CN103788413B - The method of graphene oxide chemically modified mineral filler, products obtained therefrom and application - Google Patents
The method of graphene oxide chemically modified mineral filler, products obtained therefrom and application Download PDFInfo
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- CN103788413B CN103788413B CN201410034778.4A CN201410034778A CN103788413B CN 103788413 B CN103788413 B CN 103788413B CN 201410034778 A CN201410034778 A CN 201410034778A CN 103788413 B CN103788413 B CN 103788413B
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Abstract
The invention discloses a kind of method and products obtained therefrom of graphene oxide chemically modified mineral filler, step is: mineral filler is carried out surface hydroxylation process and silane coupling agent process; Graphene oxide solution MES buffered soln is maintained pH at 5.8-6.0, adds EDC and NHS successively, supersound process 1 ~ 3h, then add the mineral filler after process, under room temperature, carry out amidate action; Filtration after reaction, washing, drying, obtain graphene oxide and modify mineral filler.The invention also discloses the method adopting this product to prepare mineral filler/epoxy resin composite material.Present invention process flow process is simple, environmental protection, adopt the method for chemically modified that GO is connected to inorganic filler surface, make between GO and inorganic particulate, to produce firmly covalent bonds, enhance the interfacial adhesion between mineral filler and polymkeric substance and physical strength, for the modification of inorganic filler surface and the preparation of high performance composite provide a new thinking.
Description
Technical field
The present invention relates to a kind of method that inorganic filler surface is processed, be specifically related to a kind of graphene oxide that adopts and the method for chemically modified is carried out to glass fibre and hollow glass micropearl, and the product of the method gained and use the mineral filler after modifying to prepare the method for the excellent polymer matrix composite of interface performance, belong to new material technology field.
Background technology
Inorganic Fillers Filled polymer composites is the important matrix material of a class, has a wide range of applications in fields such as aerospace, automotive industry and physical culture.The factor affecting Inorganic Fillers Filled polymer composites performance is a lot, and wherein interfacial adhesion effect is one of most important factor.Interface is the tie connected between wild phase and matrix phase, is also the bridge that stress and out of Memory transmit.Therefore, in the research field of Inorganic Fillers Filled polymer composites, improve interface compatibility is the focus that people pay close attention to always.
Glass fibre, hollow glass micropearl are the packing materials of two kinds of conventional polymer matrix composites.Glass fiber reinforced polymer is commonly called as glass reinforced plastic, there is important using value, however glass fibre and polymkeric substance affinity poor, compound tense is difficult to form effective interfacial adhesion, these shortcomings cause the interface adhesion of glass fibre and matrix polymer poor, have impact on the performance of matrix material.The effective ways addressed this problem to the modifying surface process of glass fibre.The features such as hollow glass micropearl has that quality is light, chemical stability and Heat stability is good, effectively can reduce the density of material with its filled polymer.The material of this kind of light overpressure resistant has become the important component part developing modern deep diving technology.But this kind of matrix material also also exists the poor defect of the consistency of hollow glass micropearl and polymkeric substance.Therefore, must to glass microballon modifying surface, to improve the physics-chem characteristic on its surface, strengthen consistency and the dispersiveness in the polymer of itself and polymkeric substance, to improve physical strength and the over-all properties of material.
At present, the classical way in order to improve mineral filler and polymeric matrix interface compatibility comprises: coupling agent treatment modification, in-situ polymerization, the modification of Cement Composite Treated by Plasma post polymerization, situ-formed graft polymer etc.Coupling agent treatment modification is simple, different matrix is adopted to the coupling agent of different structure, but effect is general.Other method of modifying technique is comparatively complicated, is often subject to the constraint of equipment, reaction conditions etc., and aftertreatment is difficult, is not easy to implement.
Graphene is the thinnest two-dimensional material found at present, receives much attention in recent years.It is a kind of novel material of the individual layer sheet structure be made up of carbon atom, be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has a carbon atom thickness.Graphene has great specific surface area (2630m
2/ g), extremely hard, there is good toughness.Graphene oxide (GO) is the intermediate product that chemical method prepares Graphene, and its Main Mechanical and Graphene are almost as broad as long, and a large amount of hydrophilic active functional group such as hydroxyl, carboxyl, epoxy group(ing) is contained on its surface, has water-soluble.Meanwhile, the existence of active function groups makes it have certain chemically reactive, and chemical reaction can be utilized to carry out functionalization to GO or GO modified the surface in other material.Patent ZL201110132533.1 provides " core/shell " structure hybridization material that a kind of graphene oxide or Graphene and the self-assembly of modified inorganic particle are formed, method is: be dispersed in water by the inorganic particulate of coupling agent treatment, then graphene dispersing solution is added, stir and obtain hud typed hybrid material, this hybrid material take inorganic particulate as core, and Graphene forms one deck putamina on its surface.Although the method improves the interface adhesion of mineral filler and polymkeric substance, but the method adopts the method for electrostatic adhesion that graphene oxide is adsorbed onto inorganic filler surface, electrostatic adsorption force limited strength, adsorption layer is easily damaged under external force, and mineral filler and polymer composites physical strength improve limited.
