CN109942611B - Preparation method of trimethylaluminum - Google Patents
Preparation method of trimethylaluminum Download PDFInfo
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- CN109942611B CN109942611B CN201711390401.2A CN201711390401A CN109942611B CN 109942611 B CN109942611 B CN 109942611B CN 201711390401 A CN201711390401 A CN 201711390401A CN 109942611 B CN109942611 B CN 109942611B
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Abstract
The invention provides a preparation method of trimethylaluminum, which comprises the following steps of I, reacting trialkyl aluminum with halogenated methane in the presence of a bismuth-based compound and a solvent to obtain a reaction product; and II, removing the halogenated alkane in the reaction product, standing the reaction product to separate out crystals, recovering the separated crystals and separating the residual reaction product to obtain the trimethylaluminum. The invention adopts high-pressure liquid phase reaction, the raw materials are fully contacted, the reaction efficiency is high, and the conversion rate of the trialkyl aluminum is high. The catalyst has simple recovery process and high recovery rate, and the production cost is obviously reduced.
Description
Technical Field
The invention belongs to the technical field of organic metal compound synthesis, and particularly relates to a preparation method of trimethylaluminum.
Background
Trimethylaluminum (TMA) is an important organic metal compound and has wide application in the fields of organic catalysts, organic synthesis, polymer chemistry industry, national defense science and technology and the like.
In the field of polymer catalysts, with the rapid development of metallocene catalyst systems, trimethylaluminum has become more and more important as a cocatalyst for synthesizing metallocene catalysts, i.e., a starting material of Methylaluminoxane (MAO). In addition, with the development of photovoltaic devices, semiconductor devices and LED devices in recent years, trimethyl aluminum has attracted attention in depositing and growing thin film materials of component chips such as photovoltaic devices, single conductors and LEDs due to excellent performance, and the application of trimethyl aluminum is wider and wider. In addition, trimethylaluminum is one of the important raw materials for producing high-purity trimethylindium and trimethylgallium.
More methods are used for preparing trimethylaluminum, but few methods are available for industrialization. The common method is to adopt industrial triethyl aluminum and alkyl halide to carry out alkyl exchange reaction. U.S. Pat. No. 5,973,537 discloses a process for the transalkylation of C2+ alkylaluminum (an alkylaluminum having at least two carbon atoms in the alkyl group) with a monohaloalkane to produce trimethylaluminum and C2+ halohydrocarbons. The preparation method uses C2+ alkyl aluminum as raw material, and uses the catalyst such as BiCl3、BiBr3And the like, introducing methyl halide at a certain temperature, and forming trimethylaluminum through ligand exchange, wherein the product C2+ alkyl halide is volatilized and removed from the reaction mixture in the reaction process. The disadvantages of this method are: the exchange reaction is not thorough, more byproducts are formed, and the conversion rate of raw materials is low; the recovery of the catalyst is complicated by adding Al powder to the reaction mixture and heating the mixture to recover the catalyst and reusing the recovered catalyst for the catalytic reaction, but the process is complicated and tends to form many by-products. In addition, in the synthesis and simulation research of trimethylaluminum, page 29-31 of 2 nd phase of 2006, chemical abstracts, bismuth-based compounds, triethylaluminum and solvents are added into a reaction kettle protected by high-purity nitrogen, halogenated methane gas is introduced at the reaction temperature for reaction, and the trimethylaluminum is obtained by rectification after the reaction is finished. In the reaction, the conversion rate of raw materials is high, but the dosage of the catalyst is large, and the catalyst recovery process is not needed after the reaction, so that the production cost is high. Therefore, in the preparation process of trimethylaluminum, a method which can improve the conversion rate of raw materials and has a simple catalyst recovery process needs to be found.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of trimethylaluminum, which adopts high-pressure liquid phase reaction, fully contacts raw materials, has high reaction efficiency and high conversion rate of trialkylaluminum, adopts a crystal precipitation mode to separate a catalyst from a reaction product, and has simple process and high recovery rate.
Specifically, the invention is realized by adopting the following technical scheme:
a preparation method of trimethylaluminum comprises the following steps:
step I, in the presence of a bismuth-based compound and a solvent, reacting trialkyl aluminum with halogenated methane to obtain a reaction product;
and II, removing the halogenated alkane in the reaction product, standing the reaction product to separate out crystals, recovering the separated crystals and separating the residual reaction product to obtain the trimethylaluminum.
