CN107523015A - CNT montmorillonite self-assembled nanometer powder is grafted the preparation method of galss fiber reinforced resin composite - Google Patents
CNT montmorillonite self-assembled nanometer powder is grafted the preparation method of galss fiber reinforced resin composite Download PDFInfo
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- 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 invention discloses a kind of preparation method of CNT montmorillonite self-assembled nanometer powder grafting glass fibre reinforced composion, comprise the following steps：CNT is scattered in non-proton organic solvent, successively obtains CNT ammonium salt through organic amine modification, hydrochloric acid salt-forming reaction；It is filtered, wash repeatedly, be spray-dried and obtain CNT montmorillonite self-assembled nanometer powder by montmorillonite and CNT ammonium salt ultrasonic disperse in water；By nano powder ultrasonic disperse in silane coupler solution, then fiberglass surfacing is uniformly sprayed on, vacuum drying obtains nano powder grafting glass fibre precast body；Precast body is produced by composite material process planning compound resin again.The present invention can effectively improve the dispersiveness of CNT and the interlamellar spacing of montmorillonite, and the nano powder grafts on glass fibre, its dispersiveness in the composite can be further improved, the interfacial adhesion of resin and fiber is improved, so as to improve the mechanics of fibrous composite and heat resistance.
Description
Technical field
The invention belongs to fiber reinforced polymer composites technical field, and in particular to a kind of CNT-montmorillonite
Self-assembled nanometer powder is grafted the preparation method of galss fiber reinforced resin composite.
Background technology
Glass fibre reinforced composion is damaged with its own high intensity, high-modulus, good formability and endurance
Deng good characteristic, it is widely used in the numerous areas such as aviation, traffic, new energy.The performance of fibre reinforced composites not only takes
Certainly in the performance of fiber and resin matrix, and it is heavily dependent on the power of interface cohesion.In order to improve traditional glass
The interfacial adhesion of fibre reinforced composites, it usually needs surface modification is carried out to glass fibre.But traditional organically-modified, table
The surface modifications such as face etching can only mechanical property that is single or limitedly improving glass fibre reinforced composion, and can not be lifted
The electric conductivity of composite, heat resistance etc., limit the further development and application of glass fibre reinforced composion.
In recent years, the interfacial adhesion performance for developing into lifting glass fibre reinforced composion of nano material is brought new
Development opportunity, wherein, the application report of montmorillonite (MMT) and CNT (CNTs) is more.MMT is a kind of inorganic laminated silicon
Silicate material, there is very strong rigidity, dimensional stability, heat endurance, ion exchange property etc., available for polymer composite
The enhancing of material, increase just, and improve its heat resistance, barrier etc..CNTs has the performances such as excellent mechanics, electricity, calorifics, and
Itself there is the malleable of superelevation, be the preferable activeness and quietness material of polymer composites.At present, there is researcher by stirring
Mix, MMT is mixed and is scattered in polymer by the means such as ultrasound, three rollers grinding with CNTs, to improve the power of polymer composites
Performance, hot property etc. are learned, but it is less that both are mixed to the research being introduced into fibre reinforced composites.Such as, Hesami etc.
[Hesami M,Bagheri R,Masoomi M.Combination effects of carbon nanotubes,MMT and
phosphorus flame retardant on fire and thermal resistance of fiber-reinforced
epoxy composites[J].Iranian Polymer Journal,2014,23(6):469-476.] by MMT and CNTs
It is scattered in by high-speed stirred and supersound process in epoxy resin, then glass fibre composite wood is prepared by manual pasting forming process
Material；The limited oxygen index ratio of gained hybrid buildup composite is not added with improving about 8% during MMT and CNTs.But natural MMT
Interlamellar spacing is smaller, and surface hydrophilic oleophobic, poor with polymer compatibility；And CNTs has compared with high length-diameter ratio and compared with Large ratio surface
Product, and there is very strong Van der Waals force between pipe, it is easy to winding and reunites.Therefore, MMT and CNTs can not in fluoropolymer resin mixing
Avoid secondary agglomeration and resin system viscosity is increased.In order to improve the dispersiveness of MMT and CNTs in resin, both can be first
Hydridization forms a kind of CNT-montmorillonite (CNTs-MMT) nano-complex of one-dimensional/two-dimensional structure of nanoscale, then divides
Dissipate in resin.Roy etc. [Roy S, Srivastava S K, Pionteck J, et al. Montmorillonite-
multiwalled carbon nanotube nanoarchitecture reinforced thermoplastic
polyurethane[J].Polymer Composites,2016,37(6):1775-1785.] CNTs and MMT are mixed in and ground
It is fully ground to obtain impurity in alms bowl, then will be scattered in thermoplastic polyurethane and obtain nano composite material.Research finds gained
The tensile strength and glass transition temperature of nano composite material more modified thermoplastic polyurethane maximum lift about 57% and 10
℃.But the pre-dispersed fibrous composite that prepared again in resin of the CNTs-MMT nano-complexes has not been reported.
