CN107324296A - The method of modifying and hydroxyl modification boron nitride of hexagonal boron nitride - Google Patents
The method of modifying and hydroxyl modification boron nitride of hexagonal boron nitride Download PDFInfo
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- CN107324296A CN107324296A CN201710703594.6A CN201710703594A CN107324296A CN 107324296 A CN107324296 A CN 107324296A CN 201710703594 A CN201710703594 A CN 201710703594A CN 107324296 A CN107324296 A CN 107324296A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0648—After-treatment, e.g. grinding, purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
Abstract
The invention provides a kind of method of modifying of hexagonal boron nitride, comprise the following steps：Hexagonal boron nitride powder is pre-processed in nitric acid, the boron nitride of nitric acid pretreatment is obtained；In the mixed aqueous solution that the boron nitride of the nitric acid pretreatment is dispersed in formic acid and sulfuric acid, dispersion liquid is obtained；The dispersion liquid is subjected to gamma-ray irradiation processing, hydroxyl modification boron nitride is obtained.Present invention also offers the hydroxyl modification boron nitride that the method for modifying described in a kind of above-mentioned technical proposal is obtained.The present invention is first pre-processed hexagonal boron nitride powder in nitric acid, in the mixed aqueous solution for being then dispersed in formic acid and sulfuric acid, is carried out radiation treatment using gamma-rays, is obtained hydroxyl modification boron nitride.The method mild condition that the present invention is provided, it is easy to operate.
Description
Technical field
Change the invention belongs to the method for modifying and hydroxyl of hexagonal boron nitride technical field, more particularly to a kind of hexagonal boron nitride
Property boron nitride.
Background technology
Hexagonal boron nitride (h-BN) is the isoelectronic species of graphite, with layer structure as graphite-like, be referred to as " white
Graphite ".In addition to excellent lubricity, mechanical performance and thermal conductivity with similar graphite, h-BN is also equipped with many unique property
Can, such as good insulating (band gap width is 5.2-5.8eV), heat endurance height (temperature in use is up to 2800 DEG C in nitrogen atmosphere)
And not oxidizable (oxidizing temperature be higher than 800 DEG C), radiation hardness and good biocompatibility (Weng QH, Wang XB, Wang X,
et al.Chemical Society Reviews,2016,45(14),3989-4012；Zhi CY,Bando Y,Tang CC,
et al.Journal of Materials Chemistry,2008,18(33),3900-3908.).In recent years, received with h-BN
The research of thermal property and flame-resistant insulation that mitron or nanometer sheet improve polymeric matrix as filler causes extensive pass
Note.Research finds that adding 1wt% BN nano-particles (2 μm of average grain diameter) in the epoxy just can make releasing for epoxy resin
Hot speed peak value reduces nearly half (Yu B, Xing W, Guo W, et al.Journal of Materials Chemistry
A,2016,4(19),7330-7340.)；Add 50wt% BN nanometer sheets (1.56 μm of average length, average thickness 2.35nm)
Compound thermal conductivity can be made to improve 40 times of (Yu JH, Mo HL, Jiang PK.Polymers for Advanced
Technologies,2015,26(5),514-520.)。
However, h-BN chemical property is stable, surface lacks active group, with most of organic molecules and polymer molecular chain
Between lack strong interaction, thus organic solvent with it is dispersed very poor in polymeric matrix, which greatly limits h-BN pairs
The improvement of polymeric material performance.On the other hand, h-BN chemical inertness makes it be difficult to carry out with other substance reactions again
Surface is modified.Therefore, exploiting economy, efficient h-BN surface modification methods, strengthen its surface-active and reactivity, are high-performance
A crucial and challenging problem in prepared by polymer/BN composites.
