CN1209280C - Method for synthesizing boron nitride from aether boron trifluoride and lithium nitride - Google Patents
Method for synthesizing boron nitride from aether boron trifluoride and lithium nitride Download PDFInfo
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- CN1209280C CN1209280C CN 200310101642 CN200310101642A CN1209280C CN 1209280 C CN1209280 C CN 1209280C CN 200310101642 CN200310101642 CN 200310101642 CN 200310101642 A CN200310101642 A CN 200310101642A CN 1209280 C CN1209280 C CN 1209280C
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- nitride
- boron
- boron trifluoride
- lithium nitride
- aether
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 46
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910015900 BF3 Inorganic materials 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract 16
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 title claims abstract 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract 2
- 238000004729 solvothermal method Methods 0.000 claims abstract 2
- 239000012467 final product Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 3
- 239000012530 fluid Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 238000005063 solubilization Methods 0.000 abstract 1
- 230000007928 solubilization Effects 0.000 abstract 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 24
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 11
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 10
- 238000000227 grinding Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 229910001573 adamantine Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
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Abstract
The present invention provides a method for synthesizing boron nitride from boron trifluoride aether and lithium nitride. A solvothermal synthesis method is adopted, benzene is used as a solvent, the lithium nitride is used as a nitrogen source, and the boron trifluoride aether is used as a boron source for synthesizing the boron nitride. The heating temperature of a reaction kettle is between 250 and 500 DEG C. Reaction products contain hexagonal boron nitride and cubic boron nitride in nanometer levels. The present invention has the concrete technology: the benzene is poured into the reaction kettle at first and the lithium nitride is added; the benzene and the lithium nitride are stirred; then, the boron trifluoride aether is added so that the proportion of the quality of the added lithium nitride, to the volume of the boron trifluoride aether is maintained in that 5 ml to 10 ml of the boron trifluoride aether is contained in each gram of lithium nitride. After sufficient stirring, the reaction kettle is sealed; then, through temperature rise, heat preservation and natural cooling, reaction products are taken out and are dissolved by deionized water, and then a centrifugal machine is used for centrifugation and supernatant fluid is removed. the processes of solubilization and centrifugation are repeated, and obtained products are soaked by 2 mol/l of hydrochloric acid; after washing and centrifugation, precipitates are taken out and are dried. The present invention has the advantages of cheap cost of raw materials, and little toxicity.
Description
Technical field
The invention belongs to the boron nitride preparing technical field, particularly providing a kind of is raw material with boron trifluoride diethyl etherate and lithium nitride, and benzene is solvent, adopts the method for solvent thermal synthesizing mean synthesis of nano hexagonal boron nitride and cubic boron nitride under the low pressure condition.
Background technology
Boron nitride mainly contains hexagonal boron nitride and two kinds of structure types of cubic boron nitride.Wherein the high reactivity that nano-hexagonal boron nitride had, high-insulativity, high thermal conductivity and low melting point characteristic make it can be used as low melting point insulating material and sealing material, the additive that is used for catalyzer and special purpose coating, and as the raw material that synthesizes the large size polycrystalline cubic boron nitride.Cubic boron nitride is that hardness only is lower than adamantine superhard material, but when the grinding ferrous metal performance more superior than diamond is arranged, and the various tool of making of cubic boron nitride is applied in field of machining.It still is the wideest semiconductor material in forbidden band, can be used for making energetic ray window and high temperature semiconductors; Its capacity of heat transmission only is lower than diamond, can be used as the radiator element of high-end electronic products such as high-power integrated circuit and computer chip.But owing to be difficult to produce large-sized cubic boron nitride monocrystal or glomerocryst, cubic boron nitride only is used as removing material at present.
Cubic boron nitride be considered in the past to use high temperature and high pressure method (＞4GPa) synthetic, research prophesy in recent years can realize the low pressure even the normal pressure synthesis of cubic boron nitride.The experiment that under the minimal pressure condition, synthesizes at present both at home and abroad cubic boron nitride be people such as Hao at Chemistry of Materials, publish an article in provide at 2001 (8): 2457～2459, solvent process for thermosynthesizing is adopted in this experiment, with boron tribromide (BBr
3) be the boron source, lithium nitride (Li
3N) being nitrogenous source, is solvent with benzene, under 200～500 ℃ of temperature of reaction, synthesizes the hexagonal boron nitride and the cubic boron nitride of nano-scale.This experiment shows that cubic boron nitride can synthesize really under very low pressure condition, but the shortcoming that exists is that raw materials used boron tribromide costs an arm and a leg, and toxicity is very big.
