CN110950911A - Preparation method of trimethylarsine - Google Patents
Preparation method of trimethylarsine Download PDFInfo
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- CN110950911A CN110950911A CN201811126784.7A CN201811126784A CN110950911A CN 110950911 A CN110950911 A CN 110950911A CN 201811126784 A CN201811126784 A CN 201811126784A CN 110950911 A CN110950911 A CN 110950911A
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- organic solvent
- methyl iodide
- preparation
- trimethyl arsine
- reaction
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- HTDIUWINAKAPER-UHFFFAOYSA-N trimethylarsine Chemical compound C[As](C)C HTDIUWINAKAPER-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011575 calcium Substances 0.000 claims abstract description 46
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 45
- 239000003960 organic solvent Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 abstract description 24
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 20
- 239000007788 liquid Substances 0.000 abstract description 20
- 239000002699 waste material Substances 0.000 abstract description 18
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- -1 arsenic alkane Chemical class 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000009489 vacuum treatment Methods 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/66—Arsenic compounds
- C07F9/70—Organo-arsenic compounds
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/66—Arsenic compounds
- C07F9/70—Organo-arsenic compounds
- C07F9/72—Aliphatic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention provides a preparation method of trimethyl arsine. The preparation method comprises the following steps: mixing raw materials comprising calcium arsenide and methyl iodide in a vacuum environment with the water content less than 100ppm for reaction to obtain the trimethyl arsine. The invention avoids the difficulty of water removal in the aspect of purification and solves the problem of water content of the produced trimethyl arsine; the invention can effectively solve the problem of incomplete trimethyl arsine generation in the trimethyl arsine production process in the prior art by adopting the reaction of calcium arsenide and methyl iodide. Preferably, in order to further solve the problem that a large amount of arsenic-containing waste liquid is generated in the production process of trimethyl arsine in the prior art, the invention adopts a specific organic solvent and recycles the organic solvent by a distillation method, thereby greatly reducing the generation of the arsenic-containing waste liquid. Therefore, the preparation method provided by the invention solves the problems of incomplete reaction, damage of arsenic-containing waste liquid to the environment and the like in the traditional method, and is beneficial to realizing large-scale production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, and particularly relates to a preparation method of trimethyl arsine.
Background
At present, arsenic-containing semiconductors are produced by arsenic alkane, arsenic alkane is high in toxicity, is gas, is high in leakage risk and high in destructiveness, and trimethyl arsine is liquid at normal temperature and is much lower in toxicity than arsenic alkane, so that the safety risk can be greatly reduced by replacing arsenic alkane with trimethyl arsine, and the arsenic-containing semiconductors are more beneficial to the long-term development.
Trimethylarsine isA molecular formula of (CH)3)3As) has a melting point of-87.3 ℃ and a boiling point of 51 ℃, is liquid at normal temperature, and has a garlic-like odor.
The traditional preparation method of trimethyl arsine generally adopts the reaction of arsenic trioxide and trimethyl aluminum. However, the method has the disadvantages of large water consumption, incomplete reaction, easy generation of a large amount of dangerous waste liquid and great damage to the environment.
Disclosure of Invention
The invention mainly aims to provide a method for preparing trimethyl arsine, which aims to solve the problem that the arsenic-containing waste liquid generated by the method for preparing trimethyl arsine in the prior art damages the environment.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for preparing trimethylarsine, comprising the steps of: mixing raw materials comprising calcium arsenide and methyl iodide in a vacuum environment with the water content less than 100ppm for reaction to obtain the trimethyl arsine.
Furthermore, the raw materials also comprise an organic solvent which does not contain active hydrogen and has a boiling point of 40-80 ℃.
Further, the water content of the organic solvent is less than 100ppm, and the organic solvent does not contain air.
Further, the preparation method comprises the following steps: s1, mixing calcium arsenide and an organic solvent in a vacuum environment to obtain a mixed solution; s2, dropwise adding methyl iodide into the mixed solution, stirring, and reacting calcium arsenide with methyl iodide at 20-80 ℃ to obtain trimethylarsine.