In addition, answered preparing fiber using resin transfer molding process such as resin transfer moulding, vacuum assisted resin perfusions
During condensation material, being stopped or filtered by fabric and disperse uneven phenomenon often occur in Nano filling.Such as, Elisabete etc.
[Elisabete F.,Reiada Costa.RTM processing and electrical performance of
carbon nanotube modified epoxy/fibre composites[J].Composites Part A,2012, 43
(4)：593-602.] find using vacuum-assisted resin transfer moulding process prepare composite material in, occur gum-injecting port and
The phenomenon of gum outlet CNTs skewness.MMT can not more avoid above mentioned problem with CNTs mixed fillers in resin.Therefore,
Urgently need to seek it is a kind of can both improve the dispersiveness of MMT and CNTs in the composite, can also avoid it by fabric mistake
The composite material and preparation method thereof of filter, so as to which high degree plays MMT and CNTs excellent properties, and widen glass fiber reinforced composite
The application of material.
The content of the invention
Goal of the invention：(1) a kind of CNTs-MMT self-assembled nanometer powder for having MMT and CNTs excellent specific properties concurrently is prepared, effectively
MMT interlamellar spacings are improved, and solve the problems, such as that CNTs easily reunites winding, unfavorable scattered；(2) a kind of CNTs-MMT self assemblies are provided
Nano powder is grafted glass fibre precast body, is stopped for preventing or solving nano powder in composite material process planning by fabric
Or filtering and caused by gather problem, realize that composite property is stable；(3) MMT and CNTs excellent specific properties are made full use of, are improved
The interfacial adhesion of fibre reinforced composites, so as to strengthen and toughness reinforcing glass fiber compound material.
Technical scheme：To realize above-mentioned technical purpose, the present invention proposes a kind of CNT-montmorillonite self-assembled nanometer powder
The preparation method of glass fibre reinforced composion is grafted, is comprised the following steps：
(1) aminated carbon nano tube：CNT is scattered in non-proton organic solvent, and adds dehydrating condensation agent
And activator, 1g/L~50g/L carbon nano tube dispersion liquid is obtained after agitated, ultrasonic；It is kept stirring for, preferably keeps rotating speed
100r/min~800r/min, organic amine is added in carbon nano tube dispersion liquid and reacted, preferably reacts 5h at room temperature~80 DEG C
After~72h, aminated carbon nano tube is filtrated to get after deionization is washed, alcohol is washed；
(2) prepared by CNT ammonium salt：The aminated carbon nano tube of step (1) is scattered in deionized water, obtained
The dispersion liquid of 10g/L~50g/L CNTs；It is 3.5~6.5 to reuse salt acid for adjusting pH, after stirring 5 h~48h, preferably
After being stirred under rotating speed 100r/min~800r/min, wash, be filtrated to get CNT ammonium salt；
(3) preparation of CNT-montmorillonite self-assembled nanometer powder：Montmorillonite is added in deionized water, stirs and surpasses
Sonication, it is preferable that under 500r/min~1000r/min stir 1h~3h after, be ultrasonically treated, obtain 10g/L~150g/L
Montmorillonite suspension；CNT ammonium salt in step (2) is added in montmorillonite suspension, preferably with 0.05g/min
~2g/min speed is added in montmorillonite suspension, and lasting stirring, preferably 100r/min~800r/min is held under rotating speed
Continuous stirring 1h~5h, after filtered, washing 3~5 times, spray drying obtains CNT-montmorillonite-based nano powder, wherein, cover de-
Native addition is 100wt%~1000wt% of carbon nanotube mass；
(4) preparation of nano powder grafting glass fibre precast body：Silane coupler is dissolved in solvent, stirred
PH to 3.5~5.5 is adjusted to silane coupler solution, or using acetic acid；By the nano-powder dispersion in step (3) in silane coupler
In solution, glass fiber material surface is uniformly sprayed on after sonicated, is dried in vacuo at 100 DEG C ± 20 DEG C and obtains nanometer
Powder is grafted glass fiber reinforcements；CNT-montmorillonite-based nano powder is 0.1~50g/ in the face content of fiberglass surfacing
m2；
(5) prepared by composite：The precast body in step (4) is answered with resin matrix using composite material process planning
Close, obtain CNT-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin composite.
