CN112028921B - Preparation method of high-purity trimethylaluminum - Google Patents
Preparation method of high-purity trimethylaluminum Download PDFInfo
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- CN112028921B CN112028921B CN202010883166.8A CN202010883166A CN112028921B CN 112028921 B CN112028921 B CN 112028921B CN 202010883166 A CN202010883166 A CN 202010883166A CN 112028921 B CN112028921 B CN 112028921B
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- trimethylaluminum
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- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 21
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 8
- -1 ether compound Chemical class 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 5
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- NEHMKBQYUWJMIP-OUBTZVSYSA-N chloromethane Chemical group Cl[13CH3] NEHMKBQYUWJMIP-OUBTZVSYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 3
- 239000012442 inert solvent Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 15
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical group [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 description 1
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical group [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Classifications
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- 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
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/062—Al linked exclusively to C
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention provides a preparation method of high-purity trimethylaluminum. The method takes aluminum trichloride as a raw material, and reacts with Grignard reagent of halomethane in nonpolar inert solvent to prepare high-purity trimethylaluminum. The solvent of the Grignard reagent is replaced by a nonpolar solvent, and a complex of trimethylaluminum and an ether compound does not exist in the reaction process, so that the yield and purity of trimethylaluminum are improved.
Description
Technical Field
The invention belongs to the field of organic metals, and relates to a preparation method of high-purity trimethylaluminum.
Background
The high-purity metal organic matters such as high-purity trimethylaluminum and the like are one of core raw materials for manufacturing high-brightness light-emitting diodes, new generation solar PERC batteries, phase change memories, semiconductor lasers, radio frequency integrated circuit chips and the like, and have important application in the electronic industries such as organic metal chemical vapor deposition, atomic layer deposition, low-temperature epitaxy and the like.
The silicon substrate LED technology is a domestic technology in China, is greatly popularized by China, and needs to adopt high-purity trimethylaluminum as a raw material. Through a series of experiments, the purity of the trimethylaluminum is found to directly influence the growth quality of the epitaxial wafer. The higher the purity of the product, the better the epitaxial wafer grows, so the synthesis of high purity trimethylaluminum becomes the current hot spot.
The Chinese patent applications with publication numbers of CN104774218A and CN102020668A both provide a method for synthesizing trimethylaluminum, and the method is simple and feasible and is suitable for industrial production. Both synthetic methods use diethyl ether as a solvent, and the diethyl ether is complex with a trimethylaluminum product, so that the separation difficulty in the later stage is high. The process is complicated, the purity of the crude product is between 95.0 and 99.0 percent, and the purity of the product can not meet the existing requirements.
Disclosure of Invention
In order to obtain high-purity trimethylaluminum, the invention provides a preparation method of high-purity trimethylaluminum.
The invention provides a preparation method of high-purity trimethylaluminum, which comprises the following steps:
(1) Adding magnesium powder and diethyl ether (or tetrahydrofuran) solvent into a reaction kettle filled with inert gas, controlling the temperature in the reaction kettle to be 15-80 ℃ and slowly adding halomethane, and reacting to obtain Grignard reagent solution;
(2) Removing diethyl ether (or tetrahydrofuran) solvent in the Grignard reagent solution by reduced pressure distillation, and then adding an inert nonpolar solvent to obtain a Grignard reagent solution dissolved by the nonpolar solvent;
(3) Slowly adding the non-polar solvent dissolved Grignard reagent solution into AlX at 30-50 ℃ under inert gas atmosphere 3 Wherein X is Cl, br or I, and separating out trimethylaluminum by rectification after the reaction is finished.
Preferably, the methyl halide is methyl chloride, methyl bromide or methyl iodide.
Preferably, the magnesium powder, diethyl ether, methyl halide and AlX 3 The molar ratio of (2) is 1.2: 4-8: 1:0.98.
preferably, the inert nonpolar solvent is n-pentane or n-hexane.
Preferably, the slow addition in step (1) and step (3) means dropwise addition.
Preferably, before step (2), a step of filtering the grignard reagent solution to remove solid substances (such as incompletely reacted magnesium powder) is further included.
Preferably, a filtration step is further included prior to the rectification of step (3).