According to a preferred embodiment of the invention, in step I, a high-pressure liquid-phase reaction is adopted, namely, the trialkyl aluminum and the halogenated methane which participate in the reaction are both in liquid state, and compared with gaseous halogenated methane, the liquid halogenated methane and the liquid trialkyl aluminum can be mixed and fully contacted quickly, so that the reaction efficiency is high. In a preferred embodiment of the present invention, trialkylaluminum and liquid methyl halide are added to a reactor at a time to perform a reaction.
According to a preferred embodiment of the invention, the reaction of step I is carried out in the presence of an inert atmosphere. The reaction temperature is 110-140 ℃, preferably 120-130 ℃; and/or the reaction time is 100-250min, preferably 120-180 min.
According to a preferred embodiment of the invention, the bismuth-based compound is a bismuth-containing compound, such as alkyl bismuth, aryl bismuth, inorganic bismuth salts and any bismuth-containing compound that can be converted into an alkyl or aryl bismuth can form the catalyst active component. Preferably, the bismuth-based compound is bismuth trihalide, preferably BiCl3Or BiBr3。
According to a preferred embodiment of the present invention, the solvent is an inert solvent selected to sufficiently dissolve the reaction raw material and the reaction product, and the inert solvent is selected to have a high boiling point, preferably, the solvent is selected from the group consisting of C9-C12Alkane, preferably decane, more preferably n-decane. The preparation of the trimethylaluminum is carried out in the presence of the solvent, and the solvent can fully dissolve the reaction raw materials and the catalyst and fully contact with each other during the reaction, thereby improving the reaction efficiency and the conversion rate of the trialkylaluminum and reducing the occurrence of side reactions.
According to a preferred embodiment of the invention, the trialkylaluminum has the general formula AlR3R is an alkyl group having 2 or more carbon atoms, preferably R is C2-C10The alkyl group, preferably trialkylaluminum, is selected from at least one of triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum and trihexylaluminum, in a preferred embodiment of the invention, trialkylaluminum is triethylaluminum.
According to a preferred embodiment of the present invention, the methyl halide is at least one of methyl chloride, methyl bromide and methyl iodide, preferably methyl bromide. In the preparation method of trimethylaluminum, the reaction is carried out under high pressure, the halogenated methane is in a liquid state, the liquid halogenated methane and the liquid trialkylaluminum can be quickly mixed and fully contacted, and the reaction efficiency is high.
The reaction of the halogenated methane and the trialkyl aluminum is a reversible reaction, the increase of the using amount of the halogenated methane is beneficial to improving the conversion rate of the trialkyl aluminum, but the increase of the using amount of the halogenated methane increases the cost, and the molar ratio of the halogenated methane to the trialkyl aluminum is (3-5) to 1, preferably (3.5-4): 1.
according to a preferred embodiment of the invention, the molar ratio of bismuth-based compound to trialkylaluminum is (0.01-0.03):1, preferably (0.015-0.02):1, calculated as elemental bismuth.
According to a preferred embodiment of the invention, the molar ratio of solvent to trialkylaluminum is (0.4-0.8):1, preferably (0.5-0.6): 1. When the using amount of the solvent is less, the conversion rate of the trialkyl aluminum is reduced because the association probability of the trialkyl aluminum is larger, the using amount of the solvent is too large, the dilution rate of the raw material is high, the probability of the trialkyl aluminum contacting with the halogenated methane is small, the conversion rate of the trialkyl aluminum is reduced, and the reaction efficiency is reduced.
According to a preferred embodiment of the present invention, in step II, the haloalkane is removed from the reaction product by a process of reducing the reaction temperature and the reaction pressure. The reaction in the step I is a high-pressure liquid-phase reaction, the temperature and the pressure are both high, and after the reaction is finished, the reaction pressure and the reaction temperature are reduced, and then the liquid halogenated hydrocarbon is converted into gaseous halogenated hydrocarbon and is removed from the system.
