CN117551123A - Chlorine removal method for trimethyl aluminum crude product - Google Patents
Chlorine removal method for trimethyl aluminum crude product Download PDFInfo
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- CN117551123A CN117551123A CN202311624130.8A CN202311624130A CN117551123A CN 117551123 A CN117551123 A CN 117551123A CN 202311624130 A CN202311624130 A CN 202311624130A CN 117551123 A CN117551123 A CN 117551123A
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- trimethylaluminum
- chlorine
- product
- halogenated hydrocarbon
- reagent
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- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000000460 chlorine Substances 0.000 title claims abstract description 78
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 78
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000012043 crude product Substances 0.000 title abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 43
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 31
- 150000008282 halocarbons Chemical class 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 15
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 12
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 claims description 10
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 9
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 claims description 8
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 7
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229940102396 methyl bromide Drugs 0.000 claims description 3
- 229940050176 methyl chloride Drugs 0.000 claims description 3
- 150000005826 halohydrocarbons Chemical class 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 35
- 239000012535 impurity Substances 0.000 abstract description 32
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 239000004065 semiconductor Substances 0.000 abstract description 19
- 238000011282 treatment Methods 0.000 abstract description 17
- 239000007818 Grignard reagent Substances 0.000 abstract description 7
- 150000004795 grignard reagents Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003303 reheating Methods 0.000 abstract description 3
- 238000013341 scale-up Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 9
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 9
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 229910002704 AlGaN Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000574 NaK Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004871 chemical beam epitaxy Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005571 anion exchange chromatography Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 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 System
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/062—Al linked exclusively to C
Abstract
The invention discloses a chlorine removal method for a crude product of trimethylaluminum. The crude trimethylaluminum product contains trimethylaluminum and methylaluminum chloride, and the chlorine removal method comprises the following steps: and (3) contacting the crude trimethylaluminum product with a format reagent, and carrying out nucleophilic substitution reaction on the format reagent and methylaluminum chloride to generate magnesium chloride for removal. The method can reduce the content of organic chlorine impurities in the trimethylaluminum to meet the semiconductor grade requirement, and removes the chlorine impurities in the trimethylaluminum by indirectly or directly using Grignard reagent reaction, so that the treatment time is short, the efficiency of the used reagent is high, the industrial scale-up production is simple and convenient, and the safety of the used reagent is high; in some preferred embodiments, the rectified front cut can be added to the next batch for reheating treatment, so that the reagent utilization rate is improved, and the cost is reduced.
Description
Technical Field
The invention relates to the technical field of preparation of metal organic compounds, in particular to a chlorine removal method of a trimethyl aluminum crude product.
Background
Trimethylaluminum (TMA) is an important feedstock for growing optoelectronic materials in metal organic vapor deposition (MOCVD) and Chemical Beam Epitaxy (CBE) processes. The method is mainly used for growing epitaxial wafers of III-nitride semiconductor materials mainly comprising AlGaN/AlN, is a core raw material for growing epitaxial wafers of third-generation semiconductors such as AlGaN, A1N and the like, and is one of core raw materials of phase-change memories, radio frequency integrated circuit chips and the like.
The quality of trimethylaluminum is mainly affected by impurities in trimethylaluminum. Specifically, due to the trimethylaluminum preparation process, organochlorine impurities are introduced during the synthesis stage. The organic chlorine impurity generally has higher vapor pressure than or similar to trimethylaluminum, so that during the subsequent rectification process, the organic chlorine is enriched in trimethylaluminum rectification equipment, thereby influencing the quality of the subsequent trimethylaluminum products after rectification, the chlorine impurity is easy to corrode metal equipment, the service life of the equipment is reduced, and during the production of the compound semiconductor material from trimethylaluminum, the quality and the service life of a downstream wafer are seriously reduced due to the chlorine impurity, and the performance of the compound semiconductor is finally influenced. Thus, there is a market demand for trimethylaluminum products having a lower chlorine content (chlorine content standard of less than 1 ppm).
