CN103965228A - Industrial purification method of triethyl gallium - Google Patents
Industrial purification method of triethyl gallium Download PDFInfo
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- CN103965228A CN103965228A CN201310037672.5A CN201310037672A CN103965228A CN 103965228 A CN103965228 A CN 103965228A CN 201310037672 A CN201310037672 A CN 201310037672A CN 103965228 A CN103965228 A CN 103965228A
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Abstract
The invention discloses an industrial purification method of triethyl gallium. The industrial purification method comprises the following steps of adding triethyl gallium or a triethyl 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 25-100 DEG C, after dropwise addition, carrying out stirring at a temperature of 60-90 DEG C for 2-4h, and carrying out decomplexation to obtain high-purity triethyl 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 triethyl-gallium.
Background technology
Because gallium nitride semiconductor material has that energy gap is 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, show in light display, the field of microelectronic devices such as opto-electronic device and high temperature, high-frequency high-power electronics such as light storage, optical detection has wide application prospects, so the development of the III A group-III nitride taking gan as representative is very fast, wherein the most noticeable is application as luminescent material, is gallium nitride based light emitting diode (LED).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, there is extraordinary prospect in the application in general lighting field especially.LED lamp, by replacing a large amount of conventional light source such as incandescent light, electricity-saving lamp that use at present, is called as the revolution of 21 century lighting source.
At present unique preparation method that can realize industrialization production gallium-nitride-based devices is MOCVD(metal organic chemical vapor deposition), 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 the carrier gas such as hydrogen or nitrogen.Large owing to thering is production capacity, feature with short production cycle, but the purity of process Raw, quality have vital impact to epitaxial wafer and even final photoelectric device or high-frequency element, especially play especially conclusive effect for the function of the higher product such as blue-light device, semiconductor laser of technology content.Triethyl-gallium be at present another kind ofly except trimethyl-gallium use the most extensively, the most important, the starting material of maturation the most, and have more advantage than trimethyl-gallium in some aspects.
Though at present about the report of triethyl-gallium purification process has, also there is no the method report of related industries purifying triethyl-gallium.Conventional purification process has: 1, with triethyl-gallium and the effect of potassium-sodium alloy, then obtain high-purity triethyl-gallium by rectification under vacuum, because potassium-sodium alloy activity is very high, requirement is larger again simultaneously, brings potential safety hazard certainly will to operation and last handling process; 2, with triethyl-gallium and N, N, N', N'-tetramethyl--4,4'-diaminodiphenylmethane forms part, then solution is joined to obtain high-purity triethyl-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 triethyl-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 triethyl-gallium of the present invention, comprises the steps:
In the reactor of inert atmosphere, add triethyl-gallium or triethyl-gallium ether title complex, then add R
1r
2r
3n part reacts, and the temperature of reaction system remains on 25～100 DEG C, after dripping, stirs 2～6 hours at 60～100 DEG C, joins and obtains high-purity triethyl-gallium finally by solution.
Ether in described triethyl-gallium ether title complex is selected from tetrahydrofuran (THF), ether, isopropyl ether or methyltetrahydrofuran, preferably ether;
Described R
1r
2r
3in N part, R
1r2R
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 triethyl-gallium is 1～1.5 ︰ 1;
R
1r
2r
3it is 25～100 DEG C that the rate of addition of N part is controlled at maintenance system temperature;
Described solution is joined and is joined that (it is 100～200mmHg that solution is joined pressure for decompression solution; Temperature is 100～200 DEG C), obtain high-purity triethyl-gallium finally by crossing rectifying.
Described inert atmosphere can be nitrogen atmosphere or argon gas atmosphere.
Before described triethyl-gallium purification, purity is 60%～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.
Based on above-mentioned advantage, the method is particularly suitable for industrialized purification triethyl-gallium.
Embodiment
Embodiment 1
Under inert atmosphere, in reactor, add 1600 grams of triethyl-galliums, under agitation condition, in reactor, drip 2200 grams of tri-n-butylamines, control the speed dripping and maintain the temperature between 25 DEG C～100 DEG C, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100～200mmHg that solution is joined pressure; Temperature is 100～200 DEG C) after obtain 1450 grams of high-purity triethyl-galliums through rectifying again, taking triethyl-gallium as calculate benchmark, productive rate 91%.
Embodiment 2
Under inert atmosphere, in reactor, add 1600 grams of triethyl-galliums, under agitation condition, in reactor, drip N, 1650 grams of N-Diethyl Anilines, control the speed dripping and maintain the temperature between 25 DEG C～100 DEG C, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100～200mmHg that solution is joined pressure; Temperature is 100～200 DEG C) after obtain 1400 grams of high-purity triethyl-galliums through rectifying again, taking triethyl-gallium as calculate benchmark, productive rate 87%.
Embodiment 3
Under inert atmosphere, in reactor, add 1150 grams of triethyl-gallium etherates, under agitation condition, in reactor, drip N, 850 grams of N-Diethyl Anilines, control the speed dripping and maintain the temperature between 25 DEG C～100 DEG C, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100～200mmHg that solution is joined pressure; Temperature is 100～200 DEG C) after obtain 640 grams of high-purity triethyl-galliums through rectifying again, taking triethyl-gallium as calculate benchmark, productive rate 82%.
