CN104860973B - The purification process of trimethyl gallium - Google Patents
The purification process of trimethyl gallium Download PDFInfo
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- CN104860973B CN104860973B CN201510239398.9A CN201510239398A CN104860973B CN 104860973 B CN104860973 B CN 104860973B CN 201510239398 A CN201510239398 A CN 201510239398A CN 104860973 B CN104860973 B CN 104860973B
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- trimethyl gallium
- chromatographic column
- filler
- purification process
- surface grafting
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- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000746 purification Methods 0.000 title claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 19
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 230000005484 gravity Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 230000000640 hydroxylating effect Effects 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- DRKSQNOZVVFYQE-UHFFFAOYSA-N n-(2-triethoxysilylethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCNC1=CC=CC=C1 DRKSQNOZVVFYQE-UHFFFAOYSA-N 0.000 claims 1
- -1 phenylaminoethyl Chemical group 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000003883 substance clean up Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000011049 filling Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 229910005263 GaI3 Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical group CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004871 chemical beam epitaxy Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- FWLGASJILZBATH-UHFFFAOYSA-N gallium magnesium Chemical compound [Mg].[Ga] FWLGASJILZBATH-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JDDAMKOBLWFNCZ-UHFFFAOYSA-N n-(2-trimethoxysilylethyl)aniline Chemical compound CO[Si](OC)(OC)CCNC1=CC=CC=C1 JDDAMKOBLWFNCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of high-efficiency purifying method of trimethyl gallium, belong to the technical field of compound purification.Purification process of the invention is comprised the following steps：First, the first chromatographic column with fixing phase as filler is filtered to trimethyl gallium crude product；Then, purified in the second chromatographic column of the filler to the trimethyl gallium crude product after filtering with fixing phase as surface grafting, and the filler of the surface grafting has the filler of tri-n-octyl amine for surface grafting.Purification process of the invention combines the means of separation of solid and liquid, and specific complexant is supported on filler, not only simple to operate, and further increases purification effect.
Description
Technical field
The invention belongs to the technical field of compound purification, more particularly, it relates to a kind of trimethyl gallium is pure
Change method.
Background technology
High-purity trimethyl gallium is widely used in the compound semiconductor film materials such as growth indium gallium phosphorus, indium gallium arsenic nitrogen, indium gallium arsenic
Material, is to grow photoelectron material most during metal organic chemical vapor deposition technology (MOCVD), chemical beam epitaxy (CBE)
Raw material that is important, being also current consumption maximum.In order to meet photoelectron material high-purity, high-precision quality requirement, (purity is not
Enough trimethyl galliums can be had a huge impact to the performance of chip, and very big infringement is also had to MOCVD device), it is desirable to it is high
The purity of pure trimethyl gallium reaches 99.9999%, is otherwise accomplished by further purification.
In the prior art, the method for preparation of industrialization trimethyl gallium, in the reactor full of inert gas, puts into gallium magnesium
Alloy raw material, in the presence of ether solvent (ether, tetrahydrofuran or methyltetrahydrofuran), is gradually added halogen under agitation
For alkane (bromoethane or iodoethane), solvent refluxing speed is controlled by controlling the rate of addition of alkyl halide, after the completion of reaction, will be molten
Agent is steamed, then obtains the complex of trimethyl gallium and ether at reduced pressure conditions, is finally de-coordinated and is obtained trimethyl gallium；The de-coordination
Temperature is 80~150 DEG C.
Trimethyl gallium is due to the limitation of preparation technology so that it is difficult to separate with reaction dissolvent, and existing mode is to select ether
The complexants such as class are coordinated, and low boiling point solvent is then removed under intensification and vacuum condition, then again under elevated temperature in vacuo
De-coordination obtains crude product, then obtains high purity product again by rectifying.Most of complexant belongs to macromolecular higher boiling liquid, and
Viscosity is higher, and small molecule low boiling impurity is easily wrapped in macromolecular higher boiling complexant the inside, it is not easy to be divided, purity
Typically it is only capable of reaching 95.0~99.0%.Another aspect prior art is the purity for ensureing trimethyl gallium, can select to abandon one
Divide trimethyl gallium, allow it to be carried in the lump with low boiling impurity, but due to trimethyl gallium self character, cause this portion to work
It is dangerous larger, not easy to operate, difficulty is higher.