Preferably, the CNT described in step (1) is single wall, double-walled or multi-walled carbon nanotube.It is it is highly preferred that described
Carbon nano tube surface is with any one or a few functional group in carboxyl, carboxylic acid halides, acid anhydrides, aldehyde radical.
Preferably, the autoprotolysis reaction of the non-proton organic solvent described in step (1) is extremely faint or without certainly
Tendency is passed, described aprotic organic solvent is carbon tetrachloride, dichloromethane, dimethyl sulfoxide (DMSO), N, N- dimethylformamides,
Any one in 1,3- dimethyl-2-imidazolinones, acetone, ether；Solvent described in step (4) is 75% ethanol water
Any one several mixture in solution, 75% methanol aqueous solution, 75% isopropanol water solution.
Dehydrating condensation agent described in step (1) is carbodiimide type condensing agent, phosphorus ionic condensing agent, urea cation
Any one in type condensing agent, including be not limited to N, N'- dicyclohexylcarbodiimides, N, N'- diisopropyls carbon two are sub-
Amine, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, hexafluorophosphoric acid BTA -1- bases-epoxide tripyrrole alkane
Base phosphine, tripyrrole alkane base phosphonium bromide hexafluorophosphate, O- (7- nitrogen BTA)-N, N, N', N'- tetramethylurea hexafluorophosphoric acids
Ester, BTA-N, N, N', N'- tetramethylurea hexafluorophosphoric acid ester, O- BTAs-N, N, N', N'- tetramethylurea four
Fluoboric acid ester, 6- Chloro-Benzotriazole -1,1,3,3- tetramethylurea hexafluorophosphoric acid esters O- (1,2- dihydro -2- Oxopyridyls) -1,
Any one in 1,3,3- tetramethylurea tetrafluoroborate, dehydrating condensation agent are 0wt%~5wt% of carbon nanotube mass；
Activator described in step (1) can be in activated carboxyl carbonyl, suppress the generation of accessory substance in reaction system, described activation
Agent is n-hydroxysuccinimide, HP, I-hydroxybenzotriazole, 1- hydroxyl -7- azos benzo three
Any one in nitrogen azoles, DMAP, 4- pyrollidinopyridines, the dosage of activator is carbon nanotube mass
0wt%~5wt%.
Preferably, the organic amine described in step (1) is ethylenediamine, 1,3- propane diamine, Putriscine, 1,5- diaminos
Base pentane, 1,6- hexamethylene diamines, 1,8- octamethylenediamines, 1,10- decamethylene diamines, diethylenetriamine, triethylene tetramine, TEPA, N-
(3- aminopropyls) -1,4- butanediamine, 2- furylamines, 5- methyl chaffs amine, 2-thenylaminine, thiophene-α-sulfonamide, 5- bromine thiophenes
Any one or a few mixture in fen -2- sulfonamide, 3- amino propylene, acrylamide, 9- octadecenyl amines；Wherein, it is organic
Amine dosage is 0.5wt%~10wt% of carbon nanotube mass.
In montmorillonite described in step (3) exchangeable cations be sodium, calcium, magnesium, in iron any one or a few is mixed
Close, the cation exchange capacity of described montmorillonite is 60~120mmol/100g, and montmorillonite addition is carbon nanotube mass
100wt%~1000wt%.
Silane coupler described in step (4) is amino silicone alkanes coupling agent, epoxy radicals silicone hydride class coupling agent or vinyl
Any one in silane coupling agent, described silane coupler carries reactable group, including is not limited to 3- ammonia third
Ethyl triethoxy silicane alkane, 3- aminopropyl trimethoxysilanes, N- (2- aminoethyls) -3- aminopropyltriethoxies dimethoxysilane, N-
(2- aminoethyls) -3- aminopropyl triethoxysilanes, diethylenetriamine hydroxypropyl methyl dimethoxysilane, 3- (2,3- epoxies third
Oxygen) propyl trimethoxy silicane, 3- (oxygen of 2,3- epoxies third) propyl-triethoxysilicane, VTES, ethene
Any one in base trimethoxy silane, vinyl three-(2- methoxyethoxies)-silane, the dosage of silane coupler is receives
0.1wt%~2wt% of ground rice quality.