The invention has the beneficial effects that: the method is characterized in that aluminum trichloride is used as a raw material, the raw material reacts with a Grignard reagent of methyl halide in a nonpolar inert solvent to prepare high-purity trimethylaluminum, the solvent of the Grignard reagent is replaced by the nonpolar solvent, a complex of trimethylaluminum and an ether compound does not exist in the reaction process, the rectification is simple and easy to separate, the product yield is more than 75%, and the purity can reach more than 99.3%.
Drawings
FIG. 1 is an NMR spectrum of trimethylaluminum prepared in accordance with the method of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Aluminum trichloride is used as a raw material, and reacts with a format reagent of methyl halide in a nonpolar inert solvent to prepare high-purity trimethylaluminum, and the preparation method comprises the following specific steps:
(1) Adding 1.2 mol of magnesium powder and 4-8 mol of diethyl ether (or tetrahydrofuran) solvent into a reaction kettle filled with inert gas, slowly adding 1 mol of halomethane (chloromethane, bromomethane or iodomethane) at 15-80 ℃, and continuing to react for 1-6 hours after the dropwise addition of the halomethane is finished, and stopping the reaction to obtain a format reagent solution;
(2) Filtering the format reagent solution obtained by the reaction, decompressing and evaporating the solvent, and then adding the same amount of inert nonpolar solvent (such as n-pentane or n-hexane) for dissolution to obtain a format reagent solution dissolved by the nonpolar solvent;
(3) Stirring under inert gas atmosphere, slowly dripping to 0.98 mol of AlX at 30-50 DEG C 3 (x=cl, br, I), after the completion of the dropwise addition for 2 to 6 hours, continuing the reaction for 2 to 5 hours, and stopping the reaction; filtering, rectifying, removing solvent, obtaining trimethylaluminum product at 127 deg.C, product yield being more than 75%, purity being up to above 99.3%.
Several exemplary embodiments are described below.
Example 1:
adding 1.2 mol of magnesium powder and 6 mol of diethyl ether solvent into a reaction kettle filled with inert gas,1 mol of methyl iodide was slowly added at 15℃and the reaction was continued for 1 hour, and the reaction was stopped. Filtering, evaporating the solvent from the Grignard reagent solution obtained by the reaction under reduced pressure, and adding n-pentane with the same amount as the Grignard reagent solution for dissolution to obtain a non-polar solvent-dissolved Grignard reagent solution. Then, under an inert gas atmosphere, stirring was carried out and slowly dropped at 30℃to 0.98 mol of AlI 3 After the completion of the 2-hour dropwise addition, the reaction was continued for 2 hours, and the reaction was stopped. Filtering, rectifying, removing solvent, obtaining trimethylaluminum product at 127 ℃, wherein the product yield is 81%, and the purity is 99.6%.
Example 2:
1.2 mol of magnesium powder and 4 mol of tetrahydrofuran are added into a reaction kettle filled with inert gas, 1 mol of bromomethane is slowly added at 40 ℃ for continuous reaction for 3 hours, and the reaction is stopped. Filtering, evaporating the solvent from the Grignard reagent solution obtained by the reaction under reduced pressure, and adding the same amount of inert nonpolar solvent n-hexane for dissolving to obtain the Grignard reagent solution dissolved by the nonpolar solvent. Then, under an inert gas atmosphere, stirring was carried out and slowly dropping to 0.98 mol of AlBr at 40 ℃ 3 After the completion of the dropwise addition for 4 hours, the reaction was continued for 3 hours, and the reaction was stopped. Filtering, rectifying, removing solvent, obtaining trimethylaluminum product at 127 ℃, wherein the product yield is more than 79%, and the purity is 99.3%.
Example 3:
1.2 mol of magnesium powder and 8 mol of tetrahydrofuran are added into a reaction kettle filled with inert gas, 1 mol of chloromethane is slowly added at 60 ℃, the reaction is continued for 6 hours, and the reaction is stopped. Filtering, evaporating the solvent from the Grignard reagent solution obtained by the reaction under reduced pressure, and adding the same amount of inert nonpolar solvent n-hexyl) for dissolving to obtain the Grignard reagent solution dissolved by the nonpolar solvent. Then, under an inert gas atmosphere, stirring and slowly dropping to 0.98 mol of AlCl at 50 DEG C 3 After the completion of the addition for 6 hours, the reaction was continued for 5 hours, and the reaction was stopped. Filtering, rectifying, removing solvent, obtaining trimethylaluminum product at 127 ℃, and obtaining the product with 76% of yield and 99.3% of purity.