According to a preferred embodiment of the invention, in step II, the reaction temperature is reduced to 20-35 ℃, preferably 25-30 ℃ after the reaction is completed; and/or, the reaction pressure is slowly reduced to a negative pressure, preferably 1-50mmHg, to remove the haloalkane. After the reaction temperature and the reaction pressure are reduced, the temperature and/or the pressure are kept low for a certain period of time, preferably 30 to 100min, such as 60 to 100min, to sufficiently remove the halogenated alkane from the reaction system. The halogenated alkane herein includes unreacted halogenated methane as well as halogenated ethane produced by the reaction. In a preferred embodiment of the present invention, after the completion of the reaction, the reaction temperature is lowered to 20 to 35 ℃, the reaction pressure is lowered to a slight positive pressure, and then vacuum is applied to a negative pressure, preferably, to a pressure of 1 to 50 mmHg. In the invention, the halogenated alkane is removed from the system and then is kept stand to separate out crystals, and the existence of the halogenated alkane can influence the separation of the crystals.
According to a preferred embodiment of the invention, in step II, the reaction product is allowed to stand at a temperature of less than 25 ℃, preferably 0 to 25 ℃, preferably 10 to 15 ℃ for 12 to 48 hours, preferably 24 to 36 hours, to precipitate crystals. Recovering the precipitated bismuth-based compound crystal. According to the invention, the bismuth-based compound crystal is precipitated by a method of standing the reaction product, most of the bismuth-based compound is recovered by the method, and the recovered bismuth-based compound has high catalytic activity and can be reused, so that the production cost is reduced. In addition, most of the bismuth-based catalyst can be recovered only by controlling the temperature of crystal precipitation, so that the method is simple and the recovery rate of the bismuth-based catalyst is high.
According to a preferred embodiment of the present invention, the separation of trimethylaluminum from the reaction product in step II can be performed by a separation method commonly used in the art, and preferably, the trimethylaluminum is separated from the remaining reaction product by vacuum distillation.
In the process of preparing the trimethylaluminum, the high-pressure liquid phase reaction is adopted, the raw materials are fully contacted, the reaction efficiency is high, and the conversion rate of the trialkylaluminum is high. The method adopts a crystal precipitation mode to recover the bismuth-based catalyst, the recovery process of the catalyst is simple, the recovery rate of the catalyst is high, the recycled catalyst has excellent recycling catalytic effect, and the production cost is obviously reduced.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
Example 1
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane as a solvent were added to the autoclave, and 8 was added thereto with stirring576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of liquid-phase methyl bromide, were heated to a reaction temperature of 125 ℃ and a reaction kettle pressure of about 1.7MPa, and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.43g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.7%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 11%.
Example 2
The only difference from example 1 is the amount of methyl bromide used, which in this example is 25.002g (0.26mol) and the molar ratio of triethylaluminium to methyl bromide is 1: 3.47.
Under the protection of high-purity nitrogen, 0.362g (1.15mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into the autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 25.002g (0.26mol) of methyl bromide in a liquid phase were added under stirring, and the mixture was heated to 125 ℃ and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.18g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 95.6%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 12%.
Example 3
The difference from example 1 is that the amount of methyl bromide used in this example was 35.696g (0.376mol) and the molar ratio of triethylaluminium to methyl bromide was 1: 5.01.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into the autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 35.696g (0.376mol) of methyl bromide in a liquid phase were added under stirring, and the mixture was heated to 125 ℃ and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.47g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.9%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 10%.
Example 4
The Bi-based catalyst recovered in example 1 was again applied to the reaction of trialkylaluminum and methyl halide, and the lost Bi-based catalyst was replenished.
The crystals from example 1 were placed in an autoclave under a high-purity nitrogen atmosphere, and 0.045g (0.14mmol) of BiCl was added3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.3mol) of liquid-phase methyl bromide were added with stirring, the temperature was raised to 125 ℃ and the reaction was carried out at this temperature to 150 ℃And (3) minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.39g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.3%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 13%.
Example 5
The Bi-based catalyst recovered in example 2 was again applied to the reaction of trialkylaluminum and methyl halide, and the lost Bi-based catalyst was replenished.
The crystals from example 3 were placed in an autoclave under high purity nitrogen and 0.045g (0.14mmol) of BiCl was added3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into the autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.3mol) of liquid-phase methyl bromide were added with stirring, and the mixture was heated to 125 ℃ and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.46g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.2%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 11%.
Example 6
The difference from the example is only the reaction temperature, which is 110 ℃.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.3mol) of methyl bromide in a liquid phase were added under stirring, and the temperature was raised to 110 ℃ and the pressure in the autoclave was about 1.5MPa, and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.15g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 95.1%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 12%.