H-BN chemical modification is the defect using h-BN surfaces earliest, makes itself and function monomer or polymer reaction,
Surface introduces alkyl chain (Zhi CY, Bando Y, Tang CC, et al.AngewandteChemie
InternationalEdition, 2005,44 (48), 7932-7935.), carbon-halogen bond (Zhi CY, Bando Y, Tang CC,
Et al.Journal of Physical Chemistry C, 2007,111 (3), 1230-1233.) and poly-methyl methacrylate
The macromolecular chains such as ester (Zhi CY, Bando Y, Wang WL, et al.Journal of Nanomaterials, 2008,1,
145.), so as to improve the dispersed and compatibilities with polymer of BN in a solvent.But the density and kind of h-BN surface defects
Class is limited to its preparation method, it is difficult to control.Afterwards, it has been proposed that using appropriate electron rich reagent such as hydrogen peroxide, organic
The elder generation such as peroxide, Cabbeen and naphthalene sodium system attack boron atom produces activated centre, then the method for being modified reaction
(Sainsbury T,O’NeillA,Passarelli MK,et al.Chemistry of Materials,2014,26(24),
7039-7050；Shin H,Guan J,Zgierski MZ,et al.ACS Nano,2015,9(12),12573-12582；Zhi
CY,Bando Y,TeraoT,et al.Chemistry-An Asian Journal,2009,4(10),1536-1540；
Sainsbury T,Satti A,May P,et al.Journal of the American Chemical Society,
2012,134(45),18758-18771.).But because B-N covalent bonds are sufficiently stable, even tried using the electron rich of high activity
Agent is also required to the harsh condition such as high temperature or strong oxidizer presence, and reaction could be carried out.Recently, Lei etc. is by BN powder and urea
Powder under 700rpm ball milling mixing 20 hours (BN is 1 with urea powder weight ratio:60), produced using high shear and collision
High-energy, obtain the thick BN nanometer sheets of 2nm, at the same time, also introduce amino on BN surfaces, substantially increase BN nano-particles
Dispersiveness in water, dispersion liquid concentration can reach 30mg/mL, and the BN nano-particles of method of modifying processing is scattered than before
Concentration improve nearly 30 times (Lei WW, Mochalin VN, Liu D, et al.NatureCommunications 2015,6,
8849.).Generally speaking, activated centre is produced on inert BN surfaces needs to inject very high energy, makes existing method of modifying
The reaction condition of harshness is directed to, therefore simple, the efficient and environmentally friendly BN method of modifying of exploitation is to promotion BN application value weight
Greatly.
The content of the invention
In view of this, nitrogenized it is an object of the invention to provide a kind of method of modifying of hexagonal boron nitride and hydroxyl modification
Boron, the method for modifying mild condition that the present invention is provided, it is easy to operate, and obtained hydroxyl modification boron nitride is easy to further change
Property.
The invention provides a kind of method of modifying of hexagonal boron nitride, comprise the following steps：
Hexagonal boron nitride powder is pre-processed in nitric acid, the boron nitride of nitric acid pretreatment is obtained；
In the mixed aqueous solution that the boron nitride of the nitric acid pretreatment is dispersed in formic acid and sulfuric acid, dispersion liquid is obtained；
The dispersion liquid is subjected to gamma-ray irradiation processing, hydroxyl modification boron nitride is obtained.
The present invention is first pre-processed hexagonal boron nitride powder in nitric acid, is then dispersed in formic acid and sulfuric acid
Mixed aqueous solution in, using gamma-rays carry out radiation treatment, obtain hydroxyl modification boron nitride.The method condition that the present invention is provided
Gently, it is easy to operate.
The present invention is first pre-processed hexagonal boron nitride powder in nitric acid, obtains the boron nitride of nitric acid pretreatment.
In one embodiment, the mass fraction of the nitric acid is 10%~30%.In one embodiment, the temperature of the pretreatment
For 80~90 DEG C, pretreatment time is 5~8h.
The pretreatment is carried out preferably under conditions of stirring, and pretreatment divides the centrifugation of obtained pretreatment fluid after finishing
From washing can obtain the boron nitride of nitric acid pretreatment after drying.Specifically, the pretreatment can be grasped according to following steps
Make：
Weigh h-BN powder to be put in round-bottomed flask, salpeter solution is added thereto, and be put into stirring magneton.Round-bottomed flask
It is placed in oil bath, starts magnetic agitation, heats and keep after certain time, naturally cool to room temperature.Pretreatment fluid is placed in height
In fast centrifuge, with 6000~10000rpm rotating speed, the BN particles of nitric acid treatment are centrifuged, and is floated with deionized water
Wash, to cleaning solution in neutrality.Treated product dries 20~30h at 40~80 DEG C.