Summary of the invention
The object of this invention is to provide a kind of method of graphene oxide chemically modified mineral filler, the method adopts chemical bond by graphene modified to inorganic filler surface, add the affinity of mineral filler and polymkeric substance, improve interface adhesion and the physical strength of mineral filler/polymer composites.
Another object of the present invention is to provide the product adopting aforesaid method gained.
Another object of the present invention is to provide the method adopting the product of aforesaid method gained and polymkeric substance to prepare matrix material.
Yet there are no so far and utilize graphene oxide chemical modification method modified inorganic filler to strengthen the bibliographical information of itself and polymeric matrix interfacial adhesion.Utilize GO to carry out mineral filler modifying the mutual supplement with each other's advantages that can realize material, when preparing mineral filler/polymer composites, making GO be filled in the interface of mineral filler and body material, forming a tough interface layer, realize the object improving interfacial adhesion.Because GO and mineral filler are chemical bonds, intensity is large, and physical strength is strong, survivable.
The present invention by GO with carboxyl and the amino of modified inorganic filling surface carry out amidate action and realize the chemically modified of GO to inorganic filler surface, obtained hybrid material, effectively can improve the avidity of filler and matrix resin, strengthen interface performance and the physical strength of polymer matrix composite.In addition, due to the protection of GO, and that cause cenosphere fragmentation in the curing process different from the thermal expansivity of hollow glass micropearl due to polymeric matrix can be avoided.Operation technological process of the present invention is simple, and the composite property of the GO/ Inorganic Fillers Filled prepared is excellent, has a good application prospect.
Concrete technical scheme is as follows:
A method for graphene oxide chemically modified mineral filler, is characterized in that comprising the following steps:
(1) mineral filler is put into the mixed solution of the vitriol oil and hydrogen peroxide, at 90 DEG C, soak 30min, carry out surface hydroxylation process, soak after washing, dry;
(2) the mineral filler silane coupling agent of step (1) is processed;
(3) graphene oxide powder or graphene oxide water solution are joined in the MES buffered soln of pH=5.8-6.0, form mixing solutions, adding the whole pH of the laggard step of graphene oxide keeps the pH of mixing solutions to be 5.8-6.0, then in mixing solutions, EDC and NHS is added successively, supersound process 1 ~ 3h;
(4) in the solution of step (3), add the mineral filler after silane coupling agent process, carry out amidate action under room temperature, with graphene oxide, mineral filler is modified; Filtration after reaction, washing, drying, obtain graphene oxide and modify mineral filler.
In aforesaid method, described mineral filler is hollow glass micropearl or glass fibre, the K46 type microballon that hollow glass micropearl can be produced for Minnesota Mining and Manufacturing Company, and glass fibre can for conventional E glass fibre.
In aforesaid method, described silane coupling agent is the silane coupling agent of one end with amino, can be the one in KH540, KH550, KH792.
In aforesaid method, the carboxyl-content of described graphene oxide is 8-12%, preferred 10-12%.
In aforesaid method, in step (1), vitriol oil concentration is 98wt%, and hydrogen peroxide concentration is 30wt%; The volume ratio of the vitriol oil and hydrogen peroxide is 7:3; The consumption of mineral filler is 10% of the vitriol oil and hydrogen peroxide mixed solution quality.
In aforesaid method, in step (3), the consumption of EDC and NHS is 1:10 ~ 20:10 ~ 20 according to the mol ratio of the carboxyl in graphene oxide: EDC:NHS, preferred 1:20:15.
In aforesaid method, in step (3), the concentration of graphene oxide in mixing solutions is 0.1 ~ 5.0mg/ml.Described mixing solutions refers to that graphene oxide powder or graphene oxide water solution join the mixing solutions formed in MES buffered soln.
In aforesaid method, in step (3), the concentration of MES buffered soln is 1mol/L.
In aforesaid method, in step (3), can by the NaOH solution adjustment pH of mixed of 1mol/L to 5.8-6.0.
In aforesaid method, in step (4), the consumption of mineral filler is 5 ~ 20% of solution quality in step (3).
In aforesaid method, in step (4), the time of amidate action is 24 ~ 48h.
In aforesaid method, the step of silane coupling agent treatment inorganic filling material is:
A. water and dehydrated alcohol are mixed with solution with the mass ratio of 45:5, with glacial acetic acid regulator solution pH=6.0, in solution, drip silane coupling agent while stirring, stop when adding to silane coupling agent concentration be in the solution 0.5wt%, continue to stir 1.5h and coupling agent is hydrolyzed;
B., after coupling agent hydrolysis, readjust pH value of solution to 6.0, then add the mineral filler of solution quality 10% wherein, at 60 DEG C, stir 40min, suction filtration, washing, dry.