Example 7
The difference from example 1 is only the reaction temperature, which is 140 ℃ in this example.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.3mol) of methyl bromide in a liquid phase were added under stirring, and the temperature was raised to 140 ℃ and the pressure in the autoclave was about 2.1MPa, and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. The stirring is closed, and the temperature is kept under the protection of high-purity nitrogenAfter standing at 15 ℃ for 24 hours, a crystal was precipitated from the reaction product, and the crystal was separated from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.49g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 99.0%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 12%.
Example 8
The difference from example 1 is the amount of bismuth-based compound used, in this example BiCl3In an amount of 0.238g (0.75mmol), BiCl3The molar ratio to triethylaluminium was 0.01: 1.
Under the protection of high-purity nitrogen, 0.238g (0.75mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into the autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.3mol) of liquid-phase methyl bromide were added with stirring, and the mixture was heated to 125 ℃ and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 2.91g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 92.3%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 12%.
Example 9
The difference from example 1 is the amount of bismuth-based compound used, in this example BiCl3In an amount of 0.710g (2.25mmol), BiCl3With triethyl radicalThe molar ratio of aluminum was 0.03: 1.
Under the protection of high-purity nitrogen, 0.710g (2.25mmol) of BiCl is added3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into the autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.3mol) of liquid-phase methyl bromide were added with stirring, and the mixture was heated to 125 ℃ and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.46g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 99.0%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 11%.
Example 10
The difference from example 1 is only in the precipitation temperature of the bismuth-based compound, and the precipitation temperature in this example is 5 ℃.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into the autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.3mol) of liquid-phase methyl bromide were added with stirring, and the mixture was heated to 125 ℃ and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 5 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.43g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.8%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 11%.
Example 11
The difference from example 1 is only in the precipitation temperature of the bismuth-based compound, and the precipitation temperature in this example is 10 ℃.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into the autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.3mol) of liquid-phase methyl bromide were added with stirring, and the mixture was heated to 125 ℃ and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 10 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.45g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.9%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 11%.
Example 12
The only difference from example 1 is that the crystal precipitation temperature in this comparative example is 25 ℃.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of methyl bromide in a liquid phase were added under stirring, the temperature was raised to 125 ℃ and the pressure in the autoclave was about 1.7MPa, and the reaction was carried out at this temperature for 150 minutesA clock. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 25 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.39g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.7%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 22%.
Example 13
The only difference from example 11 is the reaction time, which is 90 min.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into the autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.3mol) of liquid-phase methyl bromide were added with stirring, and the mixture was heated to 125 ℃ and reacted at this temperature for 90 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 10 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.05g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of the triethyl aluminum to be 93.9%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 11%.
Example 14
The only difference from example 1 is that the catalyst used in this example is BiBr3(with BiCl)3Equimolar).
Under the protection of high-purity nitrogen, 0.507g (1.13mmol) of BiBr is added3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, and 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of methyl bromide in a liquid phase were added with stirring, and the temperature was raised to 125 ℃ and the pressure in the autoclave was about 1.7MPa, and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.38g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.8%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 12%.
Example 15
The only difference from example 1 is that after the completion of the reaction, the reaction temperature was lowered to 30 ℃ and the reaction pressure was lowered to 30mmHg and then maintained for 30 minutes.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, and 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of methyl bromide in a liquid phase were added with stirring, and the temperature was raised to 125 ℃ and the pressure in the autoclave was about 1.7MPa, and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 30 minutes at 30 ℃ and 30 mmHg. Stopping stirring, maintaining the temperature at 15 deg.C under the protection of high purity nitrogen, standing for 24 hr to obtain crystalThe reaction product is precipitated and the crystals are separated from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.41g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.9%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 15%.
Example 16
The only difference from example 1 is that after the completion of the reaction, the reaction temperature was lowered to 30 ℃ and the reaction pressure was lowered to 30mmHg and then maintained for 50 minutes.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, and 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of methyl bromide in a liquid phase were added with stirring, and the temperature was raised to 125 ℃ and the pressure in the autoclave was about 1.7MPa, and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 50 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.43g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.7%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 12%.
Example 17
The only difference from example 1 is that after the reaction was completed, the reaction temperature was lowered to 30 ℃ and the reaction pressure was lowered to 30mmHg and then maintained for 80 minutes.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, and 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of methyl bromide in a liquid phase were added with stirring, and the temperature was raised to 125 ℃ and the pressure in the autoclave was about 1.7MPa, and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 80 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.39g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.9%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 11%.