The content of the invention
In order to solve above-mentioned technical problem of the prior art, it is an object of the invention to provide a kind of the pure of trimethyl gallium
Change method.
To achieve these goals, present invention employs following technical scheme：
A kind of purification process of trimethyl gallium, it is characterised in that comprise the following steps：First, with fixing phase as filler
One chromatographic column is filtered to trimethyl gallium crude product；Then, to the trimethyl gallium crude product after filtering with fixing phase as surface grafting
Filler the second chromatographic column in purified, and the filler of the surface grafting has filling out for tri-n-octyl amine for surface grafting
Material；Described filler is the one kind in aluminum oxide, titanium dioxide, zirconium dioxide or urea formaldehyde resin microsphere.
Wherein, the purity of the trimethyl gallium is 95.0~99.0%.
Wherein, the particle diameter of described filler is 3~10 μm.
Wherein, the filler of the surface grafting is prepared by the following method and obtains：It is surface-treated using amino silane,
Then tri-n-octyl amine is grafted again.
Wherein, the mass ratio of described filler, amino silane and tri-n-octyl amine is：30~120：3~6：8~12.
Wherein, the amino silane is selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, phenylamino
Base ethyl triethoxysilane, phenylaminoethyl trimethoxy silane, N- β (aminoethyl)-gamma-aminopropyl-triethoxy-silane,
In N- β (aminoethyl)-γ-aminopropyltrimethoxysilane or N- β (aminoethyl)-γ-aminopropyl ethyl diethoxy silane
At least one, preferably gamma-aminopropyl-triethoxy-silane.
Wherein, described filler first carried out hydroxylating treatment before being surface-treated using amino silane.
Wherein, the purification process is comprised the following steps：(1) trimethyl gallium crude product is poured into the first chromatographic column, is relied on
Gravity flows down naturally, treats that liquid flow is complete, collects solution；(2) solution of collection is poured into the second chromatographic column, by gravity nature
Flow down, treat the complete collection solution of liquid flow；The solution collected is poured into the second chromatographic column again again, is repeated 2~5 times；(3) it is right
Carry out heating de-coordination by the second chromatographic column after step (2) treatment, and chromatography column bottom vacuumize collection can obtain it is pure
The trimethyl gallium of change；And it is 80~100 DEG C to heat the temperature of de-coordination.
Compared with prior art, the purification process of trimethyl gallium of the present invention has the advantages that：
Purification process purification process of the invention of the invention combines the means of separation of solid and liquid, and specific complexant is born
It is loaded on filler, it is not only simple to operate, and purification effect is further increased, having obtained purity can reach the front three of 6N
Base gallium.
Specific embodiment
The purification process of trimethyl gallium of the present invention is further elaborated below with reference to specific embodiment, with
More complete explanation is made to inventive concept of the invention and its effect.
Embodiment 1
The silica white that 100g particle diameters are 5 μm is fitted into chromatographic column (internal diameter is 10mm), pressurization ensures that filling is uniform, you can
Obtain the first chromatographic column.
The amorphous silica gel that 100g particle diameters are 5 μm is dispersed in the reactor equipped with anhydrous toluene solution, then 60
Under conditions of DEG C, gamma-aminopropyl-triethoxy-silane common 6g, 12~15h of stirring reaction is added dropwise；Then tri-n-octyl amine is added dropwise to be total to
12g, stirring reaction 6h, are then filtered, washed and dried the amorphous silica gel that can obtain surface grafting.The table that will be obtained
The amorphous silica gel of face grafting is added in the second chromatographic column (internal diameter is 10mm), and pressurization ensures that filling is uniform, you can obtain second
Chromatographic column.