According to national standard electronic grade trimethylaluminum GBT36653-2018, the purity of trimethylaluminum is mainly affected by five elements Cu, fe, mg, si, zn, and the five main impurity contents are analyzed by ICP-MS test. According to the test result, the total content of five elements is 598ppm, the purity of trimethylaluminum is 99.4%, and the purity of the product is more than 99.3%.
TABLE 1 detection results of ICP-MS of trimethylaluminum products
As can be seen from the nuclear magnetic spectrum chart of FIG. 1, the left side is the position of the deuterated benzene peak of the special solvent for nuclear magnetic resonance, and the right side only shows the characteristic peak of trimethylaluminum, and no other organic impurities exist, thus indicating that no organic impurities exist in the trimethylaluminum product.
The above embodiments are only for illustrating the present invention, not for limiting the present invention, and various changes and modifications may be made by one of ordinary skill in the relevant art without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions are also within the scope of the present invention, which is defined by the claims.
Claims (7)
1. A preparation method of trimethylaluminum comprises the following steps:
(1) Adding magnesium powder and diethyl ether solvent into a reaction kettle filled with inert gas, and controlling the temperature in the reaction kettle to be 15 ～ Slowly adding methyl halide at 80 ℃ to react to obtain a Grignard reagent solution;
(2) Removing the ether solvent in the Grignard reagent solution by reduced pressure distillation, and then adding an inert nonpolar solvent to obtain a Grignard reagent solution dissolved by the nonpolar solvent; the inert nonpolar solvent is n-pentane or n-hexane;
(3) Slowly adding the non-polar solvent dissolved Grignard reagent solution into AlX3 at 30-50 ℃ in an inert gas atmosphere, wherein X is Cl, br or I, filtering after the reaction is finished, and separating trimethylaluminum by rectification.
2. The method for producing trimethylaluminum according to claim 1, wherein: the diethyl ether is replaced by tetrahydrofuran.
3. The method for producing trimethylaluminum according to claim 1 or 2, characterized in that: the methyl halide is chloromethane, bromomethane or iodomethane.
4. The method for producing trimethylaluminum according to claim 1, wherein: the molar ratio of the magnesium powder to the diethyl ether to the halomethane to the AlX3 is 1.2: 4-8: 1:0.98.
5. the method for preparing trimethylaluminum according to claim 2, wherein: the molar ratio of the magnesium powder to the tetrahydrofuran to the halomethane to the AlX3 is 1.2: 4-8: 1:0.98.
6. the method for producing trimethylaluminum according to claim 1 or 2, characterized in that: the slow addition in the step (1) and the step (3) refers to dropwise addition.
7. The method for producing trimethylaluminum according to claim 1 or 2, characterized in that: the method further comprises the step of filtering and removing solid matters from the Grignard reagent solution before the step (2).
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| CN114849671B (en) * | 2022-06-10 | 2022-11-08 | 大连科利德光电子材料有限公司 | Impurity adsorbent, preparation method and method for purifying trimethylaluminum by using impurity adsorbent |
| CN115166075B (en) * | 2022-06-24 | 2024-02-27 | 南大光电半导体材料有限公司 | Method for detecting chloride ion content in MO source |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774218A (en) * | 2015-04-23 | 2015-07-15 | 苏州普耀光电材料有限公司 | Preparation method of high-purity trimethyl aluminum |
| CN110483580A (en) * | 2019-09-06 | 2019-11-22 | 广东先导先进材料股份有限公司 | A kind of high-purity trialkyl antimony and the preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774218A (en) * | 2015-04-23 | 2015-07-15 | 苏州普耀光电材料有限公司 | Preparation method of high-purity trimethyl aluminum |
| CN110483580A (en) * | 2019-09-06 | 2019-11-22 | 广东先导先进材料股份有限公司 | A kind of high-purity trialkyl antimony and the preparation method and application thereof |
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