CN104860973A - High-efficient purifying method for trimethyl gallium - Google Patents
High-efficient purifying method for trimethyl gallium Download PDFInfo
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- CN104860973A CN104860973A CN201510239398.9A CN201510239398A CN104860973A CN 104860973 A CN104860973 A CN 104860973A CN 201510239398 A CN201510239398 A CN 201510239398A CN 104860973 A CN104860973 A CN 104860973A
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- trimethyl
- gallium
- chromatography column
- purifying method
- filler
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- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000012043 crude product Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 60
- 239000000945 filler Substances 0.000 claims description 21
- 230000005484 gravity Effects 0.000 claims description 14
- 238000000197 pyrolysis Methods 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 7
- 230000003252 repetitive effect Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- ZGSJFMIWRLMFBZ-UHFFFAOYSA-N 3-(3-aminopropyl-ethoxy-ethylsilyl)oxybutan-1-amine Chemical compound NCCC(C)O[Si](OCC)(CC)CCCN ZGSJFMIWRLMFBZ-UHFFFAOYSA-N 0.000 claims description 2
- ULRCHFVDUCOKTE-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxybutan-1-amine Chemical compound NCCC[Si](OCC)(OCC)OC(C)CCN ULRCHFVDUCOKTE-UHFFFAOYSA-N 0.000 claims description 2
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 claims description 2
- 230000033444 hydroxylation Effects 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- 239000011806 microball Substances 0.000 claims description 2
- DRKSQNOZVVFYQE-UHFFFAOYSA-N n-(2-triethoxysilylethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCNC1=CC=CC=C1 DRKSQNOZVVFYQE-UHFFFAOYSA-N 0.000 claims description 2
- JDDAMKOBLWFNCZ-UHFFFAOYSA-N n-(2-trimethoxysilylethyl)aniline Chemical compound CO[Si](OC)(OC)CCNC1=CC=CC=C1 JDDAMKOBLWFNCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 238000011068 loading method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000003883 substance clean up Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000000746 purification Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-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
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 238000004871 chemical beam epitaxy Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-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
- 238000013019 agitation Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- FWLGASJILZBATH-UHFFFAOYSA-N gallium magnesium Chemical compound [Mg].[Ga] FWLGASJILZBATH-UHFFFAOYSA-N 0.000 description 1
- 239000007789 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000000843 powder Substances 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
- 150000003384 small molecules Chemical class 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 invention relates to a high-efficient purifying method for trimethyl gallium, and belongs to the technical field of the compound purification. The purifying method comprises the following steps: firstly, filtering a trimethyl gallium crude product by a first chromatographic column using the stationary phase as the padding; secondly, purifying the filtered trimethyl gallium crude product in a second chromatographic column using the stationary phase as the padding of the surface grafting, wherein the padding of the surface grafting is the padding of which the surface is grafted with tri-n-octylamine. The purifying method is capable of combining the method of solid-liquid separation, loading a specific coordination agent on the padding, and further improving the purifying effect, and the operation is simple.
Description
Technical field
The invention belongs to the technical field that compound is purified, in particular, the present invention relates to a kind of high-efficiency purifying method of trimethyl-gallium.
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, be metal organic chemical vapor deposition technology (MOCVD), in chemical beam epitaxy (CBE) process grow light electronic material most important, be also the maximum raw material of current consumption.In order to meet photoelectron material high purity, (trimethyl-gallium that purity is inadequate can have a huge impact the performance of chip high-precision specification of quality, very large infringement is also had to MOCVD device), require that the purity of high-purity trimethyl-gallium reaches 99.9999%, otherwise just need to purify further.
In prior art, the method of preparation of industrialization trimethyl-gallium, in the reactor being full of rare gas element, drop into gallium-magnesium alloy raw material, under ether solvent (ether, tetrahydrofuran (THF) or methyltetrahydrofuran) exists, progressively add haloalkane (monobromethane or iodoethane) under agitation, solvent refluxing speed is controlled by the rate of addition controlling haloalkane, after having reacted, solvent is steamed, obtain the title complex of trimethyl-gallium and ether more at reduced pressure conditions, finally solution is joined and is obtained trimethyl-gallium; The temperature that described solution is joined is 80 ~ 150 DEG C.