In aforesaid method, the preparation method of graphene oxide is:
A. under room temperature, 0.5 weight part SODIUMNITRATE, 1 parts by weight of graphite powder and the 46 weight part 98wt% vitriol oils are mixed under condition of ice bath, stir 30min, and then slowly add 3 weight part potassium permanganate, stir 30min;
B. the reaction system in step a is heated to 35 DEG C, stirs 2 ~ 48h, obtain brown suspension; In suspension, add 50 parts by weight of deionized water lentamente, stir, be warming up to 98 DEG C and continue reaction 5 ~ 10min, be cooled to room temperature;
C. the reaction solution of step b is poured in 167 parts by weight of deionized water while stirring, add 5 weight part 30wt% hydrogen peroxide, leave standstill 24h;
D. lower sediment is got, with deionized water centrifuge washing three times under 8000r/min condition, each 5 ~ 10min; Precipitate with deionized water is dialysed, until BaCl
2detect without SO
4 2-, add in deionized water by thick liquid after dialysis, supersound process 1h, then by solution centrifugal 5 ~ 10min under the condition of 4000 ~ 8000r/min, gained supernatant liquid is graphene oxide water solution.Freeze-drying graphene oxide solution is utilized to obtain graphene oxide powder.
The graphene oxide obtained according to the method for above-mentioned graphene oxide chemically modified mineral filler modifies mineral filler also within scope.
Further, mineral filler after the present invention modifies can be used for preparing mineral filler/epoxy resin composite material, preparation method is: obtain graphene oxide according to the method for above-mentioned graphene oxide chemically modified mineral filler and modify mineral filler, then obtained mineral filler/epoxy resin composite material is reacted in the modification mineral filler of the graphene oxide of gained and epoxy resin.
The invention has the beneficial effects as follows:
1, the functional group that the present invention mainly has according to mineral filler and GO material surface designs, there is provided a kind of GO to the modifying method of mineral filler, make between GO and inorganic particulate, to produce firmly covalent bonds, enhance the interfacial adhesion between mineral filler and polymkeric substance and physical strength.
2, the mineral filler hybrid material utilizing GO to modify is applied to the preparation of matrix material, improves the interfacial adhesion of mineral filler and resin matrix, for the modification of inorganic filler surface and the preparation of high performance composite provide a new thinking and countermeasure.
3, the invention process process is carried out in aqueous phase, has operation technological process simple, the feature of environmental protection.
4, GO is present in the interfacial layer of hollow glass micropearl and polymeric matrix, can absorb energy, effectively avoids the fragmentation of the microballon caused due to thermal stresses or mechanical stress.
5, present method adopts the method for chemically modified, and bonding force is strong, be not easy to come off, and interfacial layer is survivable compared with electrostatic adhesion, and the interface binding force of the mineral filler/polymer composites of formation is stronger, and physical strength is higher.
Accompanying drawing explanation
Fig. 1 is the FTIR spectrogram of glass fibre after glass fibre after graphene oxide in embodiment 3, silane-modified process, graphene oxide chemically modified.
The stereoscan photograph of Fig. 2 comparative example 1 glass fibre.
Glass fibre stereoscan photograph after Fig. 3 embodiment 3GO chemically modified.
Fig. 4 comparative example 2 hollow glass micropearl stereoscan photograph.
Hollow glass micropearl stereoscan photograph after Fig. 5 embodiment 5GO chemically modified.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, if no special instructions, is followingly all weight percentage and weight part.The present invention's composition used all can commercially have been bought, such as:
Epoxy resin used is the Phoenix brand bisphenol A type epoxy resin E-51 that Xingchen Synthetic Matrials Co., Ltd., Nantong produces.Oxirane value is 0.510 ~ 0.533, and hydrolysis chlorine≤200ppm, color and luster number≤60, viscosity (25 DEG C) are 9000 ~ 11000mPas.
Hollow glass micropearl used is the K46 type microballon that Minnesota Mining and Manufacturing Company produces.Microballon particle diameter is 15 ~ 40 μm, and ultimate compression strength is 41.34MPa, and density is 0.46g/cm
3.
Glass fibre used is conventional E glass fibre.
In following embodiment, the measuring method of GO solid content is: the watch-glass getting dried and clean claims its quality to be designated as m
1, GO solution to be dropped on watch-glass and the total mass weighing watch-glass and GO solution is designated as m
2, then baking oven watch-glass being placed in 150 DEG C is dried to constant weight, taking-up watch-glass is put in moisture eliminator and is cooled to room temperature, and the total mass weighing cooled watch-glass and GO is designated as m
3.(1.1) calculate the solid content s of GO according to the following formula.