In order to solve the problem of chlorine content, some prior art proposes a technical solution for removing organic chlorine by chemical reaction, for example:
chinese patent No. CN111116625A proposes the use of MAl (CH 3 ) 4 The compound is used for reducing the chlorine content of trimethylaluminum and eliminating the dimethylaluminum chloride, M is an IA group element including lithium, sodium and potassium, however, the reaction temperature of the method is 150-160 ℃, and the method needs intense stirring, the reaction temperature is higher than 127 ℃ of the boiling point of trimethylaluminum, the high temperature can lead the decomposition of trimethylaluminum to cause the loss of trimethylaluminum, and the intense stirring is difficult to realize in industrial production.
Chinese patent No. 1749260A proposes a method for reducing chlorine content in trimethylaluminum by using sodium metal in a high boiling point solvent, however, when sodium reacts with chlorine impurities, the produced byproduct metal aluminum can be coated on the surface of sodium metal to form a crust, so that the sodium is prevented from continuously reacting, the reaction speed is reduced, the reaction is incomplete, the used high boiling point solvent is not completely reacted, trimethylaluminum is decomposed at high temperature to cause trimethylaluminum loss, and the sodium metal is too active and has high safety risk.
Chinese patent No. 106831841A proposes a method for removing chlorine impurity in trimethylaluminum by using potassium-sodium alloy, however, the method needs more than 20 hours to realize chlorine removal effect, and has long time consumption, low efficiency, difficult industrial production, higher activity of potassium-sodium alloy than sodium and high safety risk.
US2923725a proposes a method for removing chlorine impurities from trimethylaluminum using an organic amine by complexing the organic amine with trimethylaluminum and then performing a solution for removing chlorine impurities, in which the solution requires a temperature higher than the boiling point of trimethylaluminum, and the high temperature may cause the decomposition of trimethylaluminum to cause the loss of trimethylaluminum, and increase the risk of introducing a high boiling point solvent into the product.
Therefore, development of a method for removing chlorine impurities in trimethylaluminum, which is mild in reaction, thorough in organic chlorine removal, high in reaction speed and high in safety, and is suitable for industrial application, is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a chlorine removal method for a crude product of trimethylaluminum.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a method for chlorine removal of a crude trimethylaluminum product comprising trimethylaluminum and methylaluminum chloride, comprising:
and (3) contacting the crude trimethylaluminum product with a format reagent, and carrying out nucleophilic substitution reaction on the format reagent and methylaluminum chloride to generate magnesium chloride for removal.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
the method can reduce the content of organic chlorine impurities in the trimethylaluminum to meet the semiconductor grade requirement, and removes the chlorine impurities in the trimethylaluminum by indirectly or directly using Grignard reagent reaction, so that the treatment time is short, the efficiency of the used reagent is high, the industrial scale-up production is simple and convenient, and the safety of the used reagent is high;
in some preferred embodiments, the rectified front cut can be added to the next batch for reheating treatment, so that the reagent utilization rate is improved, and the cost is reduced.
The foregoing description is only an overview of the present invention and is intended to enable those skilled in the art to make more clear the scope of the present invention and to be practiced in accordance with the present invention as described below with reference to the preferred embodiments thereof.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
Moreover, relational terms such as "first" and "second", and the like, may be used solely to distinguish one from another component or method step having the same name, without necessarily requiring or implying any actual such relationship or order between such components or method steps.
The embodiment of the invention provides a chlorine removal method of a crude trimethylaluminum product, wherein the crude trimethylaluminum product comprises trimethylaluminum and methylaluminum chloride, and the method comprises the following steps:
and (3) contacting the crude trimethylaluminum product with a format reagent, and carrying out nucleophilic substitution reaction on the format reagent and methylaluminum chloride to generate magnesium chloride for removal.
In some embodiments, the chlorine removal process may specifically include the steps of:
and mixing the magnesium metal with the crude trimethylaluminum product to form a first mixed system.
Gradually introducing halogenated hydrocarbon into the first mixed system to enable the halogenated hydrocarbon to react with magnesium in situ to form the format reagent, and enabling the format reagent to react with the methylaluminum chloride in a nucleophilic substitution reaction.
Or in some embodiments, directly mixing the crude trimethylaluminum with a formative reagent to form a second mixed system, while simultaneously reacting the formative reagent with the methylaluminum chloride to produce the nucleophilic substitution reaction.