Further, the vacuum degree of the vacuum environment in the step S1 is 10-50 pa; the molar ratio of the calcium arsenide to the organic solvent is preferably 1: 5-10.
Further, the molar ratio of calcium arsenide to methyl iodide is 1: 6.5-9; in step S2, methyl iodide is added to the mixed solution, preferably at a temperature of 20 to 40 ℃; preferably, the reaction temperature of the calcium arsenide and the methyl iodide is 20-50 ℃; preferably, the stirring speed is 60-80 r/min.
Further, after step S2, the preparation method further includes the steps of: and S3, condensing the trimethyl arsine and the organic solvent, wherein the preferable condensing temperature is 0-20 ℃.
Further, step S3 includes a step of refluxing the condensed organic solvent and trimethylarsine.
Further, after step S3, the preparation method further includes: and heating and recovering the trimethylarsine at the temperature of 70-100 ℃.
Further, after step S3, the preparation method further includes: and heating the organic solvent in vacuum to evaporate the organic solvent, wherein the temperature of the vacuum heating is preferably 70-100 ℃, and the vacuum degree of the vacuum heating is 1-10 kpa.
The technical scheme of the invention provides a method for preparing trimethyl arsine, which adopts the reaction of calcium arsenide and methyl iodide to prepare the trimethyl arsine. In the prior art, the preparation process of the trimethyl arsine can cause that the water in the trimethyl arsine is difficult to remove, but the invention avoids the difficulty of water removal in the aspect of purification and solves the problem of water content of the produced trimethyl arsine; in addition, the invention can effectively solve the problem of incomplete trimethyl arsine generation in the trimethyl arsine production process in the prior art by adopting the reaction of calcium arsenide and methyl iodide. Preferably, in order to further solve the problem that a large amount of arsenic-containing waste liquid is generated in the production process of trimethyl arsine in the prior art, the invention adopts a specific organic solvent and recycles the organic solvent by a distillation method, thereby greatly reducing the generation of the arsenic-containing waste liquid. Therefore, the preparation method provided by the invention solves the problems of incomplete reaction, damage of arsenic-containing waste liquid to the environment and the like in the traditional method, and is beneficial to realizing large-scale production.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged under appropriate circumstances in order to facilitate the description of the embodiments of the invention herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
As described in the background, the arsenic-containing waste liquid produced by the prior art processes for the preparation of trimethylarsine is environmentally damaging. In order to solve the technical problem, the invention provides a preparation method of trimethyl arsine, which comprises the following steps: mixing raw materials comprising calcium arsenide and methyl iodide in a vacuum environment with the water content less than 100ppm for reaction to obtain the trimethyl arsine.
In the prior art, the preparation process of the trimethyl arsine can cause that the water in the trimethyl arsine is difficult to remove, but the invention avoids the difficulty of water removal in the aspect of purification and solves the problem of water content of the produced trimethyl arsine; in addition, the invention can effectively solve the problem of incomplete trimethyl arsine generation in the trimethyl arsine production process in the prior art by adopting the reaction of calcium arsenide and methyl iodide. Furthermore, in order to solve the problem that a large amount of arsenic-containing waste liquid is generated in the production process of trimethyl arsine in the prior art, the invention adopts a specific organic solvent and recycles the organic solvent by adopting a distillation method, thereby greatly reducing the generation of the arsenic-containing waste liquid. Therefore, the preparation method provided by the invention solves the problems of incomplete reaction, damage of arsenic-containing waste liquid to the environment and the like in the traditional method, and is beneficial to realizing large-scale production.
In the preparation method, the raw materials can also comprise an organic solvent which does not contain active hydrogen and has a boiling point of 40-80 ℃. Preferably, the water content of the organic solvent is less than 100ppm, and the organic solvent does not contain air; more preferably, the organic solvent is an ether. The specific organic solvent is adopted in the preparation method, and the organic solvent is evaporated after the reaction is finished, so that the difficulty of water removal in the aspect of purification can be avoided, the problem of water content of the produced trimethyl arsine is solved, and the arsenic-containing substance remained in the solvent is less, so that the preparation method is more suitable for large-scale production.