With the carboxyl-content in Boehm titration measuring GO, method is: getting 20ml concentration is M
1the NaHCO of (about 0.05mol/L)
3solution, with normal concentration (M
0=0.1mol/L) hydrochloric acid soln be titrated to NaHCO
3the pH value of solution equals 5.1, writes down the consumption V of now hydrochloric acid soln
0(ml).Analytical balance takes 3 parts of GO samples, every part of about 200mg, actual weight is W (mg), and the Erlenmeyer flask being placed in three 300ml respectively does parallel test.Add volume V
3(about 100ml) concentration is M
1naHCO
3solution, with filter paper by taper bottle sealing, stirring reaction 20 hours on magnetic stirring apparatus; Reacted rear filtration, getting volume is V
2filtrate carry out magnetic agitation and with the hydrochloric acid soln titration of normal concentration, the pH value measuring solution with pH meter changes and indicates titration end point, pH=5.1.During arrival titration end point, the volume of quota of expenditure concentration hydrochloric acid is V
1(ml).Calculate the carboxyl percentage composition on GO surface according to the following formula:
NaHCO
3strength of solution M
1calculating:
NaHCO in filtrate
3concentration M
2calculating:
The carboxyl percentage composition on GO surface:
embodiment 1
1, surface hydroxylation modification: the vitriol oil of 98wt% and the hydrogen peroxide of 30wt% are made mixing solutions according to the volume ratio of 7:3, adds the glass fibre of solution quality 10wt% wherein, soak 30min at 90 DEG C.With washed with de-ionized water glass fibre 3 times, be placed in baking oven and dry to constant weight in 100 DEG C.
2, coupling agent modified: water and dehydrated alcohol are mixed with solution with the mass ratio of 45:5, with glacial acetic acid regulator solution pH=6.0.In solution, drip coupling agent while stirring, dropping to coupling agent concentration is in the solution 0.5wt%, continues to stir 1.5h and makes it be hydrolyzed.Regulate the coupling agent solution after hydrolysis to pH=6.0, add the glass fibre of solution quality 10wt% wherein, stir 40min at 60 DEG C, suction filtration, deionized water rinsing 3 times, be placed in baking oven and dry to constant weight in 100 DEG C.
3, the preparation of the GO aqueous solution: under room temperature, by 1.5g SODIUMNITRATE, 3g Graphite Powder 99 (commercially available prod, purity 99.95%, fineness 8000mesh) and the 138g vitriol oil (98wt%) join in there-necked flask under condition of ice bath, stir 30min, then 9g potassium permanganate is slowly added in there-necked flask, stir 30min.Reaction system is heated to 35 DEG C, stirs 2h, obtain brown suspension.In suspension, add 150ml deionized water lentamente, stir, heat up, at 98 DEG C, continue reaction 8min, be cooled to room temperature.Reaction solution is poured in 500ml deionized water while stirring, adds 15mlH
2o
2(30wt%) solution, leaves standstill 24h.Get lower sediment, with deionized water centrifuge washing three times under 8000r/min condition, each 5min.Product after washing is added with deionized water dialysis (dialysis tubing molecular weight cut-off 8000-14000) in dialysis tubing, until BaCl
2detect without SO
4 2-, the liquid taking out thickness in dialysis tubing is placed in beaker, adds deionized water to 900ml, ultrasonic 1h, by solution centrifugal 5min under the condition of 4000r/min, gets the aqueous solution that supernatant liquid obtains GO.The solid content measuring GO solution is 6.2mg/ml, with the carboxyl-content in Boehm titration measuring GO, is 8.02%.Graphene oxide powder can be obtained with freeze-drying drying nest GO solution.
4, GO is to the surface chemical modification of glass fibre: join in the MES buffered soln of 1mol/L by above-mentioned obtained GO solution, with the pH=5.8-6.0 of the NaOH aqueous solution adjustment mixed solution of 1mol/L, the concentration of solid content adjustment GO in mixed solution according to GO is 0.1mg/ml; According to the content of-COOH in the GO measured, and according to-COOH:EDC(1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride): NHS(N-N-Hydroxysuccinimide) be the molar weight ratio of 1:10:10, EDC and NHS is added successively, by mixing solutions supersound process 1h in solution.
Add the glass fibre through silane coupling agent process of solution quality 5%, room temperature lower magnetic force stirs 24h, carries out amidate action.After reaction terminates, leave standstill, filter, with deionized water, glass fibre is cleaned 3 times, be placed in baking oven and dry to constant weight in 100 DEG C, obtain graphene oxide modified glass fibers.
embodiment 2
1, the preparation of GO solution, the surface hydroxylation of glass fibre and coupling agent modified method are with embodiment 1.
2, GO is to the surface chemical modification of glass fibre: GO solution being joined concentration is in the MES buffered soln of 1mol/L, and the pH of adjustment mixed solution is 5.8-6.0, and the concentration of adjustment GO in mixed solution is 2.0mg/ml; According to the content of-COOH in the GO measured, and according to-COOH:EDC(1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride): NHS(N-N-Hydroxysuccinimide) be the molar weight ratio of 1:15:20, EDC and NHS is added successively, by mixing solutions supersound process 2h in solution.
Add the glass fibre through silane coupling agent process of solution quality 10%, room temperature lower magnetic force stirs 36h, carries out amidate action.After reaction terminates, leave standstill, filter, with deionized water, glass fibre is cleaned 3 times, finally dry to constant weight with the temperature of 80 DEG C in an oven, obtain graphene oxide modified glass fibers.
embodiment 3
1, the surface hydroxylation of glass fibre and coupling agent modified method are with embodiment 1.