After the boron nitride for obtaining nitric acid pretreatment, in the mixed aqueous solution for being dispersed in formic acid and sulfuric acid, disperseed
Liquid, then carries out radiation treatment using gamma-rays, obtains hydroxyl modification boron nitride.In one embodiment, in the dispersion liquid,
Formic acid concn is 0.01~0.1mol/L, and sulfuric acid concentration is 0.4mol/L, and the concentration of the boron nitride of nitric acid pretreatment is 1~2mg/
mL。
The boron nitride of nitric acid pretreatment is dispersed in the mixing water of formic acid and sulfuric acid by the present invention preferably under conditions of stirring
In solution, and radiation treatment is carried out to obtained dispersion liquid under conditions of stirring, by obtained solution left standstill after being disposed
Make particle deposition, the cleaning of obtained particle, drying can be obtained into the boron nitride of hydroxyl modification.Specifically, can according to
Lower step process：
The BN powder of nitric acid pretreatment is put in round-bottomed flask, deionized water is added, being placed in ultrasonic disperse instrument makes powder
Last ultrasonic disperse is uniform.Formic acid and the concentrated sulfuric acid are sequentially added wherein, and are put into stirring magneton.Round-bottomed flask is fixed with iron stand
It is placed in cobalt source room, starts magnetic agitation, irradiated, round-bottomed flask is taken out in irradiation after terminating, stands after a period of time, make grain
Son deposition.Supernatant liquid is poured out, sediment is rinsed to cleaning solution in neutrality with deionized water, clean sediment is 40~80
DEG C dry 10~20h, produce hydroxyl modification BN powder (HO-BN).
In one embodiment of the invention, use60Co gamma-rays carries out radiation treatment to the dispersion liquid；The irradiation
The absorbed dose rate of processing is 80~120Gy/min, and total absorbed dose is more than 100kGy.
After the boron nitride for obtaining hydroxyl modification, it can also be further modified, obtain what other groups were modified
Boron nitride.
In one embodiment, the boron nitride of hydroxyl modification can be further modified using Functional siloxane,
Step is as follows：
The hydroxyl modification hexagonal boron nitride is dispersed in Functional siloxane solution, heating response.
In the present invention, the Functional siloxane is the silica for containing functional group, such as epoxy radicals, double bond or amino
Alkane, can be commercially available silane coupler, such as KH series.In siloxane solution the volume fraction of siloxanes be 0.5%~
3%, concentration is 1~4mg/mL after the hydroxyl modification boron nitride is dispersed in Functional siloxane solution；The heating response
Temperature be 70~130 DEG C, the reaction time be 7~10h.
The present invention preferably makes boron nitride and the Functional siloxane reaction of hydroxyl modification under conditions of stirring, and reaction is finished
Product is washed afterwards, dried, you can the boron nitride of other functional groups modification is obtained.Specifically, it can be according to following step
Rapid operation：
HO-BN nano powders are placed in three-necked flask, toluene is added, being placed in ultrasonic disperse instrument makes powder ultrasonic scattered equal
It is even, silane coupler is added, and stirring magneton is put into, heating response, reacts after terminating under magnetic stirring, and standing makes product sink
Product.Supernatant liquid is poured out, after toluene rinsing product 3 times, is placed at 40~80 DEG C and dries 10~20h, obtain other functions
Group modified BN nano powders.
In one embodiment, the boron nitride of hydroxyl modification can also be further modified using reaction monomers, step is such as
Under：
The hydroxyl modification boron nitride is dispersed in vinyl monomer solution, polymerization inhibitor is added, second is carried out and irradiates
Processing, obtains polymer modification boron nitride.
In the present invention, the vinyl monomer is preferably polar ethylene class monomer, including but not limited to acrylic acid, propylene
Sour methyl esters or GMA；The absorbed dose rate of second of the irradiation is 20~35Gy/min, total to absorb
Dosage is 20~45kGy.
