CN113797568A - Synthesis device and synthesis method of electronic grade tri (dimethylamino) silane - Google Patents
Synthesis device and synthesis method of electronic grade tri (dimethylamino) silane Download PDFInfo
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Abstract
The invention provides a synthesis device and a synthesis method of electronic grade tri (dimethylamino) silane. The synthesis device of the electronic grade trisilane comprises: the system comprises a raw material premixing device, a reaction unit, a pressurizing device and a purification unit, wherein the raw material premixing device is provided with a chlorine receiver inlet, a dimethylamino chloride inlet, a solvent inlet and a mixed liquid outlet; the reaction unit is provided with an inert atmosphere inlet, a mixed liquid inlet, a trichlorosilane inlet and a crude product outlet, and the mixed liquid inlet is communicated with the mixed liquid outlet; the pressurizing device is used for adjusting the pressure in the reaction unit; and the purification unit is provided with a purification inlet and a discharge outlet, and the purification inlet is communicated with the crude product outlet through a crude product conveying pipeline. The synthesis device is adopted to change the types and feeding modes of reaction raw materials, and the pressurizing device is arranged to reduce the fluctuation of the reaction temperature in the reaction device and reduce the process cost.
Description
Technical Field
The invention relates to the field of synthesis of electronic grade tri (dimethylamino) silane, in particular to a synthesis device and a synthesis method of electronic grade tri (dimethylamino) silane.
Background
The MOS transistor size of the basic device in very large scale integrated circuits is continuously reduced when SiO2When the thickness of the gate dielectric is reduced to nanometer level, the gate dielectric passes through SiO2The leakage current of (a) increases exponentially with decreasing thickness. The huge leakage current not only seriously affects the device performance, but also finally causes SiO2Cannot play an insulating role. Using high dielectric constant (i.e., high-K materials) instead of SiO2Is currently the most promising approach to solve this problem. The use of high-K materials enables the same capacitance density to be maintained on one hand, and enables the gate dielectric to have larger physical thickness on the other hand, thereby avoiding the use of ultra-thin SiO2Leakage current problems due to tunneling in the gate dielectric. The tris (dimethylamino) silane serving as a precursor source not only has better stability and higher vapor pressure, but also shows quite high reactivity, so that the organic silicon source becomes SiO deposited by the current atomic layer method2The focus of the study.
The prior document (CN103172653A) provides a method for synthesizing electronic grade tris (dimethylamino) silane, which comprises the following steps: under the protection of inert gas and at the reaction temperature of-78 ℃, a certain amount of dimethylamine, n-hexane, n-butyllithium and trichlorosilane are sequentially added into a reactor and react with each other to prepare the tri (dimethylamino) silane. The disadvantages of this method are: the reaction conditions in the reaction process are very harsh and need to be carried out at a low temperature of-78 ℃; however, the reaction of trichlorosilane and dimethylamine belongs to exothermic reaction, and the temperature is very difficult to control; meanwhile, hydrochloride of dimethylamine is generated in the reaction process, so that the consumption of the dimethylamine is increased, and the subsequent filtration cost is increased.
Another prior document (CN-110325539a) also provides a method for synthesizing electronic grade tris (dimethylamino) silane, comprising: the preparation method comprises the steps of taking metal Mg, dimethylamine and trichlorosilane as raw materials, taking n-heptane as a solution, and preparing tri (dimethylamino) silane at the temperature of 5-85 ℃. The method improves the control of the reaction temperature, and reduces the consumption of dimethylamine by adding Mg powder. The disadvantages are: the temperature of the process needs to be converted between 5 ℃ and 85 ℃, so that the requirement on a reaction kettle is high; meanwhile, a large amount of hydrogen is generated in the reaction process, so that the potential safety hazard of the system is increased, and the safety of the system is reduced.
In view of the above problems, it is desirable to provide a method for synthesizing electronic grade tris (dimethylamino) silane with stable reaction temperature, low cost and high safety.