The reaction formula of calcium arsenide and methyl iodide in the preparation method is as follows:
Ca3As2+6CH3I＝3CaI2+2As(CH3)3
in a preferred embodiment, the above preparation method of the present invention comprises the steps of: s1, mixing calcium arsenide and the organic solvent in a vacuum environment to obtain a mixed solution; s2, dropwise adding methyl iodide into the mixed solution, stirring, and reacting calcium arsenide with methyl iodide at 20-80 ℃ to obtain trimethylarsine. In order to enable the calcium arsenide and the methyl iodide to react at 20-80 ℃, the mixed solution can be heated at the initial stage of the methyl iodide dripping, the calcium arsenide and the methyl iodide generate heat during the reaction process through stirring, and in order to prevent the temperature from being too high during the reaction process, the heating is stopped when the calcium arsenide and the methyl iodide start to react.
In the above preferred embodiment, the vacuum degree of the vacuum environment in step S1 is preferably 10 to 50 pa; more preferably, the molar ratio of the calcium arsenide to the solvent is 1: 5-10; more preferably, the molar ratio of calcium arsenide to methyl iodide is 1: 6.5-9; more preferably, in the step S2, methyl iodide is added to the mixed solution at a temperature of 20 to 40 ℃; more preferably, the stirring speed is 60-80 r/min; more preferably, the reaction temperature of the calcium arsenide and the methyl iodide is 20 to 50 ℃. Under the reaction conditions, calcium arsenide and methyl iodide can fully react, so that the efficiency of preparing trimethyl arsine is improved, the content of arsenic in waste liquid is greatly reduced, and the emission of the waste liquid containing arsenic is greatly reduced.
In the above preferred embodiment, preferably, after step S2, the preparation method further includes the steps of: s3, condensing trimethyl arsine and an organic solvent; the condensing temperature is preferably 0-20 ℃. In the step S2, part of the organic solvent and the trimethylarsine generated by the reaction are vaporized to form a gas phase solvent; at this time, in the above step S3, trimethylarsine is condensed together with the gas-phase solvent to liquefy the gas-phase solvent to form a liquid-phase solvent. The reaction process needs heating, the generated trimethyl arsine is easy to vaporize and cause loss, and the vaporized trimethyl arsine can be effectively condensed under the condition of the condensation temperature.
In the above preferred embodiment, the step S3 further includes a step of refluxing the condensed organic solvent and trimethylarsine, and the steps S1 to S3 are repeatedly performed, where the organic solvent in the step S1 includes the liquid-phase solvent. The cost can be saved by liquefying and recycling the vaporized organic solvent in the reaction;
in the above preferred embodiment, trimethylarsine is preferably heated at a temperature of 70 to 100 ℃ and recovered.
In a preferred embodiment, the preparation method further comprises the step of heating the organic solvent in vacuum to evaporate the organic solvent, wherein the temperature of the vacuum heating is preferably 70 to 100 ℃, and the vacuum degree of the vacuum heating is preferably 1 to 10 kpa. Specifically, the raw material comprising calcium arsenide and methyl iodide may be introduced into a reaction kettle to react to obtain trimethylarsine, and after the reaction is completed, the reaction kettle may be heated to distill off the organic solvent.
In a typical embodiment of the invention, calcium arsenide is adopted as the solvent, methyl iodide is added dropwise under the condition of stirring for reaction, a condenser is used for reflux, and after methyl iodide is added dropwise, the mixture is heated to ensure that reactants are reacted completely. After the reaction is finished, transferring the reaction liquid to an evaporation kettle. The stirring is turned on and the heat is applied to completely separate the dissolved trimethylarsine from the solvent. After the trimethyl arsine is evaporated, the solvent is completely evaporated under reduced pressure for reuse, and the kettle residue is treated by 95% industrial alcohol.
The present invention is described in further detail below with reference to specific examples, which are not to be construed as limiting the scope of the invention as claimed.