The present invention preferably makes hydroxyl modification boron nitride be reacted with vinyl monomer under conditions of stirring, in stirring
Under the conditions of carry out second and irradiate, irradiation terminates rear suction filtration, dries and can obtain polymer modification boron nitride.Specifically, its
Operating procedure is as follows：
Hydroxyl modification BN nano powders are placed in round-bottomed flask, deionized water and CuSO is added4·5H2O, flask is placed in
Make powder ultrasonic be uniformly dispersed in ultrasonic disperse instrument to add vinyl monomer and be put into stirring magneton, system leads to nitrogen, sealing is put into
In cobalt source room, irradiate under magnetic stirring.After irradiation terminates, system aperture is 0.22 μm of cellulose microfiltration membranes suction filtration, institute
Filter cake is obtained again to disperse in deionized water, then suction filtration, it is repeated several times no longer muddy to filtrate.Filter cake is placed at 40~80 DEG C
Dry 10~20h.
The present invention is pre-processed hexagonal boron nitride powder in nitric acid, is then dispersed in mixing for formic acid and sulfuric acid
In Heshui solution, radiation treatment is carried out using gamma-rays, hydroxyl modification boron nitride is obtained.The present invention utilizes the aqueous solution and BN spoke
Chemical effect is penetrated, simple, the efficient active function groups for realizing h-BN nano-particles are modified, and make its dispersiveness and chemism
Increase, expands its application, possibility is provided to prepare high performance polymer/BN nano composite materials.With other modifications
Method is compared, and this method directly carries out simple efficient surface to h-BN using gamma Rays technology at normal temperatures and pressures and changed
Property, with mild condition, it is easily operated, environment-friendly and energy-efficient the characteristics of.Meanwhile, hydroxyl modification BN nano powders can be after
It is continuous to be scattered in reaction medium, further obtain other active function groups or the BN nano powders of polymer modification.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the infrared spectrum of h-BN before and after nitric acid treatment；
The TG curves that Fig. 2 is heated in atmosphere for h-BN before and after nitric acid treatment；
Fig. 3 is HO-BN prepared by embodiment 1 infrared spectrum；
Fig. 4 is the TG curves that HO-BN prepared by embodiment 1 is heated in atmosphere；
Fig. 5 is HO-BN prepared by embodiment 2 infrared spectrum；
Fig. 6 is the TG curves that HO-BN prepared by embodiment 2 is heated in atmosphere；
Fig. 7 is EP-BN infrared spectrums prepared by embodiment 3；
Fig. 8 is the TG curves that EP-BN prepared by embodiment 3 is heated in atmosphere；
Fig. 9 is PAA-BN prepared by embodiment 4 infrared spectrum；
Figure 10 is the TG curves that PAA-BN prepared by embodiment 4 is heated in atmosphere；
Figure 11 is the FT-IR spectrograms for the product that comparative example 1 of the present invention is obtained；
Figure 12 is the TG curves that the product that comparative example 1 of the present invention is obtained is heated in atmosphere；
Figure 13 is the FT-IR spectrograms for the product that comparative example 2 of the present invention is obtained.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
In following examples, commodity h-BN is purchased from GE Reagent Companies, purity >=99%, and remaining reagent is that analysis is pure.
The preparation of the hydroxyl modification boron nitride (HO-BN) of embodiment 1
1) commodity h-BN powder pre-treatings
Weigh 2g commodity h-BN powder to be put in 250mL round-bottomed flasks, 80mL10% salpeter solution is added thereto
(65% nitric acid:Water=1:5.5 (v/v)), and it is put into stirring magneton.Round-bottomed flask is placed in oil bath, starts magnetic agitation, heating
To 80 DEG C, keep after 5h, naturally cool to room temperature, obtain dispersion liquid.Dispersion liquid is placed in supercentrifuge (HC-2518),
With 8000rpm rotating speed, BN particles are centrifuged, and rinsed with deionized water, to cleaning solution in neutrality, treated product
24h is dried in 50 DEG C of electric drying oven with forced convections (GZX-9070MBE).FT-IR spectrum such as Fig. 1 institutes of BN powder before and after pretreatment
Show, Fig. 1 is the infrared spectrum of h-BN before and after nitric acid treatment, and as shown in Figure 1, both have essentially no difference, 1395cm-1Absworption peak
It is attributed to stretching vibration in the face of B-N keys, 804cm-1Absworption peak be attributed to the out-of-plane bending vibrations of B-N-B keys.But pretreatment
The front and rear aerial thermal weight loss of BN powder (TG) curve is as shown in Fig. 2 Fig. 2 is heated in atmosphere for h-BN before and after nitric acid treatment
TG curves, both, which have in bigger difference, commodity BN powder, as shown in Figure 2 may contain micro oxidizable group, cause in sky
Quality has increased slightly on the contrary when being heated in gas.And the BN after nitric acid treatment be heated in atmosphere after 300 DEG C it is slightly weightless (about
0.5%), illustrate that nitric acid can all aoxidize micro oxidizable group on BN.