Disclosure of Invention
The invention mainly aims to provide a device and a method for synthesizing electronic grade tri (dimethylamino) silane, and aims to solve the problems that the reaction temperature is difficult to control, the reaction cost is high and potential safety hazards exist in the conventional synthesis method.
In order to achieve the above object, an aspect of the present invention provides an apparatus for synthesizing electronic grade trisilane, comprising: the system comprises a raw material premixing device, a reaction unit, a pressurizing device and a purification unit, wherein the raw material premixing device is provided with a chlorine receiver inlet, a dimethylamino chloride inlet, a solvent inlet and a mixed liquid outlet; the reaction unit is provided with an inert atmosphere inlet, a mixed liquid inlet, a trichlorosilane inlet and a crude product outlet, and the mixed liquid inlet is communicated with the mixed liquid outlet; the pressurizing device is used for adjusting the pressure in the reaction unit; and the purification unit is provided with a purification inlet and a discharge outlet, and the purification inlet is communicated with the crude product outlet through a crude product conveying pipeline.
Further, the reaction unit comprises: the device comprises a reaction device and a rectification device, wherein the reaction device is provided with a mixed liquid inlet, a trichlorosilane inlet and a synthetic product outlet; the rectifying device is provided with a distillation inlet, a tower top product outlet and a crude product outlet, and the distillation inlet is communicated with the synthesized product outlet.
Further, the purification unit comprises: the device comprises a complexing device and an impurity removing device, wherein the complexing device is provided with a metal complexing agent inlet, a purification inlet and a complexing product outlet, and the purification inlet is communicated with the crude product outlet; and the impurity removing device is provided with a filtering inlet and an electronic grade trisilane outlet, and the filtering inlet is communicated with the complexing product outlet through a complexing product conveying pipeline.
Furthermore, a metal complexing agent layer is arranged in the complexing device, and is selected from an organic phosphate layer, an amino-hydroxy acid layer or a hydroxyl-amino-hydroxy acid layer.
Further, the organic phosphate layer is selected from an ethylene diamine tetra methylene phosphonic acid sodium layer, a diethylenetriamine penta methylene phosphonic acid salt layer or an amino trimethylene phosphonic acid salt layer; the amino hydroxy acid layer is selected from sodium nitrilotriacetic acid layer, ethylene diamine tetraacetic acid salt layer, diethylenetriamine pentaacetic acid or diethylenetriamine pentaacetic acid salt layer; the hydroxy amino hydroxy acid layer is selected from hydroxy ethylenediamine tetraacetic acid layer, ethylene glycol diethyl ether-N, N, N ', N' tetra acetic acid layer or dihydroxy glycine layer.
Further, the purification unit further comprises: the reboiling device is provided with a reboiling inlet and a reboiling gas outlet, and the reboiling inlet is communicated with the complexing product outlet; and the adsorption device is provided with a reboiling gas inlet and a gas phase product outlet, the reboiling gas inlet is communicated with the reboiling gas outlet, and the gas phase product outlet is communicated with the filtering inlet through a gas phase product conveying pipeline.
Further, the purification unit also comprises a sub-boiling rectification device which is arranged on the gas-phase product conveying pipeline.
Further, the electronic grade trisilane synthesizing device further comprises: the solid slag filtering device and the conveying device are sequentially arranged on a crude product conveying pipeline between the reaction device and the rectifying device along the flowing direction of the materials.
Another aspect of the present application also provides a method for synthesizing an electronic grade trisilane, the method comprising: under the conditions of solvent, inert atmosphere and pressurization, reacting a chlorine receiving agent, dimethylamine chloride and trichlorosilane to obtain a crude product of trichlorosilane, wherein the chlorine receiving agent is a metal simple substance capable of coordinating with chlorine atoms; and purifying the crude product of the trisilane to obtain the electronic grade trisilane.
Further, the chlorine acceptor is selected from one or more of the group consisting of metallic zinc, metallic aluminum, and metallic copper; preferably, the molar ratio of the trichlorosilane, the chlorine acceptor and the dimethylamino chloride is 1:.