The above is an overall process of the technical solution adopted in the embodiment of the present invention, and as some specific practical application examples, the chlorine removal method may be implemented in the following two ways:
mode one: mixing magnesium and trimethylaluminum, introducing methyl chloride or methyl bromide under heating and stirring at a certain temperature, or adding methyl iodide in a dropwise manner, converting organic chlorine in dimethyl aluminum chloride or methyl aluminum dichloride into inorganic chlorine in a magnesium chloride form through in-situ synthesis and nucleophilic substitution reaction of a Grignard reagent, and finally rectifying to obtain the semiconductor grade low-chlorine trimethylaluminum.
Mode two: directly adding methyl magnesium chloride or methyl magnesium bromide or methyl magnesium iodide into trimethylaluminum in a dropwise manner or reversely dropwise adding vice versa under the heating and stirring conditions at a certain temperature, converting organic chlorine in the dimethylaluminum chloride or methylaluminum dichloride into inorganic chlorine in a magnesium chloride form, and finally obtaining the semiconductor grade low-chlorine trimethylaluminum through rectification.
Since chlorine impurities in crude trimethylaluminum are often on the order of tens of ppm, the amount of formazan reagent consumed in the reaction is very small, but in order to achieve a more thorough removal effect, a sufficient concentration of formazan reagent still needs to be present in the reaction system, which results in a substantially higher amount of formazan reagent in the reaction system than the stoichiometric amount, whereas in the first mode, since the formazan reagent is formed in situ on the magnesium surface, a local concentration advantage on the magnesium surface is formed, a sufficient reaction trend can be formed without increasing the overall concentration, and magnesium metal may have a certain acceleration effect on the reaction, the reaction in the first mode is more thorough than in the second mode, under the same condition, the amount of formazan reagent required to be added (or the calculated equivalent formazan reagent addition amount for generating the formazan reagent) is less, the brought new impurities are also less, and the difficulty of formazan separation adopted for subsequent rectification is reduced (the compatibility of the formazan reagent with trimethylaluminum is generally higher).
With respect to specific material ratios, in some embodiments, the mass ratio of magnesium metal to crude trimethylaluminum in the first mixed system is 1:1 to 1:10000, in some preferred embodiments, is 1:10 to 1:5000.
in some embodiments, the mass ratio of the halocarbon to the crude trimethylaluminum introduced is 1:1 to 1:5000, in some preferred embodiments, is 1:5 to 1:2000.
in some embodiments, in the second mixed system, the mass ratio of the formative reagent to the crude trimethylaluminum is 1:1 to 1:5000, in some preferred embodiments 1:5 to 1:2000.
With respect to specific reaction conditions, in some embodiments, the nucleophilic substitution reaction is at a temperature of 40 to 125 ℃ for a period of 1 to 10 hours.
In some embodiments, the nucleophilic substitution reaction is performed while maintaining continuous agitation at not less than 60rpm.
Yet more finely divided, in some embodiments, the halogenated hydrocarbon comprises a gaseous halogenated hydrocarbon or a liquid halogenated hydrocarbon; when the gaseous halogenated hydrocarbon is adopted, the temperature of the nucleophilic substitution reaction is controlled to be 50-125 ℃, preferably 60-120 ℃, and more preferably 80-110 ℃; when the liquid halogenated hydrocarbon is used, the temperature of the nucleophilic substitution reaction is controlled to 40 to 100 ℃, preferably 50 to 90 ℃, and more preferably 50 to 80 ℃.
And because of the different states of the halocarbons, in some embodiments, the gaseous halocarbon is introduced by contacting the first mixed system with the gaseous halocarbon; and/or the liquid halogenated hydrocarbon is introduced by dropwise adding the liquid halogenated hydrocarbon into the first mixed system.
With respect to the specific choice of halocarbon/formative reagent, in some embodiments, the gaseous halocarbon may comprise, for example, methyl chloride and/or methyl bromide.
In some embodiments, the liquid halogenated hydrocarbon may comprise methyl iodide.
In some embodiments, the formative reagent may include any one or a combination of two or more of methyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide.
In some embodiments, the methylaluminum chloride such impurities may include methylaluminum dichloride and/or dimethylaluminum monochloride.
Before treatment, in some embodiments, 10 to 2000ppm of the crude trimethylaluminum is present.
While with respect to subsequent specific treatments, in some embodiments, the chlorine removal process may further comprise:
and rectifying the mixed system obtained after the nucleophilic substitution reaction to obtain a pure trimethylaluminum product through separation.