2) BN powder radiation hydroxylating is modified
Weigh the BN powder after 100mg nitric acid treatments to be put in 100mL round-bottomed flasks, add 50mL deionized waters, be placed in
Powder ultrasonic is set to be uniformly dispersed in ultrasonic disperse instrument.20 μ L formic acid and the 1.1mL concentrated sulfuric acids are sequentially added wherein, and are put into stirring
Magneton.Round-bottomed flask is fixed with iron stand to be placed in cobalt source room, starts magnetic agitation, irradiates 24h, and absorbed dose rate is
113.4Gy/min (ferrous sulfate dosimeter demarcation), total absorbed dose is 163.3kGy.Irradiation takes out round-bottomed flask after terminating,
Stand after a period of time, make particle deposition.Supernatant liquid is poured out, sediment is rinsed to cleaning solution in neutrality with deionized water.
Clean sediment dries 24h in 50 DEG C of electric drying oven with forced convections (GZX-9070MBE), produces hydroxyl modification BN powder (HO-
BN), its FTIR spectrum is as shown in figure 3, Fig. 3 is HO-BN prepared by embodiment 1 infrared spectrum, predose BN in comparison diagram 1
Infrared spectrum, the BN of irradiated processing is in 1155cm-1There is new absworption peak in place, and this should belong to B-O-H bendings in B-OH and shake
Dynamic (Kurapati R, Backes C, M é nard-Moyon C, et al.AngewandteChemie, 2016,128 (18),
5596-5601.), illustrate to have been introduced into-OH functional groups on BN.The TG curves that the BN of irradiated processing is heated in atmosphere are such as
Shown in Fig. 4, Fig. 4 is the TG curves that heat in atmosphere of HO-BN prepared by embodiment 1, Fig. 4 is shown sample when being heated to 300 DEG C
Start thermal weight loss occur, until 600 DEG C to constant weight, total weight loss rate is about 22%, and the BN being modified in document with other method loses
Again rate it is general below 5% (Cui Z, Oyer AJ, Glover AJ, Schniepp HC, Adamson DH.Small, 2014,
10(12),2352-2355；Yu B,Xing W,Guo W,Qiu S,Wang X,Lo S,Hu Y.Journal of
Materials Chemistry A, 2016,4 (19), 7330-7340.), this result shows hydroxyl modification journey of the radiation method to BN
Degree is much higher compared with other method.
The preparation of the hydroxyl modification boron nitride (HO-BN) of embodiment 2
1) h-BN powder pre-treatings are same as Example 1.
2) HO-BN preparation
The h-BN powder after 100mg nitric acid treatments is weighed in 100mL round-bottomed flasks, 50mL deionized waters is added, is placed in
Powder ultrasonic is set to be uniformly dispersed in ultrasonic disperse instrument.20 μ L formic acid and the 1.1mL concentrated sulfuric acids are sequentially added wherein again, and is put into and stirs
Mix magneton.Round-bottomed flask is fixed with iron stand to be placed in cobalt source room, starts magnetic agitation, irradiates 48h, and absorbed dose rate is
105.4Gy/min (ferrous sulfate dosimeter demarcation), total absorbed dose is 303.4kGy.Irradiation takes out round-bottomed flask after terminating,
Stand after a period of time, make particle deposition.Supernatant liquid is poured out, sediment is rinsed to cleaning solution in neutrality with deionized water.
Clean sediment dries 24h in 50 DEG C of electric drying oven with forced convections (GZX-9070MBE), that is, obtains HO-BN nano-particles, its
FTIR spectrograms as shown in figure 5, Fig. 5 be embodiment 2 prepare HO-BN infrared spectrum, as shown in Figure 5,1155cm-1There is B- in place
O-H characteristic absorption peak.TG curves in air are as shown in fig. 6, Fig. 6 is what HO-BN prepared by embodiment 2 was heated in atmosphere
TG curves, it will be appreciated from fig. 6 that being heated to 400 DEG C starts obvious thermal weight loss occur, until 600 DEG C.Total weight loss percentage is about
38%.