Example 18
The only difference from example 1 is that after the reaction was completed, the reaction temperature was lowered to 30 ℃ and the reaction pressure was lowered to 30mmHg and then maintained for 100 minutes.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, and 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of methyl bromide in a liquid phase were added with stirring, and the temperature was raised to 125 ℃ and the pressure in the autoclave was about 1.7MPa, and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the pressure is maintained at 30 ℃ and 30mmHg for 100 minutes. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.37g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.9%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 10%.
Example 19
The only difference from example 1 is that n-decane as a solvent was used in an amount of 6mL in this example.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 6mL (4.381g, 0.031mol) of n-decane (a) as a solvent were charged into a high-pressure autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of methyl bromide in a liquid phase were added under stirring, the temperature was raised to 125 ℃ and the pressure in the autoclave was about 1.7MPa, and the reaction was carried out at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, the pressure of the reaction kettle is slowly reduced to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept for 60 minutes at 30 ℃ and 30 mmHg. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.03g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of the triethyl aluminum to be 93.6%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 11%.
Example 20
The only difference from example 1 is that n-decane, a solvent used in this example, was 10 mL.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 10mL (7.301g, 0.051mol) of n-decane as a solvent were charged into an autoclave, 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of methyl bromide in a liquid phase were charged with stirring, the temperature was raised to 125 ℃ and the pressure in the autoclave was about 1.7MPa, and the reaction was carried out at this temperature for 150 minutes. Decrease after completion of the reactionThe temperature is increased to 30 ℃, the pressure of the reaction kettle is slowly released to micro positive pressure, then the temperature is maintained at 30 ℃, the pressure is reduced to 30mmHg by vacuumizing, and the reaction kettle is kept at 30 ℃ and 30mmHg for 60 minutes. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.41g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.7%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 13%.
Comparative example 1
The only difference from example 1 is that after the reaction was completed, the reaction temperature was lowered to 30 ℃ and the reaction vessel was depressurized without vacuum-pumping.
Under the protection of high-purity nitrogen, 0.355g (1.13mmol) of BiCl3And 8mL (5.841g, 0.041mol) of n-decane (a solvent) as a solvent were charged into a high-pressure autoclave, and 8.576g (10mL, 0.075mol) of triethylaluminum and 28.568g (0.30mol) of methyl bromide in a liquid phase were added with stirring, and the temperature was raised to 125 ℃ and the pressure in the autoclave was about 1.7MPa, and reacted at this temperature for 150 minutes. After the reaction is finished, the temperature is reduced to 30 ℃, and the pressure of the reaction kettle is slowly released to micro positive pressure. And (3) stopping stirring, keeping the temperature at 15 ℃ under the protection of high-purity nitrogen, standing for 24 hours, separating out crystals from the reaction product, and separating the crystals from the reaction product. The reaction solution from which the crystals were removed was vacuum-distilled to obtain 3.38g of trimethylaluminum.
Hydrolyzing a small amount of reaction liquid without crystal substances by using a dilute hydrochloric acid solution, and performing gas chromatography analysis on the hydrolyzed gas to obtain the contents of methane and ethane, thereby calculating the conversion rate of triethyl aluminum to be 98.7%, and performing ICP emission spectrometer analysis on the hydrolyzed reaction liquid to obtain the loss rate of Bi to be 71%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (24)
1. A preparation method of trimethylaluminum comprises the following steps:
step I, in the presence of a bismuth-based compound and a solvent, reacting trialkyl aluminum with methyl halide to obtain a reaction product, wherein the trialkyl aluminum and the methyl halide are both in a liquid state and are added into a reactor to carry out the reaction, the bismuth-based compound is at least one of alkyl bismuth, aryl bismuth, inorganic bismuth salt and any bismuth-containing compound capable of being converted into alkyl bismuth or aryl bismuth, the reaction adopts a high-pressure liquid phase reaction, the reaction temperature is 110-140 ℃, and the reaction pressure is 1.5-2.1 MPa;
step II, removing halogenated alkane in the reaction product, standing the reaction product to separate out crystals, recovering the separated out crystals and separating the residual reaction product to obtain trimethylaluminum;
wherein the molar ratio of the solvent to the trialkyl aluminum is (0.4-0.8) to 1;
and step II, reducing the reaction temperature to 20-35 ℃, reducing the reaction pressure to negative pressure, keeping the reaction pressure for 30-100min, removing the halogenated alkane, and standing the reaction product at the temperature below 25 ℃ to separate out crystals.