Trimethyl-gallium is due to the restriction of preparation technology, itself and reaction solvent is made to be difficult to be separated, existing mode selects the coordination agents such as ethers to carry out coordination, then under intensification and vacuum condition, low boiling point solvent is removed, and then under elevated temperature in vacuo, solution is joined and is obtained crude product, then obtains high purity product again through rectifying.It is liquid that major part coordination agent all belongs to macromole high boiling point, and viscosity is higher, and small molecules lower-boiling impurity is easily wrapped in inside macromole high boiling point coordination agent, is not easy to be divided, and purity generally only can reach 95.0 ~ 99.0%.Prior art is the purity ensureing trimethyl-gallium on the other hand, can select to abandon a part of trimethyl-gallium, allow it be taken out of in the lump with lower-boiling impurity, but due to trimethyl-gallium self character, the danger causing this portion to work is comparatively large, and not easy to operate, difficulty is higher.
Summary of the invention
In order to solve above-mentioned technical problem of the prior art, the object of the present invention is to provide a kind of high-efficiency purifying method of trimethyl-gallium.
To achieve these goals, present invention employs following technical scheme:
A high-efficiency purifying method for trimethyl-gallium, is characterized in that comprising the following steps: first, is that the first chromatography column of filler filters trimethyl-gallium crude product with stationary phase; Then, be purify in the second chromatography column of the filler of surface grafting with stationary phase to the trimethyl-gallium crude product after filtration, and the filler of described surface grafting is the filler that surface grafting has tri-n-octyl amine.
Wherein, the purity of described trimethyl-gallium is 95.0 ~ 99.0%.
Wherein, described filler is one or both in silica gel, aluminum oxide, titanium dioxide or zirconium dioxide.
Wherein, described filler is one or both in polystyrene microsphere, CALCIUM ACRYLATE microballoon, methacrylic acid lipoid microsphere, polyaminoester microball or urea formaldehyde resin microsphere.
Wherein, the particle diameter of described filler is 3 ~ 10 μm.
Wherein, the filler of described surface grafting prepares by the following method: utilize aminosilane to carry out surface treatment, and then grafting tri-n-octyl amine.
Wherein, the mass ratio of described filler, aminosilane and tri-n-octyl amine is: 30 ~ 120:3 ~ 6:8 ~ 12.
Wherein, described aminosilane is selected from least one in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, phenylaminoethyl triethoxyl silane, phenylaminoethyl Trimethoxy silane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane or N-β (aminoethyl)-γ-aminopropyl ethyl diethoxy silane, is preferably γ-aminopropyl triethoxysilane.
Wherein, described filler utilize aminosilane carry out surface treatment before first carry out hydroxylation process.
Wherein, described purification process comprises the following steps: trimethyl-gallium crude product is poured in the first chromatography column by (1), relies on gravity naturally dirty, treats that liquid stream is complete, collect solution; (2) solution of collection is poured in the second chromatography column, rely on gravity naturally dirty, treat the complete collection solution of liquid stream; Again the solution collected is poured in the second chromatography column again, repetitive operation 2 ~ 5 times; (3) add pyrolysis to the second chromatography column after step (2) process to join, and bottom chromatography column, vacuumize the trimethyl-gallium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 80 ~ 100 DEG C.
Compared with prior art, the high-efficiency purifying method of trimethyl-gallium of the present invention has following beneficial effect:
Purification process of the present invention purification process of the present invention combines the means of solid-liquid separation, by specific coordination agent load on filler, not only simple to operate, and further increases purification effect, obtains the trimethyl-gallium that purity can reach 6N.