Example 1
The preparation method of trimethylarsine in the embodiment comprises the following steps:
1340g of calcium arsenide is added into a reaction kettle, the reaction kettle is treated in vacuum, when the vacuum degree of the reaction kettle is 1kpa, the pressure of the reaction kettle is reduced to 10pa by using a molecular pump so as to ensure that a very small amount of air remains in the reaction kettle, and 3250g of n-butyl ether (the water content is less than 100ppm, and no air is treated) is introduced into the reaction kettle. The temperature of the reaction kettle is set to be 30 ℃, the temperature of the condenser is set to be 10 ℃, when the temperatures of the reaction kettle and the condenser reach the set temperatures, stirring is started, 45g of methyl iodide starts to be dripped, when the temperature rises to 55 ℃, dripping continues to be performed, the temperature of the reaction kettle is maintained at 65 ℃, the temperature of the reaction kettle is set to be 80 ℃ after dripping is completed, calcium arsenide reacts with methyl iodide to obtain trimethyl arsine, n-butyl ether and trimethyl arsine evaporated in the reaction kettle enter the condenser to be liquefied, the liquefied n-butyl ether and trimethyl arsine flow back to the reaction kettle, and refluxing lasts for 2 hours. After the reaction is finished, transferring the reaction liquid to an evaporation kettle. And opening the stirring, setting the temperature of the evaporation kettle to be 80 ℃, and distilling to recover the trimethyl arsine. The temperature of the evaporation kettle is maintained at 80 ℃, n-butyl ether is evaporated under the vacuum condition of 3kpa for reuse, and the kettle residue is treated by 95 percent of industrial alcohol.
Example 2
The preparation method of trimethylarsine in the embodiment comprises the following steps:
1340g of calcium arsenide is added into a reaction kettle, the reaction kettle is treated by vacuum treatment, when the vacuum degree of the reaction kettle is 1kpa, the pressure of the reaction kettle is reduced to 10pa by using a molecular pump so as to ensure that a very small amount of air remains in the reaction kettle, and 3200g of n-butyl ether is introduced into the reaction kettle. Setting the temperature of a reaction kettle to be 30 ℃, setting a condenser to be 10 ℃, starting stirring when the temperatures of the reaction kettle and the condenser reach the set temperatures, starting dropwise adding 45g of methyl iodide, starting to continuously dropwise add when the temperature rises to 55 ℃, keeping the temperature of the reaction kettle at 65 ℃, setting the temperature of the reaction kettle to be 80 ℃ after dropwise adding, reacting calcium arsenide and methyl iodide to obtain trimethyl arsine, introducing n-butyl ether and trimethyl arsine evaporated in the reaction kettle into the condenser for liquefaction, refluxing the liquefied n-butyl ether and trimethyl arsine into the reaction kettle, and continuously refluxing for 2 hours. After the reaction is finished, transferring the reaction liquid to an evaporation kettle. And opening the stirring, setting the temperature of the evaporation kettle to be 80 ℃, and distilling to recover the trimethyl arsine. The temperature of the evaporation kettle is maintained at 80 ℃, n-butyl ether is evaporated under the vacuum condition of 3kpa for reuse, and the kettle residue is treated by 95 percent of industrial alcohol.
Example 3
The preparation method of trimethylarsine in the embodiment comprises the following steps:
1340g of calcium arsenide is added into a reaction kettle, the reaction kettle is treated by vacuum treatment, when the vacuum degree of the reaction kettle is 1kpa, the pressure of the reaction kettle is reduced to 10pa by using a molecular pump so as to ensure that a very small amount of air remains in the reaction kettle, and 3100g of n-butyl ether is introduced into the reaction kettle. Setting the temperature of a reaction kettle to be 30 ℃, setting a condenser to be 10 ℃, starting stirring when the temperatures of the reaction kettle and the condenser reach the set temperatures, starting dropwise adding 45g of methyl iodide, starting to continuously dropwise add when the temperature rises to 55 ℃, keeping the temperature of the reaction kettle at 65 ℃, setting the temperature of the reaction kettle to be 80 ℃ after dropwise adding, reacting calcium arsenide and methyl iodide to obtain trimethyl arsine, introducing n-butyl ether and trimethyl arsine evaporated in the reaction kettle into the condenser for liquefaction, refluxing the liquefied n-butyl ether and trimethyl arsine into the reaction kettle, and continuously refluxing for 2 hours. After the reaction is finished, transferring the reaction liquid to an evaporation kettle. And opening the stirring, setting the temperature of the evaporation kettle to be 80 ℃, and distilling to recover the trimethyl arsine. The temperature of the evaporation kettle is maintained at 80 ℃, n-butyl ether is evaporated under the vacuum condition of 3kpa for reuse, and the kettle residue is treated by 95 percent of industrial alcohol.