Specifically, in some embodiments, the rectification treated front cut, middle cut, still residue receive ratio is (0.5-3): (5-9): (0.5-3); and collecting the pure trimethylaluminum product in the middle distillate.
After treatment, in some embodiments, the chlorine content in the trimethylaluminum neat product may preferably be less than 1ppm
As some typical application examples of the above technical solutions, the chlorine removal method provided by the embodiment of the present invention is implemented by adopting the following specific processes:
mode one:
step one, mixing trimethylaluminum and magnesium
Taking trimethylaluminum with a certain mass, and then mixing the trimethylaluminum with magnesium according to a mass ratio of 1:1 to 1:10000 adding proper amount of magnesium chips or magnesium powder or magnesium strips
Step two, reacting halomethane with the mixed solution
Adding a halomethane under the conditions of heating and stirring, wherein the mass of the halomethane and the trimethylaluminum is 1:1 to 1:5000, adding a proper amount of halomethane, and controlling the reaction temperature to be 50-125 ℃, preferably 60-120 ℃ and most preferably 80-110 ℃ when adding chloromethane or bromomethane; when methyl iodide is added, the reaction temperature is controlled to 40 to 100 ℃, preferably 50 to 90 ℃, and most preferably 50 to 80 ℃. Then heating and stirring are continuously carried out for 1-10h,
step three, rectifying and collecting the product
After heating, the front fraction, the middle fraction and the kettle residue are collected according to different proportions by rectification
Moreover, the residual magnesium metal in the kettle residue can be recycled after simple separation and cleaning, and can be used for other purposes, and can be further used for the next chlorine removal process, while in contrast, the alkali metals such as sodium, potassium and the like in the prior art mentioned above cannot be used continuously due to the formation of the surface aluminum shell.
Mode two:
step one, reacting methyl magnesium chloride, methyl magnesium bromide or methyl magnesium iodide with trimethylaluminum
Taking trimethylaluminum with a certain mass, and then mixing the trimethylaluminum with methyl magnesium chloride or methyl magnesium bromide or methyl magnesium iodide according to the mass ratio of 1:1 to 1:5000, the reaction temperature should be controlled between 40 and 125 ℃, preferably between 60 and 120 ℃ and most preferably between 80 and 110 ℃. And dropwise adding methyl magnesium chloride, methyl magnesium bromide or methyl magnesium iodide into the trimethylaluminum while stirring, or reversely dropwise adding, and continuously heating and stirring for 1-10h after the reagent is completely dripped.
Step two, rectifying and collecting the product
And after heating, collecting front fraction, middle fraction and kettle residue according to different proportions by rectification.
With respect to further technical effects of the present invention, in some embodiments, the chlorine removal process may further include: and mixing the collected front fraction with the new crude trimethylaluminum product, and removing methylaluminum chloride.
Moreover, the residual magnesium metal in the kettle residue can be recycled after simple separation and cleaning, and can be used for other purposes, and can be further used for the next chlorine removal process, while in contrast, the alkali metals such as sodium, potassium and the like in the prior art mentioned above cannot be used continuously due to the formation of the surface aluminum shell.
The technical scheme of the invention is further described in detail through a plurality of embodiments. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
In addition, because of the physicochemical characteristics of water explosion and air spontaneous combustion of trimethylaluminum, all the work in the embodiment of the invention is carried out under the atmosphere of inert gases such as nitrogen or argon, and the like, so that the environmental factors such as air, moisture and the like are strictly removed, and the used experimental instrument is cleaned according to strict cleaning standards, so that the influence of the contamination of the experimental instrument on experimental results is eliminated.
Example 1
The chlorine removal treatment process of trimethylaluminum in this example is specifically as follows:
step one, mixing trimethylaluminum and magnesium
1g of magnesium turnings was placed in a clean round bottom flask and 1000g of trimethylaluminum was added.
Step two, reacting halomethane with the mixed solution
The reaction temperature was controlled at 100℃and then 10g of chloromethane gas was charged with stirring while heating, and after the gas charging was completed, stirring was continued at 60rpm to 5 hours.
Step three, rectifying and collecting the product
After heating, rectifying the product according to 2:7:1, collecting a front cut fraction, a middle cut fraction and a residue, and collecting 680g of a trimethylaluminum middle cut fraction.