Glass fiber material described in step (4) is one-way fabric, Multi-axial stitch knitting fabric, grid fabric, plain weave are knitted
Any one in thing, twills, fibrofelt；Described glass fiber material surface density is 100~1500g/m2。
Composite material process planning described in step (5) is pultrusion, hot pressing, vacuum assisted resin instillation process, resin
Transfer modling technique, vacuum assisted resin transfer molding technique, resin dip-molding process, structural response injection molding technique,
Liquid resin soaks any one in moulding technology, Resin film infusion, vacuum bag molding moulding process.
Resin described in step (5) is epoxy resin, unsaturated polyester resin, vinyl ester resin, bismaleimide
Any one in polyimide resin, polyurethane resin.
The general principle of the present invention：The present invention successively obtains CNT through organic amine modification, Bronsted acid salt-forming reaction
CNT ammonium salt, then with montmorillonite cation exchange, obtain a kind of CNT-montmorillonite with one-dimensional/two-dimensional structure
Self-assembled nanometer powder.The self-assembled nanometer powder has montmorillonite and CNT excellent properties concurrently, and one side CNT intercalation can
The interlamellar spacing of montmorillonite is improved, the low long chain alkyl ammonium salt of traditional heat endurance can be replaced；On the other hand, the lamella of montmorillonite
Structure can obstruct and weaken the winding of CNT.Meanwhile CNT-montmorillonite self-assembled nanometer powder is grafted on into glass fibers
Dimension table face, the problem of avoiding composite material shaping process nano powder by fabric stop or filter, not only further improve and receive
The dispersiveness of ground rice in the composite, the interfacial adhesion between fiber and resin can be also improved, so as to strengthen and toughness reinforcing glass
Glass fibrous composite.
Beneficial effect：Compared with prior art, the present invention has the following technical effect that：
(1) barrier of sheet montmorillonite can effectively improve carbon nanometer in CNT-montmorillonite-based nano powder of the invention
The dispersiveness of pipe, the phenomenon that CNT easily winds, reunited is reduced or avoided；
(2) CNT-montmorillonite-based nano powder of the invention improves the interlamellar spacing of montmorillonite by CNT intercalation,
Its excellent properties is played, can partially or completely replace the low long chain alkyl modifier of traditional heat endurance；
(3) CNT of the invention-montmorillonite-based nano powder grafting glass fibre precast body can effectively solve composite
There are problems that in moulding process nano powder by fabric stop or filter and caused by gather, it is compound to effectively improve glass fibre
The interfacial adhesion of material；
(4) CNT of the invention-montmorillonite-based nano powder grafting prefabricated preparation process of glass fibre is simple, Yi great Gui
Mould produces, environmental protection, and application prospect is extensive.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of CNT intercalated montmorillonite composite nano powder；
Fig. 2 is the microscopic appearance that CNT-montmorillonite self-assembled nanometer powder is grafted glass fibre precast body in embodiment 1
Scheme (SEM)；
Fig. 3 is that CNT-montmorillonite self-assembled nanometer powder is grafted glass fiber reinforced composite material in Examples 1 and 2 example
The thermogravimetric curve figure (TG) of material；
Embodiment
The above of the present invention is described in further detail below by way of specific embodiment.But this should not be understood
Following examples are only limitted to for present disclosure.
Embodiment 1
A kind of preparation method of CNT-montmorillonite self-assembled nanometer powder grafting glass fibre reinforced composion, tool
Body step is as follows：
(1) aminated carbon nano tube：Weigh the N that 0.2g carboxyls multi-walled carbon nanotube adds 0.02L, N'- dimethyl formyls
In amine solvent, then it is separately added into 0.005g N, N'- DICs and I-hydroxybenzotriazole, agitated 5min,
Obtain 10g/L carbon nano tube dispersion liquid after ultrasonic 30min, and by its magnetic agitation, keep rotating speed 200r/min；Weigh
0.01g diethylenetriamines are added in carbon nano tube dispersion liquid, after reacting at room temperature 24h, through deionization is washed, alcohol is washed after distinguishing 2 times
Filtering, obtains diethylenetriamine modified carbon nano-tube；
(2) prepared by CNT ammonium salt：By in step (1) diethylenetriamine be modified CNT 0.02L go from
Stirring 5min, ultrasonic 30min obtain 10g/L amino carbon nano tube dispersion liquid in sub- water, use hydrochloric acid (Bronsted acid) to adjust pH
For 4.5 or so, and stir 24h under rotating speed 300r/min and obtain CNT ammonium salt, it is standby；
(3) CNT intercalated montmorillonite：1g montmorillonites (cation exchange capacity 90mmol/100g) are dissolved in 50ml
In deionized water, agitated 1.5h, ultrasonic 0.5h obtain 20g/L montmorillonite suspension, and step is added with 0.05g/min speed
Suddenly the CNT ammonium salt in (2), the magnetic agitation 3h under rotating speed 400r/min；Through standing sedimentation, deionized water washing filtering 3
~5 times, finally spray drying obtains CNT intercalated montmorillonite nano powder.