Be to purity 99.0% trimethyl gallium crude product (with ether as solvent, with CH3MgI and GaI3For prepared by raw material reaction
Obtain) purified.
The purification process is comprised the following steps：
(1) trimethyl gallium crude product is poured into the first chromatographic column, is flowed down naturally by gravity, treat that liquid flow is complete, collected molten
Liquid；
(2) solution of collection is poured into the second chromatographic column, is flowed down naturally by gravity, treat the complete collection solution of liquid flow；
The solution collected is poured into the second chromatographic column again again, is repeated 2~5 times；
(3) to carrying out heating de-coordination by the second chromatographic column after step (2) treatment, and receipts are vacuumized in chromatography column bottom
The trimethyl gallium that collection can be purified；And it is 90 DEG C to heat the temperature of de-coordination.
Embodiment 2
The aluminum oxide that 100g particle diameters are 5 μm is fitted into chromatographic column (internal diameter is 10mm), pressurization ensures that filling is uniform, you can
Obtain the first chromatographic column.
By alumina dispersion that 100g particle diameters are 5 μm in the reactor equipped with anhydrous toluene solution, then at 80 DEG C
Under the conditions of, gamma-aminopropyl-triethoxy-silane common 6g, stirring reaction 15h is added dropwise；Then the common 12g of tri-n-octyl amine is added dropwise, stirring is anti-
6h is answered, the aluminum oxide that can obtain surface grafting is then filtered, washed and dried.The aluminum oxide of the surface grafting that will be obtained
Add in the second chromatographic column (internal diameter is 10mm), pressurization ensures that filling is uniform, you can obtain the second chromatographic column.
Be to purity 99.0% trimethyl gallium crude product (with ether as solvent, with CH3MgI and GaI3For prepared by raw material reaction
Obtain) purified.
The purification process is comprised the following steps：
(1) trimethyl gallium crude product is poured into the first chromatographic column, is flowed down naturally by gravity, treat that liquid flow is complete, collected molten
Liquid；
(2) solution of collection is poured into the second chromatographic column, is flowed down naturally by gravity, treat the complete collection solution of liquid flow；
The solution collected is poured into the second chromatographic column again again, is repeated 2~5 times；
(3) to carrying out heating de-coordination by the second chromatographic column after step (2) treatment, and receipts are vacuumized in chromatography column bottom
The trimethyl gallium that collection can be purified；And it is 100 DEG C to heat the temperature of de-coordination.
Embodiment 3
The titanium dioxide that 100g particle diameters are 5 μm is fitted into chromatographic column (internal diameter is 10mm), pressurization ensures that filling is uniform, i.e.,
Available first chromatographic column.
The titanium dioxide that 100g particle diameters are 5 μm is dispersed in the reactor equipped with anhydrous toluene solution, then at 80 DEG C
Under conditions of, gamma-aminopropyl-triethoxy-silane common 6g, stirring reaction 18h is added dropwise；Then the common 12g of tri-n-octyl amine, stirring is added dropwise
Reaction 6h, is then filtered, washed and dried the titanium dioxide that can obtain surface grafting.The two of the surface grafting that will be obtained
Titanium oxide is added in the second chromatographic column (internal diameter is 10mm), and pressurization ensures that filling is uniform, you can obtain the second chromatographic column.
Be to purity 99.0% trimethyl gallium crude product (with ether as solvent, with CH3MgI and GaI3For prepared by raw material reaction
Obtain) purified.
The purification process is comprised the following steps：
(1) trimethyl gallium crude product is poured into the first chromatographic column, is flowed down naturally by gravity, treat that liquid flow is complete, collected molten
Liquid；
(2) solution of collection is poured into the second chromatographic column, is flowed down naturally by gravity, treat the complete collection solution of liquid flow；
The solution collected is poured into the second chromatographic column again again, is repeated 2~5 times；
(3) to carrying out heating de-coordination by the second chromatographic column after step (2) treatment, and receipts are vacuumized in chromatography column bottom
The trimethyl gallium that collection can be purified；And it is 85 DEG C to heat the temperature of de-coordination.