Embodiment
Be further elaborated below with reference to the high-efficiency purifying method of specific embodiment to trimethyl-gallium of the present invention, to make more complete explanation to inventive concept of the present invention and effect thereof.
Embodiment 1
Be in silica-gel powder loading chromatography column (internal diameter is 10mm) of 5 μm by 100g particle diameter, pressurization ensures to fill evenly, can obtain the first chromatography column.
Be that the amorphous silica gel of 5 μm is dispersed in and is equipped with in the reactor of anhydrous toluene solution by 100g particle diameter, then under the condition of 60 DEG C, drip γ-aminopropyl triethoxysilane 6g, stirring reaction 12 ~ 15h altogether; Then drip tri-n-octyl amine 12g, stirring reaction 6h altogether, then can obtain the amorphous silica gel of surface grafting through filtration, washing and drying.Added by the amorphous silica gel of the surface grafting obtained in the second chromatography column (internal diameter is 10mm), pressurization ensures to fill evenly, can obtain the second chromatography column.
The trimethyl-gallium crude product being 99.0% to purity (is solvent with ether, with CH
3mgI and GaI
3for raw material reaction prepares) purify.
Described purification process comprises the following steps:
(1) trimethyl-gallium crude product is poured in the first chromatography column, rely on gravity naturally dirty, treat that liquid stream is complete, collect solution;
(2) solution of collection is poured in the second chromatography column, rely on gravity naturally dirty, treat the complete collection solution of liquid stream; Again the solution collected is poured in the second chromatography column again, repetitive operation 2 ~ 5 times;
(3) add pyrolysis to the second chromatography column after step (2) process to join, and bottom chromatography column, vacuumize the trimethyl-gallium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 90 DEG C.
Embodiment 2
Be in aluminum oxide loading chromatography column (internal diameter is 10mm) of 5 μm by 100g particle diameter, pressurization ensures to fill evenly, can obtain the first chromatography column.
By 100g particle diameter be the alumina dispersion of 5 μm in the reactor that anhydrous toluene solution is housed, then under the condition of 80 DEG C, drip γ-aminopropyl triethoxysilane altogether 6g, stirring reaction 15h; Then drip tri-n-octyl amine 12g, stirring reaction 6h altogether, then can obtain the aluminum oxide of surface grafting through filtration, washing and drying.Added by the aluminum oxide of the surface grafting obtained in the second chromatography column (internal diameter is 10mm), pressurization ensures to fill evenly, can obtain the second chromatography column.
The trimethyl-gallium crude product being 99.0% to purity (is solvent with ether, with CH
3mgI and GaI
3for raw material reaction prepares) purify.
Described purification process comprises the following steps:
(1) trimethyl-gallium crude product is poured in the first chromatography column, rely on gravity naturally dirty, treat that liquid stream is complete, collect solution;
(2) solution of collection is poured in the second chromatography column, rely on gravity naturally dirty, treat the complete collection solution of liquid stream; Again the solution collected is poured in the second chromatography column again, repetitive operation 2 ~ 5 times;
(3) add pyrolysis to the second chromatography column after step (2) process to join, and bottom chromatography column, vacuumize the trimethyl-gallium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 100 DEG C.
Embodiment 3
Be in titanium dioxide loading chromatography column (internal diameter is 10mm) of 5 μm by 100g particle diameter, pressurization ensures to fill evenly, can obtain the first chromatography column.
Be that the titanium dioxide of 5 μm is dispersed in and is equipped with in the reactor of anhydrous toluene solution by 100g particle diameter, then under the condition of 80 DEG C, drip γ-aminopropyl triethoxysilane 6g, stirring reaction 18h altogether; Then drip tri-n-octyl amine 12g, stirring reaction 6h altogether, then can obtain the titanium dioxide of surface grafting through filtration, washing and drying.Added by the titanium dioxide of the surface grafting obtained in the second chromatography column (internal diameter is 10mm), pressurization ensures to fill evenly, can obtain the second chromatography column.
