CN103965227A - Industrial purification method of trimethyl gallium - Google Patents
Industrial purification method of trimethyl gallium Download PDFInfo
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- CN103965227A CN103965227A CN201310037648.1A CN201310037648A CN103965227A CN 103965227 A CN103965227 A CN 103965227A CN 201310037648 A CN201310037648 A CN 201310037648A CN 103965227 A CN103965227 A CN 103965227A
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Abstract
The invention discloses an industrial purification method of trimethyl gallium. The industrial purification method comprises the following steps of adding trimethyl gallium or a trimethyl gallium. ether complex into an inert atmosphere-containing reactor, adding a R1R2R3N ligand into the reactor, carrying out a reaction process at a reaction system temperature of 25-90 DEG C, after dropwise addition, carrying out stirring at a temperature of 60-90 DEG C for 2-6h, and carrying out decomplexation to obtain high-purity trimethyl gallium, wherein R1R2R3 is same or different C2-C6 alkyl or aryl. The industrial purification method utilizes a cheap and easily available conventional reagent as a ligand, has a mild reaction process, stable ligand properties, no safety hidden trouble and high reaction and decomplexation yield, realizes ligand recycle, does not produce waste and reduces a cost.
Description
Technical field
The present invention relates to a kind of industrialized purification method of trimethyl-gallium.
Background technology
Existing photodiode (LED), because it possesses that volume is little, shock-resistant, the life-span is long, pollution-free, reliability is high and the good characteristic such as low voltage low current operation, be applicable to use at various environment simultaneously, meet the megatrend of following environmental protection and energy saving.In recent years, the development of the III A group-III nitride that the gan of take is representative is very fast, due to gallium nitride semiconductor material, to have energy gap large, breakdown electric field is high, the saturated drift velocity of electronics is high, specific inductivity is little, strong radioprotective power and good chemical stability, in light display, show, light stores, the opto-electronic devices such as optical detection and high temperature, the field of microelectronic devices such as high-frequency high-power electronics have wide application prospects, wherein the most noticeable is application as luminescent material, the application of gallium nitride based light emitting diode (LED) in general lighting field has extraordinary prospect.LED lamp, by replacing the conventional light source such as current a large amount of incandescent light that use, electricity-saving lamp, is called as the revolution of 21 century lighting source.
MOCVD(metal organic chemical vapor deposition), large owing to thering is production capacity, feature with short production cycle, it is at present unique preparation method that gallium-nitride-based devices is produced in industrialization that realizes, its technique is to use the hydride of element as raw material, brings reaction chamber extension on the substrate of heat into become compound monocrystal film by carrier gas such as hydrogen or nitrogen.The purity of process Raw, quality have vital impact to epitaxial wafer and even final photoelectric device or high-frequency element, and especially the function for products such as the higher blue-light device of technology content, semiconductor lasers plays conclusive effect especially.Trimethyl-gallium be use the most extensively at present, the most important, the most ripe starting material.
Just because of trimethyl-gallium be growing gallium nitride the most extensively, the most important, the most ripe starting material, though the report of at present relevant trimethyl-gallium purification process has, also there is no the method report of related industries purifying trimethyl-gallium.Conventional purification process has: 1, with trimethyl-gallium and the effect of potassium-sodium alloy, then obtain high-purity trimethyl-gallium by rectifying, because potassium-sodium alloy activity is very high, requirement is large again simultaneously, brings potential safety hazard certainly will to operation and last handling process; 2, with trimethyl-gallium and N, N, N', N'-tetramethyl--4,4'-diaminodiphenylmethane forms part, then solution is joined to obtain high-purity trimethyl-gallium, because the method one is carried out N, N, N', N'-tetramethyl--4,4'-diaminodiphenylmethane is not a conventional reagent, not too easily obtain, its operating process simultaneously is also difficult to realize industrialization, so be also not too applicable to industrialized purification.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of industrialized purification method of trimethyl-gallium, the above-mentioned defect existing to overcome prior art.
For solving the problems of the technologies described above, the industrialized purification method of a kind of trimethyl-gallium of the present invention, comprises the steps:
In the reactor of inert atmosphere, add trimethyl-gallium or trimethyl-gallium ether title complex, then add R
1r
2r
3n part reacts, and the temperature of reaction system remains on 25～90 ℃, after dripping, at 60～90 ℃, stirs 2～6 hours, finally by solution, joins and obtains high-purity trimethyl-gallium.