2, the preparation of the GO aqueous solution: join in there-necked flask under condition of ice bath by 1.5g SODIUMNITRATE, 3g Graphite Powder 99 and the 138g vitriol oil (98%), stirs 30min, is then slowly added in there-necked flask by 9g potassium permanganate, stirs 30min.Be heated to 35 DEG C, and fully stir 24h, obtain brown suspension.In suspension, add 150ml deionized water lentamente, stir, heat up, at 98 DEG C, continue reaction 10min, be cooled to room temperature.Reaction solution is poured in 500ml deionized water while stirring, adds 15mlH
2o
2(30%) solution, leaves standstill 24h.Get lower sediment, with deionized water centrifuge washing three times under 8000r/min condition, each 8min.Product deionized water is dialysed, until BaCl
2detect without SO
4 2-, the liquid taking out thickness is placed in beaker, adds deionized water to 900ml, ultrasonic 1h, by solution centrifugal 8min under the condition of 8000r/min, gets the aqueous solution that supernatant liquid obtains GO.Graphene oxide powder can be obtained with freeze-drying drying nest GO solution.Measuring the solid content of GO solution, is 6.6mg/ml; With the carboxyl-content in Boehm titration measuring GO, be 10.18wt%.
3, GO is to the surface chemical modification of glass fibre: it is in the MES buffered soln of 1mol/L that above-mentioned obtained GO solution is joined concentration, and adjustment pH of mixed is 5.8-6.0, and in mixed solution, the concentration of GO is 5.0mg/ml; According to the content of-COOH in the GO measured, and according to-COOH:EDC(1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride): NHS(N-N-Hydroxysuccinimide) be the molar weight ratio of 1:20:15, EDC and NHS is added successively, by mixing solutions supersound process 3h in solution.
Add the glass fibre through silane coupling agent process of solution quality 20%, room temperature lower magnetic force stirs 48h, carries out amidate action.After reaction terminates, leave standstill, filter, with deionized water, glass fibre is cleaned 3 times, be placed in baking oven and dry to constant weight in 50 DEG C, obtain graphene oxide modified glass fibers.
Adopt Fourier transform infrared spectrometer (FTIR) chemical structure to the glass fibre that graphene oxide, silane-modified glass fibre and graphene oxide are modified to characterize, sample preparation adopts KBr pressed disc method, and resolving power is 4cm
-1, scanning times is 32 times, sweep limit 400 ~ 4000cm
-1.Gained FTIR spectrogram as shown in Figure 1, as can be seen from the figure: the characteristic peak of amide group has appearred in the glass fibre after GO chemically modified, is 3420cm respectively
-1n-H stretching vibration peak, 1640cm
-1c=O stretching vibration, 1550cm
-1n-H flexural vibration peak and 1460cm
-1c-N stretching vibration; And be positioned at 1730cm
-1hydroxy-acid group C=O stretching vibration disappear.This demonstrate that GO is successfully modified in fiberglass surfacing by amidate action.
Characterize the microscopic appearance of the glass fibre after modification, method is: stick in sample table with double faced adhesive tape by dried testing sample, and light pressure makes to treat test sample and glue surface plaster in fact, brushes from different directions remove unnecessary sample with rubber suction bulb; With ion plating instrument at sample surfaces spraying plating one deck carbonaceous conductive layer, carry out microscopic appearance observation with FEIQUANTAFEG250 type field emission scanning electron microscope and take pictures.As shown in Figure 3, as can be seen from the figure fiberglass surfacing is with GO for gained SEM photo, and compared with comparative example 1, it is coarse that surface becomes, and when carrying out compound tense with polymkeric substance, soft GO is by the interfacial layer of a generation toughness.
embodiment 4
1, the preparation of the GO aqueous solution is with embodiment 3.
2, surface hydroxylation modification: the vitriol oil of 98% and the hydrogen peroxide of 30% are made mixing solutions according to the volume ratio of 7:3, adds the hollow glass micropearl of solution quality 10% wherein, soak 30min at 90 DEG C.With washed with de-ionized water hollow glass micropearl 3 times, be placed in baking oven and dry to constant weight in 100 DEG C.
3, coupling agent modified: water is become solution with dehydrated alcohol with the proportions of 45:5, with glacial acetic acid regulator solution pH=6.0.In solution, drip coupling agent while stirring, regulate coupling agent concentrations to be 0.5%, continue to stir 1.5h and make it be hydrolyzed.Regulate the coupling agent solution after hydrolysis to pH=6.0, add the hollow glass micropearl of solution quality 10% wherein, stirring at low speed 40min at 60 DEG C, suction filtration, with deionized water rinsing 3 times, be placed in baking oven and dry to constant weight in 100 DEG C.