(4) preparation of nano powder grafting glass fibre precast body：Weigh 0.01g aminopropyl triethoxysilanes be dissolved in it is molten
In agent, amino silicane coupling agent solution is uniformly mixing to obtain；By the nano-powder dispersion in 1g steps (3) in amino silicane coupling agent
In solution, 1m is uniformly sprayed on after sonicated2Surface density be 1200g/m2One-way glass fabric surface, 100
Vacuum drying obtains nano powder grafting glass fiber reinforcements at DEG C ± 20 DEG C, wherein, 3- aminopropyl triethoxysilanes is receive
The 1wt% of ground rice quality, nano powder are 1g/m in the face content of one-way glass fabric surface2。
(5) preparation of composite：Using vacuum bag molding moulding process by the precast body and epoxy resin-matrix in step (4)
Body (SP/3486 of LY 1564, Huntsman Corporation) is compound, obtains CNT-montmorillonite self-assembled nanometer powder grafting glass fibers
Tie up reinforced epoxy composite.
Curve (b) is the XRD that the present embodiment prepares CNT-montmorillonite self-assembled nanometer powder in Fig. 1.Can by Fig. 1
See, 2 θ angles are contracted to 5.66 ° by 7.08 °.Calculated from Bragg equation (2dsin θ=n λ), montmorillonite is inserted through CNT
Interlamellar spacing increases after layer.Fig. 2 is that CNT manufactured in the present embodiment-montmorillonite self-assembled nanometer powder grafting glass fibre is pre-
The SEM figures of body processed, wherein Fig. 2 (b) is Fig. 2 (a) partial enlarged drawing.From Figure 2 it can be seen that CNT-montmorillonite-based nano powder exists
Fiberglass surfacing is uniformly dispersed.Embodiment 1 is that the present embodiment prepares CNT-montmorillonite self-assembled nanometer powder and connect in table 1
The mechanical experimental results of branch glass fiber reinforcement epoxy composite, it is glass fiber reinforced compared to pure from table 1
O compoiste material (comparative example 1, as shown in table 1), the tensile strength of carbon nanotubes-montmorillonite self-assembled nanometer powder composite material
13.8% and 15.5% is respectively increased with modulus；21.1% and 23.4% is respectively increased in bending strength and modulus；Interlayer shear is strong
Spend intensity and improve about 23.2%.The lifting of composite materials property is mainly due to CNT-montmorillonite-based nano powder in glass
The dispersed and fiber of glass fiber surface has preferable interfacial adhesion with resin.Embodiment 1 is the present embodiment system in Fig. 3
The thermal gravimetric analysis curve of standby CNT-montmorillonite self-assembled nanometer powder grafting glass fiber reinforcement epoxy composite, by Fig. 3
It can be seen that compared to pure glass fiber reinforcement epoxy composite (comparative example 1, as shown in Figure 3), carbon nanotubes-montmorillonite is certainly
For assemble nanometer powder composite material in thermogravimetric weight loss 5%, its decomposition temperature is by 294.6 DEG C of liftings to 306.6 DEG C.Composite is resistance to
Hot lifting is made mainly due to the raising of composite material interface cohesive and the enhancing of CNT-montmorillonite-based nano powder
With.
Embodiment 2
A kind of CNT-montmorillonite self-assembled nanometer powder and preparation method thereof, it is with the different places of embodiment 1,
Carboxyl CNT described in step (1) is changed into 1g, described N, N'- DICs and I-hydroxybenzotriazole
It is changed into 0.02g respectively, described organic amine is changed into 0.2g triethylene tetramines；Solution ph described in step (2) is adjusted to 4；
10g montmorillonites are added in 100mL deionized waters in step (3), 3h, ultrasonic 1h are stirred under 1000r/min；CNT ammonium
Salt mixing speed in montmorillonite suspension is 800r/min, and continues to stir 5h；Silane coupler described in step (4) becomes
For 0.03g 3- (2,3- the third oxygen of epoxy) propyl-triethoxysilicane, and silane coupler solution pH to 4.0 is adjusted with acetic acid；
Nano powder quality is changed to 3g；Composite material process planning is changed into vacuum assisted resin transfer molding technique in step (5).