After the sample is treated, the chlorine impurity in 680g of fraction in trimethylaluminum collected after the treatment is reduced from 89ppm to 0.78ppm, thereby meeting the quality requirement of semiconductors.
Comparative examples 1 to 1
This comparative example is substantially the same as example 1, except that the reaction temperature is mainly different, as shown in detail below:
step one, mixing trimethylaluminum and magnesium
1g of magnesium turnings was taken in a clean round bottom flask and 1000g of trimethylaluminum was added
Step two, reacting halomethane with the mixed solution
The reaction temperature was controlled at 40℃and then 10g of chloromethane gas was charged with stirring while heating, and after the gas charging was completed, stirring was continued at 60rpm to 5 hours.
Step three, rectifying and collecting the product
After heating, rectifying the product according to 2:7:1, collecting a front cut fraction, a middle cut fraction and a residue, and collecting 680g of a trimethylaluminum middle cut fraction.
After the sample is treated, the chlorine impurity in the fraction in 680g of trimethyl aluminum collected after the treatment is changed from 89ppm to 85ppm, and the quality requirement of the semiconductor is not met.
Comparative examples 1 to 2
This comparative example is substantially the same as example 1, with the main difference that:
in the second mode, methyl magnesium chloride is directly used for reaction, the methyl magnesium chloride is not synthesized in situ, and other reaction conditions and material proportions are kept unchanged.
The method specifically comprises the following steps:
step one, reacting methyl magnesium chloride with trimethylaluminum
1000g of trimethylaluminum was taken in a clean round-bottomed flask, after which 3.08g of methylmagnesium chloride (kept in the same amount as that of methylmagnesium chloride produced in example 1) was added dropwise with stirring at a temperature of 100℃and, after the completion of the addition of the reagent, the stirring was continued with heating for 5 hours.
Step two, rectifying and collecting the product
After heating, rectifying the product according to 2:7:1, collecting a front cut fraction, a middle cut fraction and a residue, and collecting 680g of a trimethylaluminum middle cut fraction.
After the sample is treated, the fraction chlorine impurity in the treated trimethylaluminum is reduced from 89ppm to 8.3ppm through anion chromatographic analysis, and the fraction chlorine impurity is obviously reduced but does not meet the quality requirement of semiconductor grade.
It should be noted that although the embodiment represented by this comparative example is less thorough in the removal of chlorine impurities at equivalent amounts than example 1, this does not mean that this embodiment is not an embodiment of the invention, as it still achieves a significant reduction in the chlorine impurity content.
Based on the actual experience of the present inventors, in general, to ensure thorough removal of organochlorine impurities to the semiconductor level, it is often necessary to maintain a mass ratio of grignard reagent to trimethylaluminum of 1 when processing in mode two: 100 or more.
Comparative examples 1 to 3
This example illustrates the chlorine removal treatment process of 200g of the fore-cut trimethylaluminum received in example 1 mixed with 800g of fresh trimethylaluminum, with the purpose of verifying the recycling effect of the fore-cut, as follows:
step one, trimethylaluminum mixing
200g of the front-end trimethylaluminum received in example 1 was mixed with 800g of the chlorine-containing trimethylaluminum feedstock with stirring;
2. reacting halomethane with the mixed solution
The reaction temperature was controlled at 100℃and heated and stirred at 60rpm for 5 hours.
Step three, rectifying and collecting the product
After heating, rectifying the product according to 2:7:1, collecting a front fraction, a middle fraction and a residue, and collecting 685g of a trimethylaluminum middle fraction.
The sample is obtained by anion chromatographic analysis after being treated, and the chlorine impurity in the fraction in 685g of trimethylaluminum collected after the treatment is reduced from 72ppm to 29ppm, and the chlorine removal effect is obvious although the quality requirement of the semiconductor is not met.
Example 2-1
The chlorine removal treatment process of trimethylaluminum in this example is specifically as follows:
step one, mixing trimethylaluminum and magnesium
Into a clean round bottom flask and 100g of magnesium turnings were taken 1000g of trimethylaluminum was added
Step two, reacting halomethane with the mixed solution
The reaction temperature was controlled at 70 ℃, then 200g of methyl iodide was added dropwise with heating, and after the completion of the methyl iodide dropwise addition, the heating and stirring were continued for 5 hours.