Further, the reaction process comprises: carrying out coordination reaction on a chlorine receiving agent and dimethylamine chloride to obtain a product system of the coordination reaction; carrying out substitution reaction on the product system of the coordination reaction and trichlorosilane to obtain a product system of the substitution reaction; and (3) rectifying and purifying a product system of the substitution reaction to obtain a tower bottom product and a tower top product, wherein the tower bottom product is a crude product of trisilane.
Further, the pressure of a tower kettle in the rectification and purification process is 100-150 Kpa, the temperature of the top of the tower is 145-148 ℃, the reflux-feed ratio is 15-20, and the number of theoretical plates is 80-120.
Furthermore, the temperature of the substitution reaction is 80-90 ℃, and the reaction pressure is 50-80 KPa.
Further, the purification process comprises: carrying out complexing reaction on the crude trisilane and a complexing agent to obtain mixed gas containing a complexing product; removing impurities in the mixed gas to obtain the electronic grade trisilane.
Further, the complexing agent is selected from one or more of organic phosphate, amino hydroxy acid and hydroxyl amino hydroxy acid; preferably, the organic phosphate is selected from one or more of the group consisting of sodium ethylene diamine tetra methylene phosphonate, diethylene triamine penta methylene phosphonate and amino trimethylene phosphonate; the amino hydroxy acid is selected from one or more of sodium nitrilotriacetate, ethylene diamine tetraacetic acid salt, diethylenetriamine pentaacetic acid or diethylenetriamine pentaacetic acid salt; the hydroxy amino carboxylic acid is selected from one or more of hydroxy ethylenediamine tetraacetic acid, ethylene glycol diethyl ether-N, N, N ', N' tetra acetic acid and dihydroxy glycine.
Further, before the step of removing impurities from the gas mixture containing the complex product, the purification process further comprises: reboiling the mixed gas containing the complex product to obtain reboiled gas; and adopting an adsorbent to carry out adsorption treatment on the reboiled gas to obtain a purified product; preferably, the adsorbent is selected from one or more of the group consisting of silica gel, alumina, activated carbon, polyamide, diatomaceous earth, activated carbon, and molecular sieves.
Further, after the step of treating the reboiled gas with the adsorbent, the purification process further comprises: performing sub-boiling rectification on the purified product to obtain a tower top product; removing impurities in the tower top product to obtain electronic grade trisilane; preferably, the ratio of height to diameter of an evaporation device adopted in the sub-boiling rectification process is 3-7, and the temperature is 135-140 ℃.
By applying the technical scheme of the invention, under the protection of inert atmosphere, a chlorine receiving agent and chlorine atoms in the dimethylamino chloride are subjected to coordination reaction in a raw material premixing device to form an intermediate product; and then the intermediate product and trichlorosilane are subjected to substitution reaction, so that chlorine atoms in the trichlorosilane are substituted by dimethylamino to form a tri (dimethylamino) silane crude product. The dimethylamino chloride is liquid, so that the temperature of a reaction system is stable in the reaction process. Meanwhile, in the reaction process, the pressure in the reaction device is adjusted by adopting a pressurizing device, so that the risk of violent change of reaction temperature caused by gas escape in a reaction system is favorably reduced. Compared with the existing synthesis reaction device, the synthesis device adopted by the application changes the types of reaction raw materials and the feeding mode, and meanwhile, the pressurizing device is arranged to reduce the fluctuation of the reaction temperature in the reaction device, so that the synthesis device adopting the electronic grade tri (dimethylamino) silane provided by the application is also favorable for reducing the process cost.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic structural diagram of an electronic grade tris (dimethylamino) silane synthesis device provided by the invention.