Embodiment 4
The zirconium dioxide that 120g particle diameters are 5 μm is fitted into chromatographic column (internal diameter is 10mm), pressurization ensures that filling is uniform, i.e.,
Available first chromatographic column.
The zirconium dioxide that 120g particle diameters are 5 μm is dispersed in the reactor equipped with anhydrous toluene solution, then at 80 DEG C
Under conditions of, gamma-aminopropyl-triethoxy-silane common 4g, stirring reaction 10h is added dropwise；Then the common 12g of tri-n-octyl amine, stirring is added dropwise
Reaction 6h, is then filtered, washed and dried the zirconium dioxide that can obtain surface grafting.The two of the surface grafting that will be obtained
Zirconium oxide is added in the second chromatographic column (internal diameter is 10mm), and pressurization ensures that filling is uniform, you can obtain the second chromatographic column.
Be to purity 99.0% trimethyl gallium crude product (with ether as solvent, with CH3MgI and GaI3For prepared by raw material reaction
Obtain) purified.
The purification process is comprised the following steps：
(1) trimethyl gallium crude product is poured into the first chromatographic column, is flowed down naturally by gravity, treat that liquid flow is complete, collected molten
Liquid；
(2) solution of collection is poured into the second chromatographic column, is flowed down naturally by gravity, treat the complete collection solution of liquid flow；
The solution collected is poured into the second chromatographic column again again, is repeated 2~5 times；
(3) to carrying out heating de-coordination by the second chromatographic column after step (2) treatment, and receipts are vacuumized in chromatography column bottom
The trimethyl gallium that collection can be purified；And it is 100 DEG C to heat the temperature of de-coordination.
Embodiment 5
The urea formaldehyde resin microsphere that 30g particle diameters are 5 μm is fitted into chromatographic column (internal diameter is 10mm), pressurization ensures that filling is equal
It is even, you can to obtain the first chromatographic column.
The Lauxite that 120g particle diameters are 5 μm is dispersed in the reactor equipped with anhydrous toluene solution, then at 50 DEG C
Under conditions of, gamma-aminopropyl-triethoxy-silane common 4g, stirring reaction 10h is added dropwise；Then the common 10g of tri-n-octyl amine, stirring is added dropwise
Reaction 6h, is then filtered, washed and dried the Lauxite that can obtain surface grafting.The urea of the surface grafting that will be obtained
Urea formaldehyde is added in the second chromatographic column (internal diameter is 10mm), and pressurization ensures that filling is uniform, you can obtain the second chromatographic column.
Be to purity 99.0% trimethyl gallium crude product (with ether as solvent, with CH3MgI and GaI3For prepared by raw material reaction
Obtain) purified.
The purification process is comprised the following steps：
(1) trimethyl gallium crude product is poured into the first chromatographic column, is flowed down naturally by gravity, treat that liquid flow is complete, collected molten
Liquid；
(2) solution of collection is poured into the second chromatographic column, is flowed down naturally by gravity, treat the complete collection solution of liquid flow；
The solution collected is poured into the second chromatographic column again again, is repeated 2~5 times；
(3) to carrying out heating de-coordination by the second chromatographic column after step (2) treatment, and receipts are vacuumized in chromatography column bottom
The trimethyl gallium that collection can be purified；And it is 100 DEG C to heat the temperature of de-coordination.
ICP-OES and NMR analyses are carried out to the trimethyl gallium that embodiment 1~5 is obtained after purification, can confirm that collection is obtained
The purity of trimethyl gallium can reach 99.9999% (6N).
Comparative example
Real tri-n-octyl amine is substituted with di-n-butylamine, tripropyl amine (TPA) and makes chromatographic column, using the purification operations of embodiment, passed through
ICP-OES and NMR analyses find, can not only remove ether solvent therein and metal impurities ion, but also can introduce
Di-n-butylamine and tripropyl amine (TPA).