4, GO is to the surface chemical modification of hollow glass micropearl: joined by GO solution in the MES buffered soln of 1mol/L, and adjustment pH of mixed is 5.8-6.0, and in mixed solution, the concentration of GO is 0.5mg/ml; According to the content of-COOH in the GO measured, and according to-COOH:EDC(1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride): NHS(N-N-Hydroxysuccinimide) be the molar weight ratio of 1:10:10, EDC and NHS is added successively, by mixing solutions supersound process 1h in solution.
Add the hollow glass micropearl through silane coupling agent process of solution quality 5%, room temperature lower magnetic force stirs 24h, carries out amidate action.After reaction terminates, leave standstill, filter, with deionized water, hollow glass micropearl is cleaned 3 times, finally dry to constant weight with the temperature of 60 DEG C in an oven, obtain graphene oxide and modify hollow glass micropearl.
embodiment 5
1, the surface hydroxylation of hollow glass micropearl and coupling agent modified method are with embodiment 4.
2, the preparation of the GO aqueous solution: join in there-necked flask under condition of ice bath by 1.5g SODIUMNITRATE, 3g Graphite Powder 99 and the 138g vitriol oil (98%), stirs 30min, is then slowly added in there-necked flask by 9g potassium permanganate, stirs 30min.Reaction system is heated to 35 DEG C, and fully stirs 48h, obtain brown suspension.In suspension, add 150ml deionized water lentamente, stir, heat up, at 98 DEG C, continue reaction 5min, be cooled to room temperature.Reaction solution is poured in 500ml deionized water while stirring, adds 15mlH
2o
2(30%) solution, leaves standstill 24h.Get lower sediment, with deionized water centrifuge washing three times under 8000r/min condition, each 10min.Product deionized water is dialysed, until BaCl
2detect without SO
4 2-, the liquid taking out thickness is placed in beaker, adds deionized water to 900ml, ultrasonic 1h, by solution centrifugal 10min under the condition of 6000r/min, gets the aqueous solution that supernatant liquid obtains GO.Graphene oxide powder can be obtained with freeze-drying drying nest GO solution.Measuring the solid content of GO solution, is 6.8mg/ml; With the carboxyl-content in Boehm titration measuring GO, be 11.96wt%.
3, GO is to the surface chemical modification of hollow glass micropearl: join in the MES buffered soln of 1mol/L by above-mentioned obtained GO solution, and the pH of adjustment mixed solution is 5.8-6.0, and in mixed solution, the concentration of GO is 5.0mg/ml; According to the content of-COOH in the GO measured, and according to-COOH:EDC(1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride): NHS(N-N-Hydroxysuccinimide) be the molar weight ratio of 1:20:15, EDC and NHS is added successively, by mixing solutions supersound process 2h in solution.
Add the hollow glass micropearl through silane coupling agent process of solution quality 12%, room temperature lower magnetic force stirs 36h, carries out amidate action.After reaction terminates, leave standstill, filter, with deionized water, hollow glass micropearl is cleaned 3 times, finally dry to constant weight with the temperature of 70 DEG C in an oven, obtain graphene oxide and modify hollow glass micropearl.
As shown in Figure 5, as can be seen from the figure: the surface smooth from comparative example 3 is different, hollow glass micropearl surface is connected with the GO of silk shape to the SEM photo of products obtained therefrom, like this at hollow glass micropearl and polymkeric substance compound tense, will produce tough interface layer.
embodiment 6
1, the surface hydroxylation of hollow glass micropearl and coupling agent modified method with the preparation of embodiment 4, GO with embodiment 5.
2, GO is to the surface chemical modification of hollow glass micropearl: joined by GO solution in the MES buffered soln of 1mol/L, and in adjustment mixed solution, the concentration of GO is 1.0mg/ml, pH is 5.8-6.0; According to the content of-COOH in the GO measured, and according to-COOH:EDC(1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride): NHS(N-N-Hydroxysuccinimide) be the molar weight ratio of 1:10:15, EDC and NHS is added successively, by mixing solutions supersound process 3h in solution.
Add the hollow glass micropearl through silane coupling agent process of solution quality 20%, room temperature lower magnetic force stirs 48h, carries out amidate action.After reaction terminates, leave standstill, filter, with deionized water, hollow glass micropearl is cleaned 3 times, finally dry to constant weight with the temperature of 90 DEG C in an oven, obtain graphene oxide and modify hollow glass micropearl.
comparative example 1
The surface hydroxylation of glass fibre and coupling agent modified method, with embodiment 1, obtain surface hydroxylation and coupling agent modified glass fibre.Products obtained therefrom SEM schemes as shown in Figure 2, and as can be seen from the figure fiberglass surfacing is smooth.
comparative example 2
The surface hydroxylation of hollow glass micropearl and coupling agent modified method, with embodiment 4, obtain surface hydroxylation and coupling agent modified hollow glass micropearl.Products obtained therefrom SEM schemes as shown in Figure 4, as can be seen from the figure hollow glass micropearl smooth surface.
comparative example 3
1, the preparation of the GO aqueous solution, the surface hydroxylation of glass fibre and coupling agent modified method are with embodiment 3.