Ether in described trimethyl-gallium ether title complex is selected from tetrahydrofuran (THF), ether, isopropyl ether or methyltetrahydrofuran, preferably ether;
Described R
1r
2r
3in N part, R
1r
2r
3for the identical of C2～C6 or not identical alkyl or aryl, described R
1r
2r
3the preferred tri-n-butylamine of N part or N, N-Diethyl Aniline;
Described R
1r
2r
3the mol ratio of N part and trimethyl-gallium is 1～1.5 ︰ 1;
R
1r
2r
3it is 25～90 ℃ that the rate of addition of N part is controlled in maintenance system temperature; Described solution is joined for decompression solution and is joined, and it is 100～200mmHg that solution is joined pressure; It is 90 ℃～180 ℃ that solution is joined temperature, then obtains high-purity trimethyl-gallium through rectifying.
Described inert atmosphere can be nitrogen atmosphere or argon gas atmosphere.
Before described trimethyl-gallium purification, purity is 55%～97%, after purification, can reach 99%～99.999%.
Above-mentioned raw materials all adopts conventional commercially available prod.
The present invention has following beneficial effect:
1, selected part is conventional reagent, is very easy to obtain, simultaneously low price;
2, reaction process is more gentle, and part stable in properties, does not have potential safety hazard;
3, reaction conciliates that to join productive rate all very high, R
1r
2r
3n part can be reused, and there is no waste, also
Can reduce costs.
Embodiment
Embodiment 1
Under inert atmosphere, in reactor, add 1100 grams of trimethyl-galliums, under agitation condition, in reactor, drip 2200 grams of tri-n-butylamines, control the speed dripping and maintain the temperature between 25 ℃～90 ℃, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100-200mmHg that solution is joined pressure; It is 90 ℃-180 ℃ that solution is joined temperature) after rectifying obtain 1020 grams of high-purity trimethyl-galliums, take trimethyl-gallium as calculating benchmark, productive rate 92.7%.
Embodiment 2
Under inert atmosphere, in reactor, add 1100 grams of trimethyl-galliums, under agitation condition, in reactor, drip N, 1600 grams of N-Diethyl Anilines, control the speed dripping and maintain the temperature between 25 ℃～90 ℃, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100-200mmHg that solution is joined pressure; It is 90 ℃-180 ℃ that solution is joined temperature) after rectifying obtain 990 grams of high-purity trimethyl-galliums, take trimethyl-gallium as calculating benchmark, productive rate 90%.
Embodiment 3
Under inert atmosphere, in reactor, add 1100 grams of trimethyl-gallium etherates, under agitation condition, in reactor, drip N, 1000 grams of N-Diethyl Anilines, control the speed dripping and maintain the temperature between 25 ℃～90 ℃, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100-200mmHg that solution is joined pressure; It is 90 ℃-180 ℃ that solution is joined temperature) after rectifying obtain 580 grams of high-purity trimethyl-galliums, take trimethyl-gallium as calculating benchmark, productive rate 86.8%.
Embodiment 4
Under inert atmosphere, in reactor, add 1100 grams of trimethyl-gallium etherates, under agitation condition, in reactor, drip 1200 grams of tri-n-butylamines, control the speed dripping and maintain the temperature between 25 ℃～90 ℃, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100-200mmHg that solution is joined pressure; It is 90 ℃-180 ℃ that solution is joined temperature) after rectifying obtain 600 grams of high-purity trimethyl-galliums, take trimethyl-gallium as calculating benchmark, productive rate 89.8%.
Embodiment 5
Under inert atmosphere, in reactor, add 1100 grams of trimethyl-gallium isopropyl ether title complexs, under agitation condition, in reactor, drip 1050 grams of tri-n-butylamines, control the speed dripping and maintain the temperature between 25 ℃～90 ℃, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100-200mmHg that solution is joined pressure; It is 90 ℃-180 ℃ that solution is joined temperature) after rectifying obtain 480 grams of high-purity trimethyl-galliums, take trimethyl-gallium as calculating benchmark, productive rate 82.5%.
Embodiment 6
Under inert atmosphere, in reactor, add 1100 grams of trimethyl-gallium isopropyl ether title complexs, under agitation condition, in reactor, drip N, 850 grams of N-Diethyl Anilines, control the speed dripping and maintain the temperature between 25 ℃～90 ℃, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100-200mmHg that solution is joined pressure; It is 90 ℃-180 ℃ that solution is joined temperature) after rectifying obtain 450 grams of high-purity trimethyl-galliums, take trimethyl-gallium as calculating benchmark, productive rate 77.3%.
Embodiment 7
Under inert atmosphere, in reactor, add 1100 grams of trimethyl-gallium tetrahydrofuran (THF) title complexs, under agitation condition, in reactor, drip 1200 grams of tri-n-butylamines, control the speed dripping and maintain the temperature between 25 ℃～90 ℃, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100-200mmHg that solution is joined pressure; It is 90 ℃-180 ℃ that solution is joined temperature) after rectifying obtain 490 grams of high-purity trimethyl-galliums, take trimethyl-gallium as calculating benchmark, productive rate 72.5%.