Curve (c) is the XRD that the present embodiment prepares CNT-montmorillonite self-assembled nanometer powder in Fig. 1.Can by Fig. 1
See, 2 θ angles by 7.08 ° by being contracted to 5.57 °.Calculated from Bragg equation (2dsin θ=n λ), montmorillonite is through CNT
Interlamellar spacing increases after intercalation.Embodiment 2 is that the present embodiment prepares CNT-montmorillonite self-assembled nanometer powder grafting glass in table 1
The mechanical experimental results of glass fibre enhancement epoxy composite material, from table 1, answered compared to pure glass fiber reinforcement epoxy
Condensation material (comparative example 1, as shown in table 1), the tensile strength and mould of carbon nanotubes-montmorillonite self-assembled nanometer powder composite material
17.0% and 18.6% is respectively increased in amount；25.8% and 27.2% is respectively increased in bending strength and modulus；Interlaminar shear strength is strong
Degree improves about 26.5%.Embodiment 2 is that the present embodiment prepares CNT-montmorillonite self-assembled nanometer powder grafting glass in Fig. 3
The thermal gravimetric analysis curve of fibre enhancement epoxy composite material, as seen from Figure 3, compared to pure glass fiber reinforcement epoxy composite
(comparative example 1, as shown in Figure 3), carbon nanotubes-montmorillonite self-assembled nanometer powder composite material is in thermogravimetric weight loss 5%, its point
Temperature is solved by 294.6 DEG C of liftings to 314.5 DEG C.
Embodiment 3
A kind of CNT-montmorillonite self-assembled nanometer powder and preparation method thereof, it is with the different places of embodiment 1,
Carboxyl CNT described in step (1) is changed into 1g, and described aprotic organic solvent is changed into carbon tetrachloride, described dehydration
Condensing agent is changed into ethyl-(3- dimethylaminopropyls) carbodiimide hydrochloride (EDC) and n-hydroxysuccinimide (NHS),
Described organic amine is changed into 0.05g TEPAs；Solution ph is adjusted to 3.5 with hydrochloric acid in step (2), and the rotating speed is adjusted
For 600r/min；Montmorillonite quality described in step (3) is changed into 5g, and the cation exchange capacity of montmorillonite is changed into 100mmol/
100g, described CNT ammonium salt mixing speed in montmorillonite suspension is 600r/min.Silane described in step (4)
Coupling agent is changed into N- (2- aminoethyls) -3- aminopropyl triethoxysilanes；Described glass fiber material is that surface density is
400g/m2Woven roving；Composite material process planning described in step (5) is changed into die press technology for forming；Described resin is
Polyurethane resin (78BD075/44CP20, Bayer Material Science Co., Ltd).
Curve (d) is the XRD that the present embodiment prepares CNT-montmorillonite self-assembled nanometer powder in Fig. 1.Can by Fig. 1
See, 2 θ angles of the present embodiment nano powder are contracted to 5.5 ° by 7.08 °, it is seen that montmorillonite interlamellar spacing after CNT intercalation increases
Greatly, CNT intercalated montmorillonite success.
Embodiment 4
A kind of CNT-montmorillonite self-assembled nanometer powder and preparation method thereof, it is with the different places of embodiment 1,
Aprotic organic solvent described in step (1) is changed into acetone solvent, and 1, the 8- that described organic amine material is changed into 0.02g is pungent
Diamines, described dehydrating condensation agent are changed into 0.01g hexafluorophosphoric acid BTA -1- bases-epoxide tripyrrole alkylphosphines (PyBOP)；
It is 3.5 that salt acid for adjusting pH value is used in step (2), and stirs 12h under 800r/min；Montmorillonite described in step (3) is changed into
4g montmorillonites, the cation exchange capacity of montmorillonite are changed into 70mmol/100g, and described CNT ammonium salt is suspended in montmorillonite
Mixing speed is 600 r/min in liquid.Silane coupler described in step (4) is changed into VTES, is used in combination
Acetic acid adjusts silane coupler solution pH to 3.5；Described glass fiber material is that surface density is 400g/m2Woven roving；Step
Suddenly the composite material process planning described in (5) is changed into resin transfer molding (RTM) process；Described resin is 191 unsaturated polyester (UP)s
Resin.
Curve (e) is the XRD that the present embodiment prepares CNT-montmorillonite self-assembled nanometer powder in Fig. 1.Can by Fig. 1
See, 2 θ angles of the present embodiment nano powder are contracted to 5.46 ° by 7.08 °, it is seen that montmorillonite interlamellar spacing after CNT intercalation increases
Greatly, CNT intercalated montmorillonite success.