2, the method for modifying of GO to glass fibre is as follows: get the GO solution that 300ml concentration is 1.0mg/ml, regulates pH=6.0 after ultrasonic 30min with the sodium hydroxide solution of 1mol/L; Add the glass fibre through silane coupling agent process of solution quality 10%, ultrasonic 2h under room temperature, makes GO by electrostatic adhesion at fiberglass surfacing.Leave standstill, filter, with deionized water, hollow glass micropearl is cleaned 3 times, finally dry to constant weight with the temperature of 100 DEG C in an oven, obtain GO modified glass-fiber.
comparative example 4
1, the preparation of the GO aqueous solution, the surface hydroxylation of hollow glass micropearl and coupling agent modified method are with embodiment 5.
2, the method for modifying of GO to hollow glass micropearl is as follows: get the GO solution that 300ml concentration is 1.0mg/ml, regulates pH=6.0 after ultrasonic 30min with the sodium hydroxide solution of 1mol/L; Add the hollow glass micropearl through silane coupling agent process of solution quality 10%, ultrasonic 2h under room temperature, make GO by electrostatic adhesion on hollow glass micropearl surface.Leave standstill, filter, with deionized water, hollow glass micropearl is cleaned 3 times, finally dry to constant weight with the temperature of 100 DEG C in an oven, obtain GO modification hollow glass micropearl.
The glass fibre of modification above-described embodiment 1-6 and comparative example 1-4 method obtained or hollow glass micropearl and epoxy resin react makes mineral filler/epoxy resin composite material.The preparation process of hollow glass micropearl/epoxy resin composite material is as follows:
Choose the thinner acetone of epoxy resin quality 20%, the modification hollow glass micropearl of epoxy resin quality 20%, add in epoxy resin successively and be uniformly mixed 10min, then material is put into vacuum tank, vacuum tightness is more than 0.1kPa, a vacuum defoamation process 20min is carried out to mixture, the resin slurry that must mix; The solidifying agent of extracting epoxy resin quality 20% is mixed in resin slurry, stirs and secondary vacuum deaeration process 10min to resin slurry; Take out mould in 25 DEG C of ambient cure 24h, then at 80 DEG C, after fixing 2h, obtains hollow glass micropearl filling epoxy resin composite foam material.
The preparation process of glass fiber/epoxy composite material is as follows:
The preparation of glass fiber compound material adopts vacuum infusion molding process for compound: be coated with demoulding wax on the surface of fiber reinforced plastic mold, and per half an hour is coated with once, is coated with three times altogether.Unidirectional modified fibre is pasted onto fiber reinforced plastic mold on the surface successively, modified fibre surface coverage one deck release cloth, release cloth upper berth flow-guiding screen; Start to vacuumize, by epoxy resin: thinner (acetone): solidifying agent according to the quality of 100:20:13 than mix and blend, by the resin slurry that mixes by adhesive pouring nozzle suction vacuum bag; After having poured into, normal temperature 25 DEG C solidification 24h, then at 80 DEG C, after fixing 2h, obtains unidirectional glassfiber reinforced epoxy based composites.
Measure the interlaminar shear strength of gained glass fiber reinforced epoxy resin matrix material, method is: the interlaminar shear strength of glass fiber compound material measures gained according to GB3357-1982.The parameter of the one-way glass fiber-reinforced resin sample of preparation is: sample size is thick 3mm × wide 6mm × long 25mm, and span and Thickness Ratio are 5, and loading velocity is 2mm/min.
Measure the flexural strength of gained hollow glass micropearl/epoxy resin composite material, method is: the flexural strength of hollow glass micropearl matrix material measures gained with reference to GB9341-2000.The parameter of the hollow glass micropearl filling epoxy resin sample of preparation is: sample size is thick 5mm × wide 10mm × long 100mm, and span and Thickness Ratio are 15, and loading velocity is 2mm/min.
The performance test results of the epoxy resin-matrix epoxy resin composite material that each embodiment and comparative example modified inorganic filler are made is listed in the table below 1.
As can be seen from upper table data: after GO chemically modified, comparatively comparative example 1 and comparative example 3 improve a lot the interlaminar shear strength of glass fiber reinforced epoxy resin matrix material, wherein embodiment 3 effect is the most outstanding, comparatively comparative example 1 improves 31.8%, improves 17.9% compared with the comparative example 3 of physical adsorption; After GO chemically modified the flexural strength of hollow glass micropearl reinforced epoxy matrix material comparatively comparative example 2 and comparative example 4 improve a lot, wherein embodiment 5 effect is the most outstanding, and comparatively comparative example 2 improves 33.8%, improves 18.4% compared with the comparative example 4 of physical adsorption.Illustrate, through GO chemically modified mineral filler, the interface performance of matrix material effectively improves, and than electrostatic adhesion method Be very effective.