2. The method as claimed in claim 1, wherein the reaction temperature in step I is 120-130 ℃.
3. The method as claimed in claim 1, wherein the reaction time in step I is 100-250 min.
4. The method as claimed in claim 3, wherein the reaction time in step I is 120-180 min.
5. The production method according to claim 1, wherein the bismuth-based compound is bismuth trihalide.
6. The method according to claim 5, wherein the bismuth-based compound is BiCl3Or BiBr3。
7. The method of claim 1, wherein the solvent is selected from the group consisting of C9-C12An alkane.
8. The method according to claim 7, wherein the solvent is decane.
9. The method according to claim 8, wherein the solvent is n-decane.
10. The method according to claim 1, wherein the trialkyl aluminum has a general formula of AlR3R is an alkyl group having 2 or more carbon atoms.
11. The method according to claim 10, wherein R is C in the general formula of the trialkylaluminum2-C10An alkyl group.
12. The production method according to claim 11, wherein the trialkylaluminum is at least one selected from the group consisting of triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum and trihexylaluminum.
13. The method according to claim 1, wherein the methyl halide is at least one of methyl chloride, methyl bromide and methyl iodide.
14. The method according to claim 1, wherein the molar ratio of the halogenated methane to the trialkylaluminum is (3-5): 1.
15. The process according to claim 14, wherein the molar ratio of the halogenated methane to the trialkylaluminum is (3.5-4): 1.
16. the process according to claim 1, wherein the molar ratio of the bismuth-based compound to the trialkylaluminum is (0.01-0.03):1, in terms of elemental bismuth.
17. The production method according to claim 16, wherein the molar ratio of the bismuth-based compound to the trialkylaluminum is (0.015 to 0.02) in terms of elemental bismuth: 1.
18. the production method according to claim 1, wherein the molar ratio of the solvent to the trialkylaluminum is (0.5-0.6): 1.
19. the method of claim 1, wherein in the step II, the reaction temperature is lowered to 25 to 30 ℃, the reaction pressure is lowered to 1 to 50mmHg and maintained for 50 to 100min, and the haloalkane is removed from the reaction product.
20. The process according to claim 1, wherein in the step II, the reaction product is allowed to stand at 0 to 25 ℃ to precipitate crystals.
21. The method according to claim 20, wherein in the step II, the reaction product is allowed to stand at 10 to 15 ℃ to precipitate crystals.
22. The method according to claim 1, wherein in step II, the time for allowing the crystals to precipitate by the standing is 12 to 48 hours.
23. The method according to claim 22, wherein the standing is carried out for a period of time of 24 to 36 hours to precipitate crystals in step II.
24. The preparation method according to claim 1, wherein in the step II, trimethylaluminum is separated from the rest of the reaction products by vacuum rectification.
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| US4364872A (en) * | 1981-07-13 | 1982-12-21 | Ethyl Corporation | Method of making aluminum alkyls |
| US4925962A (en) * | 1988-10-24 | 1990-05-15 | Ethyl Corporation | Trimethylaluminum process |
| US4948906A (en) * | 1990-02-16 | 1990-08-14 | Ethyl Corporation | Trimethylaluminum process |
| US5543537A (en) * | 1995-05-08 | 1996-08-06 | Albemarle Corporation | Process for preparing trimethylaluminum |
| CN1597685A (en) * | 2003-09-19 | 2005-03-23 | 中国石油天然气股份有限公司 | Preparation method of aluminium methide oxyalkane |
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| GB2432364B (en) * | 2005-11-18 | 2009-11-11 | Rohm & Haas Elect Mat | Organometallic compound purification |
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| US4364872A (en) * | 1981-07-13 | 1982-12-21 | Ethyl Corporation | Method of making aluminum alkyls |
| US4925962A (en) * | 1988-10-24 | 1990-05-15 | Ethyl Corporation | Trimethylaluminum process |
| US4948906A (en) * | 1990-02-16 | 1990-08-14 | Ethyl Corporation | Trimethylaluminum process |
| US5543537A (en) * | 1995-05-08 | 1996-08-06 | Albemarle Corporation | Process for preparing trimethylaluminum |
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