The trimethyl-gallium crude product being 99.0% to purity (is solvent with ether, with CH
3mgI and GaI
3for raw material reaction prepares) purify.
Described purification process comprises the following steps:
(1) trimethyl-gallium crude product is poured in the first chromatography column, rely on gravity naturally dirty, treat that liquid stream is complete, collect solution;
(2) solution of collection is poured in the second chromatography column, rely on gravity naturally dirty, treat the complete collection solution of liquid stream; Again the solution collected is poured in the second chromatography column again, repetitive operation 2 ~ 5 times;
(3) add pyrolysis to the second chromatography column after step (2) process to join, and bottom chromatography column, vacuumize the trimethyl-gallium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 85 DEG C.
Embodiment 4
Be in zirconium dioxide loading chromatography column (internal diameter is 10mm) of 5 μm by 120g particle diameter, pressurization ensures to fill evenly, can obtain the first chromatography column.
Be that the zirconium dioxide of 5 μm is dispersed in and is equipped with in the reactor of anhydrous toluene solution by 120g particle diameter, then under the condition of 80 DEG C, drip γ-aminopropyl triethoxysilane 4g, stirring reaction 10h altogether; Then drip tri-n-octyl amine 12g, stirring reaction 6h altogether, then can obtain the zirconium dioxide of surface grafting through filtration, washing and drying.Added by the zirconium dioxide of the surface grafting obtained in the second chromatography column (internal diameter is 10mm), pressurization ensures to fill evenly, can obtain the second chromatography column.
The trimethyl-gallium crude product being 99.0% to purity (is solvent with ether, with CH
3mgI and GaI
3for raw material reaction prepares) purify.
Described purification process comprises the following steps:
(1) trimethyl-gallium crude product is poured in the first chromatography column, rely on gravity naturally dirty, treat that liquid stream is complete, collect solution;
(2) solution of collection is poured in the second chromatography column, rely on gravity naturally dirty, treat the complete collection solution of liquid stream; Again the solution collected is poured in the second chromatography column again, repetitive operation 2 ~ 5 times;
(3) add pyrolysis to the second chromatography column after step (2) process to join, and bottom chromatography column, vacuumize the trimethyl-gallium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 100 DEG C.
Embodiment 5
Be in urea formaldehyde resin microsphere loading chromatography column (internal diameter is 10mm) of 5 μm by 30g particle diameter, pressurization ensures to fill evenly, can obtain the first chromatography column.
Be that the urea-formaldehyde resin of 5 μm is dispersed in and is equipped with in the reactor of anhydrous toluene solution by 120g particle diameter, then under the condition of 50 DEG C, drip γ-aminopropyl triethoxysilane 4g, stirring reaction 10h altogether; Then drip tri-n-octyl amine 10g, stirring reaction 6h altogether, then can obtain the urea-formaldehyde resin of surface grafting through filtration, washing and drying.Added by the urea-formaldehyde resin of the surface grafting obtained in the second chromatography column (internal diameter is 10mm), pressurization ensures to fill evenly, can obtain the second chromatography column.
The trimethyl-gallium crude product being 99.0% to purity (is solvent with ether, with CH
3mgI and GaI
3for raw material reaction prepares) purify.
Described purification process comprises the following steps:
(1) trimethyl-gallium crude product is poured in the first chromatography column, rely on gravity naturally dirty, treat that liquid stream is complete, collect solution;
(2) solution of collection is poured in the second chromatography column, rely on gravity naturally dirty, treat the complete collection solution of liquid stream; Again the solution collected is poured in the second chromatography column again, repetitive operation 2 ~ 5 times;
(3) add pyrolysis to the second chromatography column after step (2) process to join, and bottom chromatography column, vacuumize the trimethyl-gallium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 100 DEG C.
Carry out ICP-OES and NMR to the trimethyl-gallium obtained after embodiment 1 ~ 5 purifying to analyze, the purity that can confirm to collect the trimethyl-gallium obtained can reach 99.9999% (6N).