Wherein the figures include the following reference numerals:
100. a raw material premixing device; 101. a chlorine receiver inlet; 102. a dimethyl ammonium chloride inlet; 103. a solvent inlet; 104. a mixed liquid outlet;
200. a reaction unit; 210. a reaction device; 211. a trichlorosilane inlet; 212. an inert atmosphere inlet; 213. a mixed liquid inlet; 214. a coarse product outlet; 220. a rectification device; 221. a distillation inlet; 222. a product outlet at the top of the column; 230. a solid slag filtering device; 240. a conveying device;
300. a pressurizing device;
400. a purification unit; 410. a complexing device; 411. a metal complexing agent layer; 420. an impurity removal device; 430. a reboiling unit; 440. an adsorption device; 450. a sub-boiling rectifying device.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing synthesis method of electronic grade tri (dimethylamino) silane has the problems of difficult control of reaction temperature, high reaction cost and potential safety hazard. In order to solve the above technical problem, as shown in fig. 1, the present application provides an apparatus for synthesizing electronic grade tris (dimethylamino) silane, comprising: a raw material premixing device 100, a reaction device 210, a pressurizing device 300 and a purifying unit 400. The raw material premixing device 100 is provided with a chlorine receiver inlet 101, a dimethyl ammonium chloride inlet 102, a solvent inlet 103 and a mixed liquid outlet 104; the reaction device 210 is provided with an inert atmosphere inlet 212, a mixed liquid inlet 213, a trichlorosilane inlet 211 and a crude product outlet 214, and the mixed liquid inlet 213 is communicated with the mixed liquid outlet 104; the pressurizing means 300 is used to adjust the pressure in the reaction unit 200; and the purification unit 400 is provided with a purification inlet and a discharge outlet, the purification inlet being communicated with the crude product outlet 214 through a crude product conveying pipe.
Under the protection of inert atmosphere, the chlorine receiving agent and chlorine atoms in the dimethylamino chloride are subjected to coordination reaction in the raw material premixing device 100 to form an intermediate product; and then the intermediate product and trichlorosilane are subjected to substitution reaction, so that chlorine atoms in the trichlorosilane are substituted by dimethylamino to form a tri (dimethylamino) silane crude product. The dimethylamino chloride is liquid, so that the temperature of a reaction system is stable in the reaction process. Meanwhile, in the reaction process, the pressure in the reaction device 210 is adjusted by the pressurizing device 300, which is beneficial to reducing the risk of violent change of reaction temperature caused by gas escape in the reaction system. Compared with the existing synthesis reaction device, the synthesis device provided by the application changes the types and feeding modes of reaction raw materials, and meanwhile, the pressurizing device 300 is arranged, so that the fluctuation of the reaction temperature in the reaction device 210 can be reduced, and the synthesis device adopting the electronic grade tris (dimethylamino) silane provided by the application is also beneficial to reducing the process cost.
In a preferred embodiment, the reaction unit 200 includes a reaction apparatus 210 and a rectification apparatus 220. The reaction device 210 is provided with a mixed liquid inlet 213, a trichlorosilane inlet 211 and a synthesized product outlet; the rectifying device 220 is provided with a distillation inlet 221, an overhead product outlet 222 and a crude product outlet 214, wherein the distillation inlet 221 is communicated with the synthesized product outlet.
The tris (dimethylamino) silane product system may contain solvent, unreacted raw material dimethylamino chloride, metal ions formed by a chlorine acceptor and the like besides crude tris (dimethylamino) silane. The crude tris (dimethylamino) silane product can be separated from the bottom of the column by the rectifying device 220, and the solvent with low boiling point and the chlorodimethylamine are discharged from the top of the column, thereby realizing the primary purification process.
In a preferred embodiment, the raw material premixing device 100 is a stirrer, a pipeline mixing device or a static mixing device, and the reaction device 210 is a high pressure reaction tank or a stirred bed reaction tank.
Alternatively, in a preferred embodiment, the raw material premixing device 100 and the reaction device 210 are combined into a single unit and replaced with a stirred bed reactor.
The crude tris (dimethylamino) silane obtained by the reaction can be purified by a purification apparatus commonly used in the art, as long as electronic grade tris (dimethylamino) silane can be obtained, and the specific structure thereof is not particularly limited. In a preferred embodiment, the purification unit 400 includes a complexation device 410 and a purge device 420. The complexing device 410 is provided with a metal complexing agent inlet, a purification inlet and a complexing product outlet; the impurity removal device 420 is provided with a filtering inlet and an electronic grade tri (dimethylamino) silane outlet, and the filtering inlet is communicated with the complexing product outlet through a complexing product conveying pipeline.