Summary of the invention
The object of the present invention is to provide a kind of method with boron trifluoride diethyl etherate and the synthetic boron nitride of lithium nitride, the raw materials used boron tribromide that do not contain has solved synthetic boron nitride material toxicity and has reached expensive problem greatly
The present invention adopts solvent process for thermosynthesizing, is solvent with benzene, and lithium nitride is a nitrogenous source, take the boron trifluoride diethyl etherate as the synthetic boron nitride in boron source.250～500 ℃ of reactor Heating temperatures.Comprise nano level hexagonal boron nitride and cubic boron nitride in the reaction product.Concrete technology is:
Earlier benzene is poured in the reactor, the adding lithium nitride also fully stirs, add boron trifluoride diethyl etherate again, make the ratio of the volume of the quality of lithium nitride of adding and boron trifluoride diethyl etherate remain on the corresponding 5ml of every gram lithium nitride～10ml boron trifluoride diethyl etherate, it is airtight reactor fully to stir the back.Then reactor is warming up to 250～500 ℃ with the heat-up rate of 5～6 ℃ of per minutes, stops heating after 50～72 hours in this temperature insulation.Open reactor behind the naturally cooling, take out reaction product.Reaction product is the canescence bulky powder, and slight ammonia flavor is arranged.With the product deionized water dissolving, centrifugal with whizzer, remove supernatant liquor.Repeat this dissolving, centrifugally operated 3～5 times to remove unreacted lithium nitride and other water-soluble thing mutually.With the product that obtains with 2mol/L salt acid soak, washing again, centrifugal 3～5 times.Take out drying precipitate, get final product.Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of final product, and wherein hexagonal boron nitride is main thing phase, and cubic boron nitride thing phase diffraction peak exists but relative content is less.Fig. 2 is the Fourier transform infrared collection of illustrative plates (FTIR) of final product, and the charateristic avsorption band 801cm of hexagonal boron nitride is arranged among the figure
-1And 1449cm
-1Have (respectively the B-N stretching vibration in the respective layer and the B-N-B flexural vibration of interlayer), can know unique charateristic avsorption band 1013cm of identification cubic boron nitride simultaneously
-1Exist, can confirm to have in the product two kinds of things of hexagonal boron nitride and cubic boron nitride to coexist mutually.Calculated by XRD diffraction peak collection of illustrative plates and Scherrer formula, the mean particle size of hexagonal boron nitride particles is 40nm.
The invention has the advantages that: be the boron source with the boron trifluoride diethyl etherate, its price is far below boron tribromide, and therefore toxicity can reduce the cost of synthesis of nano boron nitride also much smaller than boron tribromide, and increases the operability in the building-up process.Boron trifluoride diethyl etherate is the complex compound that boron fluoride and ether form, and exists with the liquid phase that the phenomenon of being fuming is arranged under the normal temperature.Liquid phase carries out the mixing of raw material and makes being encapsulated in raw material in the reactor convenient than gas phase is easier.Boron trifluoride diethyl etherate is decomplexing in heat-processed, emits boron triflouride gas as the boron source that participates in reaction.
Description of drawings
Fig. 2 is the infared spectrum of present embodiment 1, and wherein X-coordinate is wave number (cm
-1), ordinate zou is transmitance (%)
Fig. 3 is the x-ray diffracting spectrum of present embodiment 2, and wherein X-coordinate is diffraction angle (2 θ/°), and ordinate zou is intensity (arbitrary unit).
Fig. 4 is the infared spectrum of present embodiment 2, and wherein X-coordinate is wave number (cm
-1), ordinate zou is transmitance (%).
Embodiment:
Embodiment 1:
(1) 50ml benzene is poured in the linerless stainless steel cauldron
(2) with the 5g lithium nitride after grinding to form fine powder in the exhausting cupboard, put into reactor
(3) in the exhausting cupboard 25ml boron trifluoride diethyl etherate is slowly poured in the reactor, stirred while pour into and make the raw material uniform mixing, sealed reactor is warming up to 300 ℃ with 5 ℃ of heat-up rates of per minute then, and insulation is 72 hours under this temperature
(4) after the cooling of question response still, open reactor and take out reaction product.Reaction product with deionized water dissolving and centrifugally remove water-soluble material, is carried out repeatedly 3 times, and then was soaked 1 hour with the dilute hydrochloric acid of 2mol/L, again with deionized water wash, centrifugal 3 times.With final product oven dry, grinding, obtain final reacting product.
Fig. 1 and Fig. 2 are respectively the X-ray diffraction spectrogram and the fourier-transform infrared collection of illustrative plates of reaction product.Test result shows, hexagonal boron nitride and cubic boron nitride two-phase coexistent in the reaction product.
Specific embodiment 2:
(1) 50ml benzene is poured in the linerless stainless steel cauldron
(2) with the 5g lithium nitride after grinding to form fine powder in the exhausting cupboard, put into reactor
(3) in the exhausting cupboard 50ml boron trifluoride diethyl etherate is slowly poured in the reactor, stirred while pour into and make the raw material uniform mixing, sealed reactor is warming up to 400 ℃ with 5 ℃ of heat-up rates of per minute then, and insulation is 60 hours under this temperature
(4) after the cooling of question response still, open reactor and take out reaction product.Reaction product with deionized water dissolving and centrifugally remove water-soluble material, is carried out repeatedly 5 times, and then was soaked 1 hour with the dilute hydrochloric acid of 2mol/L, again with deionized water wash, centrifugal 3 times.With final product oven dry, grinding, obtain final reacting product.
Fig. 3 and Fig. 4 are respectively the X ray diffracting spectrum and the fourier-transform infrared collection of illustrative plates of reaction product, and test result shows, hexagonal boron nitride and cubic boron nitride two-phase coexistent in the reaction product.Become sharp by hexagonal boron nitride X-ray diffraction peak in the reaction product, illustrate with synthesis temperature and improve that boron nitride degree of crystallinity improves.
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310101642 CN1209280C (en) | 2003-10-27 | 2003-10-27 | Method for synthesizing boron nitride from aether boron trifluoride and lithium nitride |
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| CN 200310101642 CN1209280C (en) | 2003-10-27 | 2003-10-27 | Method for synthesizing boron nitride from aether boron trifluoride and lithium nitride |
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| CN1539729A CN1539729A (en) | 2004-10-27 |
| CN1209280C true CN1209280C (en) | 2005-07-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7341702B2 (en) | 2004-12-28 | 2008-03-11 | Momentive Performance Materials Inc. | Process for producing boron nitride |
| CN106517112B (en) * | 2016-12-07 | 2019-05-07 | 湖北第二师范学院 | A kind of boron nitride nanotube for hydrogen storage and synthesis method |
| CN111268688A (en) * | 2020-03-23 | 2020-06-12 | 河北工业大学 | Method for low-temperature synthesis of boron nitride and ammonium fluoroborate |
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