Step three, rectifying and collecting the product
After heating, the product was rectified according to 3:6:1, collecting a front fraction, a middle fraction and a kettle residue, and collecting 700g of a trimethylaluminum middle fraction.
After the sample is processed, the fraction chlorine impurity in the processed trimethylaluminum is reduced to 0.69ppm from 98ppm by anion chromatography analysis, so that the quality requirement of the semiconductor is met.
Example 2-2
The magnesium chips in the residue of example 2 were filtered through a 300 mesh sieve, vacuum dried, washed with ethanol and water, vacuum dried again, and weighed to have 69g of magnesium chips remaining, indicating that about 31g of the initial 100g of magnesium chips in example 2 reacted with 200g of methyl iodide.
Step one, mixing trimethylaluminum and magnesium
69g of residual magnesium turnings were placed in a clean round bottom flask and 1000g of chlorine-containing trimethylaluminum stock was added
Step two, reacting halomethane with the mixed solution
The reaction temperature was controlled at 70 ℃, then 200g of methyl iodide was added dropwise with heating, and after the completion of the methyl iodide dropwise addition, the heating and stirring were continued for 5 hours.
Step three, rectifying and collecting the product
After heating, the product was rectified according to 3:6:1, collecting a front fraction, a middle fraction and a kettle residue.
After the sample is treated, the fraction chlorine impurity in the treated trimethylaluminum is reduced to 0.61ppm from 98ppm, and the quality requirement of a semiconductor is met, which indicates that the mixture of magnesium chips and halogenated hydrocarbon recycled from the kettle still has the same chlorine removal capability until the magnesium chips react with Grignard reagent until the magnesium chips and Grignard reagent are consumed.
Example 3
The chlorine removal treatment process of trimethylaluminum in this example is specifically as follows:
step one, reacting methyl magnesium iodide with trimethylaluminum
1000g of trimethylaluminum was taken in a clean round bottom flask, then 20g of methylmagnesium iodide was added dropwise with stirring at a dropping rate of 0.5g/min at a temperature of 80℃and stirring was continued for 5 hours after the completion of the dropwise addition of the reagent.
Step two, rectifying and collecting the product
After heating, the product was rectified according to 1:8:1, collecting a front fraction, a middle fraction and a residue, and collecting 780g of a trimethylaluminum middle fraction.
After the sample is processed, the fraction chlorine impurity in the processed trimethylaluminum is reduced from 80ppm to 0.66ppm by anion chromatographic analysis, and the quality requirement of the semiconductor is met.
Example 4
The chlorine removal treatment process of trimethylaluminum in this example is specifically as follows:
step one, reacting methyl magnesium bromide with trimethylaluminum
2500g of trimethylaluminum were taken in a clean round-bottomed flask, after which 300g of methylmagnesium bromide was added dropwise with stirring at a temperature of 100℃and, after the reagent had been added dropwise, stirring was continued with heating for 2 hours.
Step two, rectifying and collecting the product
After heating, the product was rectified according to 3:6:1, collecting a front fraction, a middle fraction and a residue, and collecting 1480g of a middle fraction of trimethylaluminum.
After the sample is processed, the fraction chlorine impurity in the processed trimethylaluminum is reduced from 100ppm to 0.72ppm by anion chromatographic analysis, so that the quality requirement of the semiconductor is met.
Comparative example 4-1
This comparative example is substantially the same as example 4, except that the reaction temperature is mainly different, as shown in detail below:
step one, reacting methyl magnesium bromide with trimethylaluminum
2500g of trimethylaluminum were taken in a clean round-bottomed flask, after which 300g of methylmagnesium bromide was added dropwise with stirring at a temperature of 30℃and, after the reagent had been added dropwise, stirring was continued with heating for 10 hours.
Step two, rectifying and collecting the product
After heating, the product was rectified according to 3:6:1, collecting a front fraction, a middle fraction and a residue, and collecting 1880g of a trimethylaluminum middle fraction.
After the sample is processed, the sample is obtained through anion chromatographic analysis, and the fraction chlorine impurity in the processed trimethylaluminum is changed from 100ppm to 89ppm, so that the quality requirement of the semiconductor is not met.