The crude tris (dimethylamino) silane is transferred to a complexing device 410, and then in the complexing device 410, metal ions formed by the chlorine acceptor are combined with a complexing agent to form a complex having only a coordination bond and no covalent bond, or a chelate having both a coordination bond and a covalent bond, thereby removing residual metal ions. The remaining impurities are then removed by the impurity removal device 420, which is advantageous for further improving the purification degree of the target product.
The metal complexing agent layer 411 provided in the complexing device 410 may be formed using a complexing agent commonly used in the art. In a preferred embodiment, the interior of the complexing device 410 is provided with a metal complexing agent layer 411, the metal complexing agent layer 411 being selected from an organic phosphate layer, an amino-hydroxy acid layer or a hydroxyamino-hydroxy acid layer. Compared with the existing complexing agent, the metal complexing agent layer 411 has stronger coordination capacity with metal ions, and the metal complexing agent is added in a layered structure to be beneficial to improving the removal capacity of the metal ions, so that the metal complexing agent layer 411 is beneficial to further improving the removal capacity of the metal ions formed by the chlorine acceptor and improving the cleanliness of a target product.
More preferably, the organophosphate layer includes, but is not limited to, a sodium ethylenediaminetetramethylenephosphonate layer, a diethylenetriaminepentamethylenephosphonate layer, or an aminotrimethylenephosphonate layer; the amino carboxylic acid layer includes, but is not limited to, a sodium nitrilotriacetic acid layer, an ethylenediaminetetraacetic acid salt layer, diethylenetriaminepentaacetic acid, or a diethylenetriaminepentaacetic acid salt layer; the hydroxyaminocarboxylic acid layer includes, but is not limited to, a layer of hydroxyethylenediaminetetraacetic acid, a layer of ethylene glycol bis (. beta. -diaminoethyl) ethyl ether-N, N, N ', N' tetraacetic acid, or a layer of dihydroxyglycine.
The ability of purification unit 400 to purify the crude tris (dimethylamino) silane can be further enhanced as needed by the actual level of purification of the tris (dimethylamino) silane. In a preferred embodiment, the purification unit 400 further comprises: the device comprises a reboiling device 430 and an adsorption device 440, wherein the reboiling device 430 is provided with a reboiling inlet and a reboiling gas outlet, and the reboiling inlet is communicated with a complex product outlet; and the adsorption device 440 is provided with a reboiling gas inlet and a gas phase product outlet, the reboiling gas inlet is communicated with the reboiling gas outlet, and the gas phase product outlet is communicated with the filtering inlet through a gas phase product conveying pipeline.
The complex product system obtained after the treatment of the complexing device 410 comprises solid materials and tris (dimethylamino) silane existing in a liquid form. After being conveyed to the reboiling device 430, the liquid-phase material can escape in a gaseous state, so that the solid-phase material and the liquid-phase material can be separated. The escaped gas phase product is then passed through an adsorption unit 440 to remove by-product high boiling point impurities. A further purification process can be achieved by means of the reboiling unit 430 and the adsorption unit 440.
In a preferred embodiment, the purification unit 400 further comprises a sub-boiling rectification apparatus 450, the sub-boiling rectification apparatus 450 being disposed in the vapor phase product transfer line.
In the sub-boiling rectification process, when the liquid to be purified is heated to a temperature lower than the boiling point by 5 ℃, the material is basically in a molecular state because the boiling point of a target object is not reached, so that metal ions and solid particles are not entrained in steam. Thus, the gas phase product discharged from the adsorption apparatus 440 is subjected to the sub-boiling rectification by the sub-boiling rectification apparatus 450, and metal ions and solid particles contained therein can be further removed, thereby reducing the content of impurities in the target product. Meanwhile, the enriched metal impurities and solid particles can be discharged in a mode of periodically discharging residual liquid from the tower bottom.