Embodiment 4
Under inert atmosphere, in reactor, add 1150 grams of triethyl-gallium etherates, under agitation condition, in reactor, drip 1050 grams of tri-n-butylamines, control the speed dripping and maintain the temperature between 25 DEG C～100 DEG C, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100～200mmHg that solution is joined pressure; Temperature is 100～200 DEG C) after obtain 686 grams of high-purity triethyl-galliums through rectifying again, taking triethyl-gallium as calculate benchmark, productive rate 88%.
Embodiment 5
Under inert atmosphere, in reactor, add 1150 grams of triethyl-gallium isopropyl ether title complexs, under agitation condition, in reactor, drip 850 grams of tri-n-butylamines, control the speed dripping and maintain the temperature between 25 DEG C～100 DEG C, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100～200mmHg that solution is joined pressure; Temperature is 100～200 DEG C) after obtain 490 grams of high-purity triethyl-galliums through rectifying again, taking triethyl-gallium as calculate benchmark, productive rate 81%.
Embodiment 6
Under inert atmosphere, in reactor, add 1150 grams of triethyl-gallium isopropyl ether title complexs, under agitation condition, in reactor, drip N, 680 grams of N-Diethyl Anilines, control the speed dripping and maintain the temperature between 25 DEG C～100 DEG C, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100～200mmHg that solution is joined pressure; Temperature is 100～200 DEG C) after obtain 460 grams of high-purity triethyl-galliums through rectifying again, taking triethyl-gallium as calculate benchmark, productive rate 73%.
Embodiment 7
Under inert atmosphere, in reactor, add 1150 grams of triethyl-gallium tetrahydrofuran (THF) title complexs, under agitation condition, in reactor, drip 950 grams of tri-n-butylamines, control the speed dripping and maintain the temperature between 25 DEG C～100 DEG C, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100～200mmHg that solution is joined pressure; Temperature is 100～200 DEG C) after obtain 500 grams of high-purity trimethyl-galliums through rectifying again, taking triethyl-gallium as calculate benchmark, productive rate 71%.
Embodiment 8
Under inert atmosphere, in reactor, add 1150 grams of triethyl-gallium tetrahydrofuran (THF) title complexs, under agitation condition, in reactor, drip N, 800 grams of N-Diethyl Anilines, control the speed dripping and maintain the temperature between 25 DEG C～100 DEG C, after dropping finishes, continue reaction 4 hours.Solution joins that (it is 100～200mmHg that solution is joined pressure; Temperature is 100～200 DEG C) after obtain 470 grams of high-purity triethyl-galliums through rectifying again, taking triethyl-gallium as calculate benchmark, productive rate 65%.
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 triethyl-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 hardly any waste, is particularly suitable for industrialized purification.
Claims (7)
1. a triethyl-gallium industrialized purification method, is characterized in that, comprises the steps: to add triethyl-gallium or triethyl-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 25～100 DEG C, after dripping, stirs 2～4 hours at 60～100 DEG C, joins and obtains high-purity triethyl-gallium finally by solution; Wherein R
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 triethyl-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 triethyl-gallium is 1～1.5 ︰ 1.
5. method according to claim 1, is characterized in that, described R
1r
2r
3the rate of addition of N part is controlled at rate of addition, and to be controlled at maintenance system temperature be 25～100 DEG C.
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; Temperature is 100～200 DEG C.
7. method according to claim 6, is characterized in that, described inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
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| CN201310037672.5A CN103965228A (en) | 2013-01-30 | 2013-01-30 | Industrial purification method of triethyl gallium |
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| CN201310037672.5A CN103965228A (en) | 2013-01-30 | 2013-01-30 | Industrial purification method of triethyl gallium |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108822142A (en) * | 2018-09-03 | 2018-11-16 | 上海芯渊光电科技有限公司 | A kind of preparation method of triethyl-gallium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603328A (en) * | 2003-06-19 | 2005-04-06 | 信越化学工业株式会社 | Method for purifying metal hydrocarbons |
| JP2008081451A (en) * | 2006-09-28 | 2008-04-10 | Ube Ind Ltd | High-purity trialkylgallium and its preparation method |
| CN102718784A (en) * | 2012-07-05 | 2012-10-10 | 广东先导稀材股份有限公司 | Decomplexation method of metal organic compound and ether complex |
-
2013
- 2013-01-30 CN CN201310037672.5A patent/CN103965228A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603328A (en) * | 2003-06-19 | 2005-04-06 | 信越化学工业株式会社 | Method for purifying metal hydrocarbons |
| JP2008081451A (en) * | 2006-09-28 | 2008-04-10 | Ube Ind Ltd | High-purity trialkylgallium and its preparation method |
| CN102718784A (en) * | 2012-07-05 | 2012-10-10 | 广东先导稀材股份有限公司 | Decomplexation method of metal organic compound and ether complex |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108822142A (en) * | 2018-09-03 | 2018-11-16 | 上海芯渊光电科技有限公司 | A kind of preparation method of triethyl-gallium |
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Application publication date: 20140806 |