The epoxide group of embodiment 3 is modified the preparation of boron nitride (EP-BN)
1) h-BN powder pre-treatings are same as Example 1.
2) HO-BN preparation
The h-BN powder after 100mg nitric acid treatments is weighed in 100mL round-bottomed flasks, 50mL deionized waters is added, is placed in
Powder ultrasonic is set to be uniformly dispersed in ultrasonic disperse instrument.20 μ L formic acid and the 1.1mL concentrated sulfuric acids are sequentially added wherein again, and is put into and stirs
Mix magneton.Round-bottomed flask is fixed with iron stand to be placed in cobalt source room, starts magnetic agitation, irradiates 18h, and absorbed dose rate is
101.3Gy/min (ferrous sulfate dosimeter demarcation), total absorbed dose is 109kGy.Irradiation takes out round-bottomed flask after terminating, quiet
Put after a period of time, make particle deposition.Supernatant liquid is poured out, sediment is rinsed to cleaning solution in neutrality with deionized water.Wash
Net sediment dries 24h in 50 DEG C of electric drying oven with forced convections (GZX-9070MBE), that is, obtains HO-BN nanometer powders.
3) EP-BN preparation
Weigh 80mg steps 2) prepare HO-BN nano powders in 50mL three-necked flasks, add 20mL toluene, be placed in ultrasound
Powder ultrasonic is set to be uniformly dispersed in separating apparatus.Weigh 360mg silane couplers KH560 and add above-mentioned dispersion liquid, and be put into stirring
Magneton.115 DEG C are heated under magnetic stirring, react 7h.After reaction terminates, standing makes product deposition.Supernatant liquid is poured out,
After toluene rinsing product 3 times, it is placed in 50 DEG C of electric drying oven with forced convections (GZX-9070MBE) and dries 12h, obtain EP-BN and receive
Ground rice, FTIR spectrograms are as shown in fig. 7, Fig. 7 is EP-BN infrared spectrums prepared by embodiment 3.Contrast HO-BN infrared spectrum (figure
3 and Fig. 5), it can be seen that in 917cm-1And 840cm-1There is new absworption peak in left and right, and this is respectively belonging to the ring of epoxide group
The in-plane deformation vibration of symmetrical stretching vibration and ring, illustrates that epoxide group has been introduced on BN nano-particles.EP-BN nano powders exist
The TG curves that are heated in air, can be with as shown in figure 8, Fig. 8 is the TG curves that EP-BN prepared by embodiment 3 is heated in atmosphere
See there are two thermal weight loss intervals, respectively 270~400 DEG C and 400~600 DEG C.Contrast HO-BN TG curves (Fig. 4 and figure
6), 270~400 DEG C of thermal weight loss should correspond to the decomposition of epoxide group.
The preparation of the polyacrylic acid modified boron nitride nanometer particle (PAA-BN) of embodiment 4
The HO-BN nano powders prepared in 40mg embodiments 3 are weighed to be placed in 50mL round-bottomed flasks.Add 25mL deionized waters
And 34.5mgCuSO4·5H2After O, flask, which is placed in ultrasonic disperse instrument, makes powder ultrasonic be uniformly dispersed.Weigh 2.5mL and refine propylene
Acid is added in dispersion liquid, and is put into stirring magneton.System leads to nitrogen 10min, and sealing is put into cobalt source room.Spoke under magnetic stirring
According to 18h, absorbed dose rate is 22.8Gy/min (ferrous sulfate dosimeter demarcation), and total absorbed dose is 24.6kGy.Irradiation terminates
Afterwards, system aperture is 0.22 μm of cellulose microfiltration membranes suction filtration.Gained filter cake disperses in deionized water again, then suction filtration.
