CN104817580A - Efficient purifying method of trimethylindium - Google Patents
Efficient purifying method of trimethylindium Download PDFInfo
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- CN104817580A CN104817580A CN201510239891.0A CN201510239891A CN104817580A CN 104817580 A CN104817580 A CN 104817580A CN 201510239891 A CN201510239891 A CN 201510239891A CN 104817580 A CN104817580 A CN 104817580A
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- filler
- chromatography column
- purifying method
- solution
- trimethyl indium
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- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000945 filler Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 230000005484 gravity Effects 0.000 claims abstract description 16
- 239000012043 crude product Substances 0.000 claims abstract description 15
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000000197 pyrolysis Methods 0.000 claims description 14
- 238000003756 stirring 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
- 238000000746 purification Methods 0.000 claims description 10
- 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 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 7
- 230000003252 repetitive effect Effects 0.000 claims description 7
- 238000005406 washing Methods 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
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000004381 surface treatment Methods 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
- 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
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000003883 substance clean up Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 239000006227 byproduct Substances 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
- 238000001704 evaporation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-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
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to an efficient purifying method of trimethylindium, belonging to the technical field of compound purification. The purifying method comprises the following steps of (1) pouring a crude product of trimethylindium into a first chromatographic column with a stationary phase as filler, naturally and downwards flowing the crude product of trimethylindium by virtue of gravity, and collecting a solution when all the liquid flows up; (2) pouring the collected solution into a second chromatographic column with a stationary phase as surface grafted filler, naturally and downwards flowing the solution by virtue of gravity, and collecting the solution when all the liquid flows up; then, pouring the collected solution into the second chromatographic column, and repeating the operation 2-5 times, wherein the surface grafted filler is filler of which the surface is grafted with tri-n-octylamine; and (3) heating and disassembling the second chromatographic column treated in the step (2), and collecting by vacuumizing at the bottom of the chromatographic column to obtain purified trimethylindium. The purifying method disclosed by the invention is combined with a solid-liquid separation means, and a specific coordination agent is loaded on the filler, so that not only is the method simple, but also the purifying effect is further improved.
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 indium.
Background technology
High-purity trimethyl indium 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 indium 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 indium reaches 99.9999%, otherwise just need to purify further.
Chinese invention patent application CN102020668A discloses a kind of method of preparation of industrialization trimethyl indium, in the reactor being full of rare gas element, drop into indium-magnesium alloy raw material, under ether, tetrahydrofuran (THF) or methyltetrahydrofuran exist, progressively add haloalkane (monobromethane or methyl iodide) 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 indium and ether more at reduced pressure conditions, finally solution is joined and is obtained trimethyl indium.The mode that the method adopts reactor to be separated with evaporating kettle, unreacted alloy still continues reaction in a kettle., and overall yield is close to 95%, and by product can be recycled, and does not almost have waste material; And there is no spontaneous combustible substance due to the raw material adopted in reaction process, reaction process safety, is particularly suitable for large-scale industrial production.
Trimethyl indium 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 indium on the other hand, can select to abandon a part of trimethyl indium, allow it be taken out of in the lump with lower-boiling impurity, but due to trimethyl indium 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 indium.
To achieve these goals, present invention employs following technical scheme:
A kind of high-efficiency purifying method of trimethyl indium, it is characterized in that described purification process comprises the following steps: (1) trimethyl indium crude product is poured into stationary phase be filler the first chromatography column in, rely on gravity naturally dirty, treat that liquid stream is complete, collect solution; (2) solution of collection is poured into stationary phase in the second chromatography column of the filler being surface grafting, 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, the filler of wherein said surface grafting is the filler that surface grafting has tri-n-octyl amine; (3) add pyrolysis to the second chromatography column after step (2) process to join, and bottom chromatography column, vacuumize the trimethyl indium collected and can obtain purifying.
Wherein, adding the temperature that pyrolysis joins is 100 ~ 120 DEG C.
Wherein, the purity of described trimethyl indium 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 filler of described surface grafting prepares by the following method: by fillers dispersed in the reactor that organic solvent is housed, and then drips aminosilane stirring reaction; Then drip tri-n-octyl amine stirring reaction, eventually pass the filler that filtration, washing and drying can obtain surface grafting.
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 can carry out hydroxylation process.
Compared with prior art, the high-efficiency purifying method of trimethyl indium 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 indium that purity can reach 6N.
Embodiment
Be further elaborated below with reference to the high-efficiency purifying method of specific embodiment to trimethyl indium 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 indium 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 indium 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 vacuumize collection bottom chromatography column
The trimethyl indium of purifying can be obtained; And adding the temperature that pyrolysis joins is 110 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 indium 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 indium 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 indium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 120 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 indium 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 indium 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 indium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 105 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 indium 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 indium 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 indium collected and can obtain purifying; And adding the temperature that pyrolysis joins is 120 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 indium 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 indium 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 indium 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 indium obtained after embodiment 1 ~ 5 purifying to analyze, the purity that can confirm to collect the trimethyl indium 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. the high-efficiency purifying method of a trimethyl indium, it is characterized in that described purification process comprises the following steps: (1) trimethyl indium crude product is poured into stationary phase be filler the first chromatography column in, rely on gravity naturally dirty, treat that liquid stream is complete, collect solution; (2) solution of collection is poured into stationary phase in the second chromatography column of the filler being surface grafting, 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, the filler of wherein said surface grafting is the filler that surface grafting has tri-n-octyl amine; (3) add pyrolysis to the second chromatography column after step (2) process to join, and bottom chromatography column, vacuumize the trimethyl indium collected and can obtain purifying.
2. high-efficiency purifying method according to claim 1, is characterized in that: adding the temperature that pyrolysis joins is 100 ~ 120 DEG C.
3. high-efficiency purifying method according to claim 1, is characterized in that: the purity of described trimethyl indium is 95.0 ~ 99.0%.
4. high-efficiency purifying method according to claim 1, is characterized in that: described filler is one or both in silica gel, aluminum oxide, titanium dioxide or zirconium dioxide.
5. high-efficiency purifying method 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.
6. high-efficiency purifying method according to claim 1, is characterized in that: the particle diameter of described filler is 3 ~ 10 μm.
7. high-efficiency purifying method 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.
8. high-efficiency purifying method according to claim 7, is characterized in that: the filler of described surface grafting prepares by the following method: by fillers dispersed in the reactor that organic solvent is housed, and then drips aminosilane stirring reaction; Then drip tri-n-octyl amine stirring reaction, eventually pass the filler that filtration, washing and drying can obtain surface grafting.
9. high-efficiency purifying method according to claim 7, is characterized in that: the mass ratio of described filler, aminosilane and tri-n-octyl amine is: 30 ~ 120:3 ~ 6:8 ~ 12.
10. high-efficiency purifying method according to claim 7, 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.
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| JP2008024617A (en) * | 2006-07-19 | 2008-02-07 | Ube Ind Ltd | High-purity trialkylaluminum and method for producing the same |
| JP2012062331A (en) * | 2011-12-27 | 2012-03-29 | Ube Industries Ltd | High-purity trialkyl indium, and its production method |
| 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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| JP2008024617A (en) * | 2006-07-19 | 2008-02-07 | Ube Ind Ltd | High-purity trialkylaluminum and method for producing the same |
| JP2012062331A (en) * | 2011-12-27 | 2012-03-29 | Ube Industries Ltd | High-purity trialkyl indium, and its production method |
| 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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