Embodiment 8
Under inert atmosphere, in reactor, add 1100 grams of trimethyl-gallium tetrahydrofuran (THF) title complexs, under agitation condition, in reactor, drip N, 1000 grams of N-Diethyl Anilines, control the speed dripping and maintain the temperature between 25 ℃～90 ℃, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100-200mmHg that solution is joined pressure; It is 90 ℃-180 ℃ that solution is joined temperature) after rectifying obtain 465 grams of high-purity trimethyl-galliums, take trimethyl-gallium as calculating benchmark, productive rate 68.8%.
In technique of the present invention, it is steady that reaction and solution are joined condition, is easy to control, with conventional use potassium-sodium alloy or N, N, N', N'-tetramethyl--4,4'-diaminodiphenylmethane purifying trimethyl-gallium is compared, and has that materials safety is stablized, easily obtained, low price, solution join the advantages such as yield height.The still title complex that solution is not joined completely in the end can be retained in still, continues solution and joins, and overall yield can approach 95%, and the part after simultaneously dissociating can be reused, and can produce any waste hardly, is particularly suitable for industrialized purification.
Claims (7)
1. a trimethyl-gallium industrialized purification method, is characterized in that, comprises the steps: to add trimethyl-gallium or trimethyl-gallium ether title complex in the reactor of inert atmosphere, then adds R
1r
2r
3n part reacts, and the temperature of reaction system remains on 25～90 ℃, after dripping, at 60～90 ℃, stirs 2～6 hours, finally by solution, joins and obtains high-purity trimethyl-gallium; R wherein
1r
2r
3for the identical of C2～C6 or not identical alkyl or aryl.
2. method according to claim 1, is characterized in that, the ether in described trimethyl-gallium ether title complex is selected from tetrahydrofuran (THF), ether, isopropyl ether or methyltetrahydrofuran.
3. method according to claim 1, is characterized in that, described R
1r
2r
3n part is selected from tri-n-butylamine or N, N-Diethyl Aniline.
4. method according to claim 1, is characterized in that, described R
1r
2r
3the mol ratio of N part and trimethyl-gallium is 1～1.5 ︰ 1.
5. method according to claim 1, is characterized in that, described R
1r
2r
3it is 25～90 ℃ that the rate of addition of N part is controlled at maintenance system temperature.
6. according to the method described in claim 1～5 any one, it is characterized in that, described solution is joined for decompression solution and is joined, and it is 100～200mmHg that solution is joined pressure, and it is 90 ℃～180 ℃ that solution is joined temperature.
7. method according to claim 6, is characterized in that, described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
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| CN201310037648.1A CN103965227A (en) | 2013-01-30 | 2013-01-30 | Industrial purification method of trimethyl gallium |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193773A (en) * | 2014-09-05 | 2014-12-10 | 安徽亚格盛电子新材料有限公司 | Industrial purification method of trimethylindium |
| 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 |
| CN104860973A (en) * | 2015-05-12 | 2015-08-26 | 苏州普耀光电材料有限公司 | High-efficient purifying method for trimethyl gallium |
| JP2016056160A (en) * | 2014-02-07 | 2016-04-21 | 宇部興産株式会社 | Method for producing trialkylgallium |
| 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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| GB2432364A (en) * | 2005-11-18 | 2007-05-23 | Rohm & Haas Elect Mat | Improved method for purifying organometallic compounds |
| JP2010195690A (en) * | 2009-02-23 | 2010-09-09 | Ube Ind Ltd | High-purity trialkyl gallium, and method of producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016056160A (en) * | 2014-02-07 | 2016-04-21 | 宇部興産株式会社 | Method for producing trialkylgallium |
| CN104193773A (en) * | 2014-09-05 | 2014-12-10 | 安徽亚格盛电子新材料有限公司 | Industrial purification method of trimethylindium |
| CN104193773B (en) * | 2014-09-05 | 2017-11-07 | 安徽亚格盛电子新材料有限公司 | Trimethyl indium industrial purifying process |
| 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 |
| CN104744500B (en) * | 2015-04-23 | 2016-06-15 | 苏州普耀光电材料有限公司 | The purification process of the trialkyl compound of liquid state III family metal |
| CN104860973A (en) * | 2015-05-12 | 2015-08-26 | 苏州普耀光电材料有限公司 | High-efficient purifying method for trimethyl gallium |
| CN104860973B (en) * | 2015-05-12 | 2017-06-09 | 苏州普耀光电材料有限公司 | The purification process of trimethyl gallium |
| 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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Application publication date: 20140806 |
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