Embodiment 5
A kind of CNT-montmorillonite self-assembled nanometer powder and preparation method thereof, it is with the different places of embodiment 1,
The inactive functional group of carbon nano tube surface described in step (1), carbon nanotube mass are changed into non-proton organic described in 0.5g
Solvent is changed into dimethyl sulfoxide solvent, and described dehydrating condensation agent is changed into 0g, and described organic amine material is changed into 0.02g 2-
Furylamine, 48h is reacted at 50 DEG C；PH value described in step (2) is adjusted to 5.5；CNT ammonium described in step (3)
Salt speed of agitator in montmorillonite suspension is changed into 300r/min, and mixing time is changed into 8h.It is silane coupled described in step (4)
Agent is changed into vinyltrimethoxy silane, and adjusts silane coupler solution pH to 3.5 with acetic acid；Described glass fiber material
It is 400g/m for surface density2Plain cloth；Composite material process planning described in step (5) is changed into vacuum assisted resin biography
Pass moulding technology；Described resin is 3201 vinyl ester resins.
Curve (f) is the XRD that the present embodiment prepares CNT-montmorillonite self-assembled nanometer powder in Fig. 1.Can by Fig. 1
See, 2 θ angles of the present embodiment nano powder are contracted to 5.68 ° by 7.08 °, it is seen that montmorillonite interlamellar spacing after CNT intercalation increases
Greatly.
Embodiment 6
A kind of CNT-montmorillonite self-assembled nanometer powder and preparation method thereof, it is with the different places of embodiment 1,
The inactive functional group of carbon nano tube surface described in step (1), carbon nanotube mass are changed into 1g, and described is non-proton organic molten
Agent is changed into HMPA, and described dehydrating condensation agent is changed into 0g, and described organic amine material is changed into 0.04g 3- ammonia
Base propylene, 36h is reacted at 50 DEG C；Bronsted acid described in step (2) is changed into nitric acid, and pH value is adjusted to 5；Described in step (3)
CNT ammonium salt in montmorillonite suspension speed of agitator be changed into 200r/min mixings time and be changed into 6h；Institute in step (4)
The silane coupler stated is changed into 0.02g N- (2- aminoethyls) -3- aminopropyl triethoxysilanes；Described glass fiber material
It is 1500g/m for surface density2S- glass fibre one-way fabrics；Nano powder quality is changed into 1.5g；In step (5) composite into
Type technique is changed into vacuum assisted resin transfer molding technique；Described resin is 5406 bimaleimide resins.
Curve (g) is the XRD that the present embodiment prepares CNT-montmorillonite self-assembled nanometer powder in Fig. 1.Can by Fig. 1
See, 2 θ angles of the present embodiment nano powder are contracted to 5.56 ° by 7.08 °, and montmorillonite interlamellar spacing after CNT intercalation increases.
Comparative example 1
By 1200g/m2One-way glass fabric be layed in vacuum bag, it is standby；By epoxy resin-base (LY
1564 SP/3486, Huntsman Corporation) it is well mixed in injection vacuum bag, the preparation of vacuum-bag process technique is can obtain after solidification
Glass fiber reinforcement epoxy composite.
The mechanical experimental results of table 1
Claims (10)
1. a kind of preparation method of CNT-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin composite,
It is characterised in that it includes following steps：
(1) aminated carbon nano tube：CNT is scattered in non-proton organic solvent, and adds dehydrating condensation agent and work
Agent, 1g/L~50g/L carbon nano tube dispersion liquid is obtained after agitated, ultrasonic；It is kept stirring for organic amine adding carbon nanometer
Reacted in pipe dispersion liquid, aminated carbon nano tube is filtrated to get after deionization is washed, alcohol is washed；
(2) prepared by CNT ammonium salt：The aminated carbon nano tube of step (1) is scattered in deionized water, obtain 10g/L~
The dispersion liquid of 50g/L CNTs；It is 3.5~6.5 to reuse salt acid for adjusting pH, after stirring 5h~48h, washes, is filtrated to get
CNT ammonium salt；
(3) preparation of CNT-montmorillonite self-assembled nanometer powder：Montmorillonite is added in deionized water, stirred and at ultrasound
Reason, obtains 10g/L~150g/L montmorillonite suspension；CNT ammonium salt in step (2) is added into montmorillonite suspension
In persistently stir, it is filtered, washing after, spray drying obtain CNT-montmorillonite-based nano powder, wherein, montmorillonite addition
For 100wt%~1000wt% of carbon nanotube mass；
(4) preparation of nano powder grafting glass fibre precast body：Silane coupler is dissolved in solvent, is uniformly mixing to obtain silicon
Alkane coupling agent solution, or adjust pH to 3.5~5.5 using acetic acid；By the nano-powder dispersion in step (3) in silane coupler solution
In, glass fiber material surface is uniformly sprayed on after sonicated, is dried in vacuo at 100 DEG C ± 20 DEG C and obtains nano powder grafting
Glass fiber reinforcements；CNT-montmorillonite-based nano powder is 0.1~50g/m in the face content of fiberglass surfacing2；
(5) prepared by composite：It is using composite material process planning that the precast body in step (4) is compound with resin matrix, obtain
To CNT-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin composite.