Comparative example
Substitute real tri-n-octyl amine with Di-n-Butyl Amine, tripropyl amine and make chromatography column, adopt the purification operations of embodiment, analyze through ICP-OES and NMR and find, not only can not remove ether solvent wherein and metallic impurity ion, but also Di-n-Butyl Amine and tripropyl amine can be introduced.
For the ordinary skill in the art; specific embodiment is just to invention has been exemplary description; specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the improvement of the various unsubstantialities that method of the present invention is conceived and technical scheme is carried out; or design of the present invention and technical scheme directly applied to other occasion, all within protection scope of the present invention without to improve.
Claims (10)
1. a high-efficiency purifying method for trimethyl-gallium, is characterized in that comprising the following steps: first, is that the first chromatography column of filler filters trimethyl-gallium crude product with stationary phase; Then, be purify in the second chromatography column of the filler of surface grafting with stationary phase to the trimethyl-gallium crude product after filtration, and the filler of described surface grafting is the filler that surface grafting has tri-n-octyl amine.
2. the high-efficiency purifying method of trimethyl-gallium according to claim 1, is characterized in that: the purity of described trimethyl-gallium is 95.0 ~ 99.0%.
3. the high-efficiency purifying method of trimethyl-gallium according to claim 1, is characterized in that: described filler is one or both in silica gel, aluminum oxide, titanium dioxide or zirconium dioxide.
4. the high-efficiency purifying method of trimethyl-gallium according to claim 1, is characterized in that: described filler is one or both in polystyrene microsphere, CALCIUM ACRYLATE microballoon, methacrylic acid lipoid microsphere, polyaminoester microball or urea formaldehyde resin microsphere.
5. the high-efficiency purifying method of trimethyl-gallium according to claim 1, is characterized in that: the particle diameter of described filler is 3 ~ 10 μm.
6. the high-efficiency purifying method of trimethyl-gallium according to claim 1, is characterized in that: the filler of described surface grafting prepares by the following method: utilize aminosilane to carry out surface treatment, and then grafting tri-n-octyl amine.
7. the high-efficiency purifying method of trimethyl-gallium according to claim 1, is characterized in that: the mass ratio of described filler, aminosilane and tri-n-octyl amine is: 30 ~ 120:3 ~ 6:8 ~ 12.
8. the high-efficiency purifying method of trimethyl-gallium according to claim 1, it is characterized in that: described aminosilane is selected from least one in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, phenylaminoethyl triethoxyl silane, phenylaminoethyl Trimethoxy silane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane or N-β (aminoethyl)-γ-aminopropyl ethyl diethoxy silane, be preferably γ-aminopropyl triethoxysilane.
9. the high-efficiency purifying method of trimethyl-gallium according to claim 1, is characterized in that: described filler utilize aminosilane carry out surface treatment before first carry out hydroxylation process.
10. the high-efficiency purifying method of trimethyl-gallium according to claim 1, is characterized in that comprising the following steps: trimethyl-gallium crude product is poured in the first chromatography column by (1), relies on gravity naturally dirty, treats that liquid stream is complete, collect solution; (2) solution of collection is poured in the second chromatography column, rely on gravity naturally dirty, treat the complete collection solution of liquid stream; Again the solution collected is poured in the second chromatography column again, repetitive operation 2 ~ 5 times; (3) add pyrolysis to the second chromatography column after step (2) process to join, and bottom chromatography column, vacuumize the trimethyl-gallium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 80 ~ 100 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510239398.9A CN104860973B (en) | 2015-05-12 | 2015-05-12 | The purification process of trimethyl gallium |
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| CN109575064A (en) * | 2018-12-30 | 2019-04-05 | 江西师范大学 | A kind of method of purification of high pure metal organic source |
| CN110343124A (en) * | 2019-07-31 | 2019-10-18 | 苏州普耀光电材料有限公司 | A method of trimethyl gallium is de-coordinated using mixed ligand agent |
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