Example 4
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
the molar ratio of calcium arsenide to solvent is 1: 5.
Example 5
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
the molar ratio of calcium arsenide to solvent is 1: 10.
Example 6
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
the molar ratio of calcium arsenide to methyl iodide is 1: 6.5.
Example 7
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
the molar ratio of calcium arsenide to methyl iodide is 1: 9.
Example 8
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
the reaction temperature of calcium arsenide and methyl iodide is 20 ℃.
Example 9
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
the reaction temperature of calcium arsenide and methyl iodide is 50 ℃.
Example 10
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
adding methyl iodide to the mixed solution at a temperature of 20 ℃; the stirring speed of the calcium arsenide and the methyl iodide is 80 r/min.
Example 11
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
adding methyl iodide to the mixed solution at a temperature of 40 ℃; the stirring speed of the calcium arsenide and the methyl iodide is 60 r/min.
Example 12
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
the temperature of the condenser was 0 ℃.
Example 13
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
the temperature of the condenser was 20 ℃.
Example 14
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
when the trimethyl arsine is distilled, the temperature of an evaporation kettle is 70 ℃.
Example 15
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
when the trimethyl arsine is distilled, the temperature of an evaporation kettle is 100 ℃.
Example 16
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
when n-butyl ether is evaporated, the temperature of the evaporation kettle is 70 ℃, and the vacuum degree is 1 kpa.
Example 17
The preparation method of trimethylarsine in the embodiment is different from that in the embodiment 1 in that:
when n-butyl ether is evaporated, the temperature of the evaporation kettle is 100 ℃, and the vacuum degree is 10 kpa.
The product specifications for trimethylarsine prepared in examples 1-17 above are given in Table 1.
TABLE 1
| Weight/g of trimethylarsine | Yield/%) | |
| Example 1 | 944 | 80.0 |
| Example 2 | 1003 | 85.0 |
| Example 3 | 1005 | 85.0 |
| Example 4 | 882 | 76.2 |
| Example 5 | 887 | 76.4 |
| Example 6 | 869 | 75.6 |
| Example 7 | 857 | 75.3 |
| Example 8 | 832 | 74.8 |
| Example 9 | 843 | 75.2 |
| Example 10 | 886 | 77.4 |
| Example 11 | 898 | 76.9 |
| Example 12 | 926 | 78.4 |
| Example 13 | 913 | 77.6 |
| Example 14 | 935 | 79.1 |
| Example 15 | 923 | 78.4 |
| Example 16 | 945 | 79.8 |
| Example 17 | 948 | 80.0 |
As can be seen from the above test results, the yield of trimethylarsine produced by the preparation method of the invention is high, and the arsenic content in the generated waste liquid is low.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
1. in the prior art, the preparation process of the trimethyl arsine can cause that the water in the trimethyl arsine is difficult to remove, but the invention avoids the difficulty of water removal in the aspect of purification and solves the problem of water content of the produced trimethyl arsine;
2. the invention can effectively solve the problem of incomplete trimethyl arsine generation in the trimethyl arsine production process in the prior art by adopting the reaction of calcium arsenide and methyl iodide;
3. in order to solve the problem that a large amount of arsenic-containing waste liquid is generated in the production process of trimethyl arsine in the prior art, the invention adopts a specific organic solvent and a distillation method to recycle the organic solvent, thereby greatly reducing the generation of the arsenic-containing waste liquid;
4. the preparation method provided by the invention solves the problems that the traditional method is incomplete in reaction, arsenic-containing waste liquid causes damage to the environment and the like, and is beneficial to realizing large-scale production.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of trimethyl arsine is characterized by comprising the following steps:
and mixing the raw materials comprising calcium arsenide and methyl iodide in a vacuum environment with the water content of less than 100ppm for reaction to obtain the trimethylarsine.