2. CNT according to claim 1-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin is compound
The preparation method of material, it is characterised in that the CNT described in step (1) is single wall, double-walled or multi-walled carbon nanotube.
3. CNT according to claim 1-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin is compound
The preparation method of material, it is characterised in that the autoprotolysis reaction of the non-proton organic solvent described in step (1) is extremely micro-
Weak or not from passing tendency, described aprotic organic solvent is carbon tetrachloride, dichloromethane, dimethyl sulfoxide (DMSO), N, N- diformazans
Any one in base formamide, DMI, acetone, ether；Solvent described in step (4) is
Any one or a few mixture in 75% ethanol water, 75% methanol aqueous solution, 75% isopropanol water solution.
4. CNT according to claim 1-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin is compound
The preparation method of material, it is characterised in that dehydrating condensation agent described in step (1) is carbodiimide type condensing agent, phosphorus just from
Any one in subtype condensing agent, urea ionic condensing agent, dehydrating condensation agent for carbon nanotube mass 0wt%~
5wt%；Described activator is n-hydroxysuccinimide, HP, I-hydroxybenzotriazole, 1- hydroxyls
Any one in base -7- azos BTA, DMAP, 4- pyrollidinopyridines；The dosage of activator is
0wt%~5wt% of carbon nanotube mass.
5. CNT according to claim 1-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin is compound
The preparation method of material, it is characterised in that the organic amine described in step (1) is ethylenediamine, 1,3- propane diamine, Isosorbide-5-Nitrae-fourth two
Amine, 1,5- 1,5-DAPs, 1,6- hexamethylene diamines, 1,8- octamethylenediamines, 1,10- decamethylene diamines, diethylenetriamine, triethylene tetramine, four
The amine of ethene five, N- (3- aminopropyls)-Putriscine, 2- furylamines, 5- methyl chaffs amine, 2-thenylaminine, thiophene-α-sulphur
Any one or a few mixing in acid amides, 5- bromothiophene -2- sulfonamide, 3- amino propylene, acrylamide, 9- octadecenyl amines
Thing；Wherein, organic amine amount is 0.5wt%~10wt% of carbon nanotube mass.
6. CNT according to claim 1-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin is compound
The preparation method of material, it is characterised in that exchangeable cations is in sodium, calcium, magnesium, iron in the montmorillonite described in step (3)
Any one or a few mixing, the cation exchange capacity of described montmorillonite is 60~120mmol/100g, montmorillonite
Addition is 100wt%~1000wt% of carbon nanotube mass.
7. CNT according to claim 1-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin is compound
The preparation method of material, it is characterised in that silane coupler described in step (4) is amino silicone alkanes coupling agent, epoxy radicals silicon
Any one in alkanes coupling agent or vinyl silanes class coupling agent, the dosage of silane coupler is nano powder quality
0.1wt%~2wt%.
8. CNT according to claim 1-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin is compound
The preparation method of material, it is characterised in that the glass fiber material described in step (4) is one-way fabric, Multi-axial stitch knitting is knitted
Any one in thing, grid fabric, plain cloth, twills, fibrofelt；Described glass fiber material surface density is
100~1500g/m2。
9. CNT according to claim 1-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin is compound
The preparation method of material, it is characterised in that the composite material process planning described in step (5) is pultrusion, hot pressing, vacuum aided
Resin infusion technique, resin transfer molding (RTM) process, vacuum assisted resin transfer molding technique, resin dip-molding process, structure
It is any in reaction injection molded technique, liquid resin wetting moulding technology, Resin film infusion, vacuum bag molding moulding process
It is a kind of.
10. CNT according to claim 1-montmorillonite self-assembled nanometer powder grafting galss fiber reinforced resin is compound
The preparation method of material, it is characterised in that the resin described in step (5) is epoxy resin, unsaturated polyester resin, vinyl
Any one in ester resin, bimaleimide resin, polyurethane resin.
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