Based on the above examples and comparative examples, it is clear that the present invention can reduce the content of organochlorine impurities in trimethylaluminum to meet the semiconductor grade requirement, and removes chlorine impurities in trimethylaluminum by indirect or direct Grignard reagent reaction, with short treatment time, high efficiency of reagents used, simple and convenient industrial scale-up production, and high safety of reagents used.
In some preferred embodiments, the rectified front cut can be added to the next batch for reheating treatment, so that the reagent utilization rate is improved, and the cost is reduced.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (10)
1. The chlorine removal method of the crude trimethylaluminum product comprises trimethylaluminum and methylaluminum chloride, and is characterized by comprising the following steps:
and (3) contacting the crude trimethylaluminum product with a format reagent, and carrying out nucleophilic substitution reaction on the format reagent and methylaluminum chloride to generate magnesium chloride for removal.
2. The chlorine removal process of claim 1, comprising in particular:
mixing metal magnesium with the crude trimethylaluminum product to form a first mixed system;
gradually introducing halogenated hydrocarbon into the first mixed system to enable the halogenated hydrocarbon to react with magnesium in situ to form the format reagent, and enabling the format reagent to react with the methylaluminum chloride in a nucleophilic substitution reaction;
or directly mixing the crude trimethylaluminum product with a format reagent to form a second mixed system, and simultaneously enabling the format reagent and the methylaluminum chloride to generate nucleophilic substitution reaction.
3. The chlorine removal process according to claim 2, wherein the mass ratio of magnesium metal to crude trimethylaluminum in the first mixed system is 1:1 to 1:10000, preferably 1:10 to 1:5000.
And/or the mass ratio of the halocarbon to the crude trimethylaluminum product is 1:1-1:5000, preferably 1:5-1:2000.
And/or, in the second mixed system, the mass ratio of the format reagent to the crude trimethylaluminum product is 1:1-1:5000, preferably 1:5-1:2000.
4. The chlorine removal process of claim 2, wherein said nucleophilic substitution reaction is carried out at a temperature of from 40 to 125 ℃ for a period of from 1 to 10 hours;
and/or, maintaining continuous stirring at not less than 60rpm while performing the nucleophilic substitution reaction;
preferably, the halogenated hydrocarbon comprises a gaseous halogenated hydrocarbon or a liquid halogenated hydrocarbon; when the gaseous halogenated hydrocarbon is adopted, the temperature of the nucleophilic substitution reaction is controlled to be 50-125 ℃, preferably 60-120 ℃, and more preferably 80-110 ℃; when the liquid halogenated hydrocarbon is adopted, the temperature of the nucleophilic substitution reaction is controlled to be 40-100 ℃, preferably 50-90 ℃, and more preferably 50-80 ℃;
preferably, the gaseous halohydrocarbon is introduced by contacting the first mixed system with the gaseous halohydrocarbon; and/or the liquid halogenated hydrocarbon is introduced by dropwise adding the liquid halogenated hydrocarbon into the first mixed system.
5. The chlorine removal process of claim 4, wherein said gaseous halogenated hydrocarbon comprises methyl chloride and/or methyl bromide;
and/or, the liquid halogenated hydrocarbon comprises methyl iodide;
and/or the format reagent comprises any one or more than two of methyl magnesium chloride, methyl magnesium bromide and methyl magnesium iodide.
6. The chlorine removal process of claim 1, wherein said methylaluminum chloride comprises methylaluminum dichloride and/or dimethylaluminum monochloride;
and/or the chlorine content in the crude trimethylaluminum product is 10-2000 ppm.
7. The chlorine removal process of claim 1, further comprising:
and rectifying the mixed system obtained after the nucleophilic substitution reaction to obtain a pure trimethylaluminum product through separation.
8. The method for chlorine removal of claim 7, wherein said pure trimethylaluminum product has a chlorine content of 1ppm or less.
9. The chlorine removal process of claim 7, wherein said rectification is carried out at a ratio of (0.5-3) to (5-9) to (0.5-3) for the front fraction, middle fraction and residue of the still.
And collecting the pure trimethylaluminum product in the middle distillate.
10. The chlorine removal process of claim 9, further comprising: and mixing the collected front fraction with the new crude trimethylaluminum product, and removing methylaluminum chloride.
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