It is repeated several times no longer muddy to filtrate.Filter cake is placed in 50 DEG C of electric drying oven with forced convections (GZX-9070MBE) and dries 12h, is obtained
To PAA-BN, as shown in Figure 9, Fig. 9 is PAA-BN prepared by embodiment 4 infrared spectrum to its FTIR spectrogram, as shown in Figure 9,
875cm-1And 1795cm-1There is B-C and C=O characteristic absorption peak in place, illustrates to be grafted PAA on BN.PAA-BN is in atmosphere
As shown in Figure 10, Figure 10 is the TG curves that PAA-BN prepared by embodiment 4 is heated in atmosphere to the TG curves of heating, can by Figure 10
Know occur thermal weight loss since 220 DEG C, also illustrate the presence of organic carbon skeleton in PAA-BN.
Comparative example 1
Identical with the operating procedure of embodiment 1, difference is, does not carry out nitric acid pretreatment to hexagonal boron nitride.Products therefrom
FT-IR spectrograms as shown in Figure 11, Figure 11 is the FT-IR spectrograms for the product that comparative example 1 of the present invention is obtained, itself and raw material nitrogen
The infrared spectrum for changing boron has essentially no difference, not in 1155cm-1There is B-O-H flexural vibrations absworption peak in B-OH in place.Together
When, the aerial thermal weight loss of the product (TG) curve see Figure 12, Figure 12 be the product that obtains of comparative example 1 of the present invention in atmosphere
The TG curves of heating, it is also without obvious thermal weight loss.This result shows, to obtaining hydroxyl modification nitrogen the step of nitric acid pretreatment
It is necessary to change boron.
Comparative example 2
Identical with the operating procedure of embodiment 1, difference is, the hexagonal boron nitride of Nitric Acid Modified is dispersed in the sulphur of same concentrations
In acid solution.As shown in Figure 13, Figure 13 is the FT-IR for the product that comparative example 2 of the present invention is obtained to the FT-IR spectrograms of products therefrom
Spectrogram, the infrared spectrum of itself and feedstock boron nitride has essentially no difference, and occurs B-O-H in B-OH at 1155cm-1
Flexural vibrations absworption peak.This result shows that the presence of formic acid is also necessary to obtaining hydroxyl modification boron nitride.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method of modifying of hexagonal boron nitride, it is characterised in that comprise the following steps：
Hexagonal boron nitride powder is pre-processed in nitric acid, the boron nitride of nitric acid pretreatment is obtained；
In the mixed aqueous solution that the boron nitride of the nitric acid pretreatment is dispersed in formic acid and sulfuric acid, dispersion liquid is obtained；
The dispersion liquid is subjected to gamma-ray irradiation processing, hydroxyl modification boron nitride is obtained.
2. method of modifying according to claim 1, it is characterised in that the mass fraction of the nitric acid is 10%~30%；
The temperature of the pretreatment is 80~90 DEG C, and pretreatment time is 5~8h.
3. method of modifying according to claim 2, it is characterised in that in the dispersion liquid, formic acid concn is 0.01~
0.1mol/L, sulfuric acid concentration is 0.4mol/L, and the concentration of the boron nitride of nitric acid pretreatment is 1~2mg/mL.
4. method of modifying according to claim 3, it is characterised in that use60Co gamma-rays carries out spoke to the dispersion liquid
According to processing.
5. method of modifying according to claim 4, it is characterised in that the absorbed dose rate of the radiation treatment is 80~
120Gy/min, total absorbed dose is more than 100kGy.
6. the method for modifying according to Claims 1 to 5 any one, it is characterised in that also include：
The hydroxyl modification boron nitride is dispersed in Functional siloxane solution, heating response.
7. method of modifying according to claim 6, it is characterised in that the hydroxyl modification boron nitride is dispersed in feature silicon
Concentration is 1~4mg/mL after in oxygen alkane solution；
The temperature of heating response is 70~130 DEG C, and the reaction time is 7~10h.
8. the method for modifying according to Claims 1 to 5 any one, it is characterised in that also include：
The hydroxyl modification boron nitride is dispersed in vinyl monomer solution, polymerization inhibitor is added, second of radiation treatment is carried out.
9. method of modifying according to claim 8, it is characterised in that the vinyl monomer is selected from acrylic acid, acrylic acid
Methyl esters or GMA；
The absorbed dose rate of second of the irradiation is 20~35Gy/min, and total absorbed dose is 20~45kGy.
10. the hydroxyl modification boron nitride that the method for modifying described in Claims 1 to 5 any one is obtained.
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