Claims (12)
1. a method for graphene oxide chemically modified mineral filler, is characterized in that comprising the following steps:
(1) mineral filler is put into the mixed solution of the vitriol oil and hydrogen peroxide, at 90 DEG C, soak 30min, carry out surface hydroxylation process, soak after washing, dry;
(2) the mineral filler silane coupling agent of step (1) is processed;
(3) graphene oxide powder or graphene oxide water solution are joined in the MES buffered soln of pH=5.8-6.0, form mixing solutions, adding the whole pH of the laggard step of graphene oxide keeps the pH of mixing solutions to be 5.8-6.0, then in mixing solutions, EDC and NHS is added successively, supersound process 1 ~ 3h;
(4) in the solution of step (3), add the mineral filler after silane coupling agent process, carry out amidate action under room temperature, with graphene oxide, mineral filler is modified; Filtration after reaction, washing, drying, obtain graphene oxide and modify mineral filler;
Described silane coupling agent is the silane coupling agent of one end with amino; Described EDC is 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, and described NHS is N-hydroxy-succinamide, and described MES buffered soln is 2-(N-morpholine) ethyl sulfonic acid buffered soln.
2. method according to claim 1, is characterized in that: described mineral filler is hollow glass micropearl or glass fibre; The carboxyl-content of described graphene oxide is 8-12%.
3. method according to claim 2, is characterized in that: the carboxyl-content of described graphene oxide is 10-12%.
4. the method according to claim 1,2 or 3, is characterized in that: in step (3), and the consumption of EDC and NHS is 1:10 ~ 20:10 ~ 20 according to the mol ratio of the carboxyl in graphene oxide: EDC:NHS.
5. method according to claim 4, is characterized in that: in step (3), and the consumption of EDC and NHS is 1:20:15 according to the mol ratio of the carboxyl in graphene oxide: EDC:NHS.
6. method according to claim 1 and 2, is characterized in that: in step (3), and the concentration of graphene oxide in mixing solutions is 0.1 ~ 5.0mg/ml; In step (4), the consumption of mineral filler is 5 ~ 20% of solution quality in step (3).
7. method according to claim 1 and 2, is characterized in that: in step (3), and the concentration of MES buffered soln is 1mol/L, adjusts pH of mixed to 5.8-6.0 by the NaOH solution of 1mol/L; In step (4), the time of amidate action is 24 ~ 48h.
8. method according to claim 1, is characterized in that: in step (1), and vitriol oil concentration is 98wt%, and hydrogen peroxide concentration is 30wt%; The volume ratio of the vitriol oil and hydrogen peroxide is 7:3; The consumption of mineral filler is 10% of the vitriol oil and hydrogen peroxide mixed solution quality.
9. method according to claim 1, is characterized in that the step of silane coupling agent treatment inorganic filling material is:
A. water and dehydrated alcohol are mixed with solution with the mass ratio of 45:5, with glacial acetic acid regulator solution pH=6.0, in solution, drip silane coupling agent while stirring, stop when adding to silane coupling agent concentration be in the solution 0.5wt%, continue to stir 1.5h and coupling agent is hydrolyzed;
B., after coupling agent hydrolysis, readjust pH value of solution to 6.0, then add the mineral filler of solution quality 10% wherein, at 60 DEG C, stir 40min, suction filtration, washing, dry.
10. method according to claim 1, is characterized in that the preparation method of graphene oxide water solution or powder is:
A. under room temperature, 0.5 weight part SODIUMNITRATE, 1 parts by weight of graphite powder and the 46 weight part 98wt% vitriol oils are mixed under condition of ice bath, stir 30min, and then slowly add 3 weight part potassium permanganate, stir 30min;
B. the reaction system in step a is heated to 35 DEG C, stirs 2 ~ 48h, obtain brown suspension; In suspension, add 50 parts by weight of deionized water lentamente, stir, be warming up to 98 DEG C and continue reaction 5 ~ 10min, be cooled to room temperature;
C. the reaction solution of step b is poured in 167 parts by weight of deionized water while stirring, add 5 weight part 30wt% hydrogen peroxide, leave standstill 24h;
D. lower sediment is got, with deionized water centrifuge washing three times under 8000r/min condition, each 5 ~ 10min; Precipitate with deionized water is dialysed, until BaCl
2detect without SO
4 2-after dialysis, thick liquid is added in deionized water, supersound process 1h, then by solution centrifugal 5 ~ 10min under the condition of 4000 ~ 8000r/min, gained supernatant liquid is graphene oxide water solution, graphene oxide solution is utilized freeze-drying to obtain graphene oxide powder.
The 11. graphene oxide modification mineral fillers obtained according to the method for the graphene oxide chemically modified mineral filler according to any one of claim 1-10.
The preparation method of 12. 1 kinds of mineral filler/epoxy resin composite materials, it is characterized in that: obtain graphene oxide according to the method for the graphene oxide chemically modified mineral filler according to any one of claim 1-10 and modify mineral filler, then obtained mineral filler/epoxy resin composite material is reacted in the modification mineral filler of the graphene oxide of gained and epoxy resin.
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