For the ordinary skill in the art, specific embodiment is that the present invention is exemplarily described,
The present invention is implemented and is not subject to the restrictions described above, as long as employing what method of the present invention design and technical scheme were carried out
The improvement of various unsubstantialities, or it is not improved by it is of the invention design and technical scheme directly apply to other occasions,
Within protection scope of the present invention.
Claims (8)
1. a kind of purification process of trimethyl gallium, it is characterised in that comprise the following steps：First, first with fixing phase as filler
Chromatographic column is filtered to trimethyl gallium crude product；Then, to the trimethyl gallium crude product after filtering with fixing phase as surface grafting
Purified in second chromatographic column of filler, and the filler of the surface grafting has the filler of tri-n-octyl amine for surface grafting；
Described filler is the one kind in aluminum oxide, titanium dioxide, zirconium dioxide or urea formaldehyde resin microsphere.
2. the purification process of trimethyl gallium according to claim 1, it is characterised in that：The purity of the trimethyl gallium is
95.0~99.0%.
3. the purification process of trimethyl gallium according to claim 1, it is characterised in that：The particle diameter of described filler is 3~10 μ
m。
4. the purification process of trimethyl gallium according to claim 1, it is characterised in that：The filler of the surface grafting passes through
Following methods are prepared：It is surface-treated using amino silane, tri-n-octyl amine is then grafted again.
5. the purification process of trimethyl gallium according to claim 4, it is characterised in that：Described filler, amino silane and
The mass ratio of tri-n-octyl amine is：30~120：3~6：8~12.
6. the purification process of trimethyl gallium according to claim 4, it is characterised in that：The amino silane is selected from γ-ammonia
Propyl-triethoxysilicane, γ-aminopropyltrimethoxysilane, phenylaminoethyl triethoxysilane, phenylaminoethyl front three
TMOS, N- β (aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane
Or at least one in N- β (aminoethyl)-γ-aminopropyl ethyl diethoxy silane.
7. the purification process of trimethyl gallium according to claim 1, it is characterised in that：Described filler is utilizing amino silane
Hydroxylating treatment is first carried out before being surface-treated.
8. the purification process of trimethyl gallium according to claim 1, it is characterised in that comprise the following steps：(1) by front three
Base gallium crude product is poured into the first chromatographic column, is flowed down naturally by gravity, treats that liquid flow is complete, collects solution；(2) solution that will be collected
Pour into the second chromatographic column, flowed down naturally by gravity, treat the complete collection solution of liquid flow；The solution collected is poured into second again again
In chromatographic column, repeat 2~5 times；(3) to carrying out heating de-coordination by the second chromatographic column after step (2) treatment, and in layer
Analysis column bottom vacuumizes the trimethyl gallium collected and can be purified；And it is 80~100 DEG C to heat the temperature of de-coordination.
Priority Applications (1)
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| JPS62185090A (en) * | 1986-02-10 | 1987-08-13 | Sumitomo Chem Co Ltd | Purification of alkylgallium |
| JP2010195690A (en) * | 2009-02-23 | 2010-09-09 | Ube Ind Ltd | High-purity trialkyl gallium, and method of producing the same |
| JP2011173935A (en) * | 2006-09-28 | 2011-09-08 | Ube Industries Ltd | Highly pure trialkyl gallium and method for producing the same |
| JP2011173934A (en) * | 2011-06-16 | 2011-09-08 | Ube Industries Ltd | Highly pure trialkyl gallium and method for producing the same |
| JP2014037424A (en) * | 2013-10-07 | 2014-02-27 | Ube Ind Ltd | High-purity trialkyl gallium, and method of producing the same |
| CN103965227A (en) * | 2013-01-30 | 2014-08-06 | 上海宏锐新材料科技有限公司 | Industrial purification method of trimethyl gallium |
| CN104744500A (en) * | 2015-04-23 | 2015-07-01 | 苏州普耀光电材料有限公司 | Purification method for triallyl compounds of liquid state group III metals |
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| JP2011173935A (en) * | 2006-09-28 | 2011-09-08 | Ube Industries Ltd | Highly pure trialkyl gallium and method for producing the same |
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