6. preparation method according to claim 5, it is characterised in that described preparation method includes：By CNT with
Oligomer of phenylamine and/or oligomer of phenylamine derivative mix in a solvent, and carry out ultrasonically treated, the dispersion of acquisition CNT
Liquid；And/or, described preparation method includes：Solvent in the mixture is removed by vacuum distillation mode.
7. preparation method according to claim 5, it is characterised in that described preparation method also includes：By epoxy resin
Carbon mano-tube composite uniformly mixes with epoxy hardener, and vacuum defoamation is carried out afterwards, then carries out illumination curing and/or thermosetting
Change is processed.
8. preparation method according to claim 5, it is characterised in that：The CNT and oligomer of phenylamine and/or benzene
The mass ratio of amine oligomer derivative is 1：10~1：0.1, preferably 1：1~3：1；And/or, the epoxy resin CNT
The mass ratio of compound institute carbon nanotubes, oligomer of phenylamine and/or oligomer of phenylamine derivative and epoxy resin is 0.15：
79.88~75：20, preferably 0.75：79.4~7.5：74；And/or, the epoxy resin is with the mass ratio of epoxy hardener
3：1~5：1, preferably 4：1.
9. the preparation method as any one of claim 5-8, it is characterised in that：The oligomer of phenylamine and/or aniline
Oligomer derivative includes any one of aniline tripolymer, Tetraaniline, aniline pentamer and the aggressiveness of aniline six or any
The derivative of person；Preferably, the oligomer of phenylamine derivative includes organic molecule or high score containing oligomer of phenylamine grafting
Son；And/or, the epoxy resin includes bisphenol A type epoxy resin or phenolic aldehyde based epoxy resin；And/or, the epoxy hardener
Including polyamide-based curing agent, acid anhydride type curing agent or imidazole type curing agent；And/or, the solvent include water, tetrahydrofuran,
Ethanol one or two and two or more mixtures therein.
10. the epoxy resin carbon nano tube compound material that prepared by the method as any one of claim 5-9.
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Cited By (3)
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| CN110003618A (en) * | 2019-03-14 | 2019-07-12 | 西安理工大学 | A kind of preparation method of carbon nano tube/epoxy resin composite material |
| CN110128890A (en) * | 2019-06-04 | 2019-08-16 | 江南大学 | A kind of hydridization acrylic acid electrophoretic paint and preparation method thereof |
| CN111978841A (en) * | 2020-08-31 | 2020-11-24 | 东莞狐马商贸有限公司 | Preparation method of polyurethane rubber coating modified based on high-elasticity polyisoprene |
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| CN102875973A (en) * | 2012-09-28 | 2013-01-16 | 苏州大学 | Modified carbon nanotube/thermosetting resin composite and preparation method thereof |
| CN105645387A (en) * | 2014-12-02 | 2016-06-08 | 中国科学院宁波材料技术与工程研究所 | Graphene dispersant and applications thereof |
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| CN102875973A (en) * | 2012-09-28 | 2013-01-16 | 苏州大学 | Modified carbon nanotube/thermosetting resin composite and preparation method thereof |
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| CN110128890A (en) * | 2019-06-04 | 2019-08-16 | 江南大学 | A kind of hydridization acrylic acid electrophoretic paint and preparation method thereof |
| CN111978841A (en) * | 2020-08-31 | 2020-11-24 | 东莞狐马商贸有限公司 | Preparation method of polyurethane rubber coating modified based on high-elasticity polyisoprene |
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