2. The preparation method according to claim 1, wherein the raw material further comprises an organic solvent which does not contain active hydrogen and has a boiling point of 40 to 80 ℃.
3. The method according to claim 2, wherein the organic solvent contains less than 100ppm of water and does not contain air.
4. The method of manufacturing according to claim 2, comprising the steps of:
s1, mixing the calcium arsenide and the organic solvent in a vacuum environment to obtain a mixed solution;
and S2, dropwise adding the methyl iodide into the mixed solution, stirring, and reacting the calcium arsenide with the methyl iodide at 20-80 ℃ to obtain the trimethylarsine.
5. The method according to any one of claims 2 to 4, wherein a degree of vacuum of the vacuum environment in the step S1 is 10 to 50 pa; preferably, the molar ratio of the calcium arsenide to the organic solvent is 1: 5-10.
6. The preparation method according to claim 4, wherein the molar ratio of the calcium arsenide to the methyl iodide is 1: 6.5-9; in the step S2, the methyl iodide is added to the mixed solution preferably at a temperature of 20 to 40 ℃; preferably, the reaction temperature of the calcium arsenide and the methyl iodide is 20-50 ℃; preferably, the stirring speed is 60-80 r/min.
7. The method according to claim 4, characterized in that after the step S2, the method further comprises the steps of:
s3, condensing the trimethyl arsine and the organic solvent, wherein the condensing temperature is preferably 0-20 ℃.
8. The method according to claim 7, wherein the step S3 further comprises a step of refluxing the condensed organic solvent and the trimethylarsine.
9. The method according to claim 7, characterized in that after the step S3, the method further comprises: and heating the trimethyl arsine at the temperature of 70-100 ℃ and recovering.
10. The production method according to any one of claims 4 to 8, characterized in that, after the step S3, the production method further includes: and heating the organic solvent in vacuum to evaporate the organic solvent, wherein the temperature of the vacuum heating is preferably 70-100 ℃, and the vacuum degree of the vacuum heating is 1-10 kpa.
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|---|---|---|---|
| CN201811126784.7A CN110950911B (en) | 2018-09-26 | 2018-09-26 | Preparation method of trimethylarsine |
| PCT/CN2018/116433 WO2020062503A1 (en) | 2018-09-26 | 2018-11-20 | Method for preparing trimethylarsine |
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| CN201811126784.7A CN110950911B (en) | 2018-09-26 | 2018-09-26 | Preparation method of trimethylarsine |
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| CN110950911B CN110950911B (en) | 2021-10-08 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03181309A (en) * | 1989-11-21 | 1991-08-07 | Phillips Petroleum Co | Method for removing trialkylarsine from gas |
| CN1400214A (en) * | 2001-04-06 | 2003-03-05 | 希普雷公司 | Trialkyl VA metal compound |
| CN102020668A (en) * | 2010-12-22 | 2011-04-20 | 江苏南大光电材料股份有限公司 | Method for industrially preparing trimethyl indium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2561482B2 (en) * | 1987-08-27 | 1996-12-11 | 住友化学工業株式会社 | Method for producing trialkylarsenic compound |
-
2018
- 2018-09-26 CN CN201811126784.7A patent/CN110950911B/en not_active Expired - Fee Related
- 2018-11-20 WO PCT/CN2018/116433 patent/WO2020062503A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03181309A (en) * | 1989-11-21 | 1991-08-07 | Phillips Petroleum Co | Method for removing trialkylarsine from gas |
| CN1400214A (en) * | 2001-04-06 | 2003-03-05 | 希普雷公司 | Trialkyl VA metal compound |
| CN102020668A (en) * | 2010-12-22 | 2011-04-20 | 江苏南大光电材料股份有限公司 | Method for industrially preparing trimethyl indium |
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| CN110950911B (en) | 2021-10-08 |
| WO2020062503A1 (en) | 2020-04-02 |
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