In order to improve the purification degree of the reaction raw material and reduce the introduction of impurities from the reaction raw material end, it is preferable that the electronic grade tris (dimethylamino) silane synthesis apparatus further includes a solid residue filtering device 230 and a conveying device 240, and the solid residue filtering device 230 and the conveying device 240 are sequentially disposed on the crude product conveying pipeline between the reaction device 210 and the rectification device 220 along the flow direction of the material.
Another aspect of the present application also provides a method for synthesizing electronic grade tris (dimethylamino) silane, comprising: under the conditions of inert atmosphere and pressurization, performing coordination reaction on a chlorine receiving agent, dimethylamine chloride and trichlorosilane to obtain a tris (dimethylamino) silane crude product, wherein the chlorine receiving agent is a metal simple substance capable of coordinating with chlorine atoms; and purifying the crude product of the tri (dimethylamino) silane to obtain the electronic grade tri (dimethylamino) silane.
Under the protection of inert atmosphere, a chlorine receiving agent, dimethylamino chloride and trichlorosilane are subjected to substitution reaction, so that chlorine atoms in the trichlorosilane are substituted by dimethylamino to form a tris (dimethylamino) silane crude product. Compared with dimethylamine as gas, the dimethylamino chloride is liquid, and the adoption of the dimethylamino chloride as a raw material is beneficial to ensuring that the temperature of a reaction system is relatively stable in the reaction process. Meanwhile, the pressurization in the reaction process is beneficial to reducing the risk of violent change of the reaction temperature caused by the escape of gas in the reaction system. In addition, compared with the existing synthesis reaction, the method for synthesizing the electronic-grade tri (dimethylamino) silane changes the types and the feeding modes of the reaction raw materials, and can reduce the fluctuation of the reaction temperature by carrying out the reaction under the pressurized condition, so that the synthesis method of the electronic-grade tri (dimethylamino) silane is favorable for reducing the process cost.
The chlorine acceptor used in the above substitution reaction is a compound having a coordination ability with a chlorine atom in dimethylamine chloride. In a preferred embodiment, the chlorine acceptor includes, but is not limited to, one or more of the group consisting of metallic zinc, metallic aluminum, and metallic copper. Compared with metal lithium and magnesium, metal zinc and aluminum have more coordination sites with dimethylamine chloride, so that the adoption of the chlorine acceptors is beneficial to further improving the binding capacity of the chlorine acceptors to the dimethylamine chloride, reducing the probability of influencing the reaction temperature due to escape, and further improving the temperature property of the reaction temperature.
In order to further improve the reaction rate of trichlorosilane and the conversion rate of tris (dimethylamino) silane, the molar ratio of trichlorosilane, chlorine acceptor and dimethylamino chloride is preferably 1 (2.5-3.5) to (3.0-4.5).
Preferably, the reaction process of the chlorine acceptor, the dimethylamine chloride and the trichlorosilane comprises the following steps: carrying out coordination reaction on a chlorine receiving agent and dimethylamine chloride to obtain a product system of the coordination reaction; carrying out substitution reaction on the product system of the coordination reaction and trichlorosilane to obtain a product system of the substitution reaction; and (3) rectifying and purifying a product system of the substitution reaction to obtain a tower bottom product and a tower top product, wherein the tower bottom product is a crude product of the tri (dimethylamino) silane.
The chlorine acceptor and the dimethylamine chloride are subjected to coordination reaction, and then are subjected to substitution reaction with the trichlorosilane, so that the binding capacity between the chlorine acceptor and the dimethylamine chloride can be improved, the substitution degree in the trichlorosilane can be improved, and the generation of byproducts can be reduced. The tris (dimethylamino) silane product system may contain solvent, unreacted raw material dimethylamino chloride, metal ions formed by a chlorine acceptor and the like besides crude tris (dimethylamino) silane. The crude tris (dimethylamino) silane product can be separated from the low-boiling solvent and the chlorodimethylamine by the rectification purification process, thereby realizing the primary purification process.
In a preferred embodiment, the reaction process of the chlorine acceptor, dimethylamine chloride and trichlorosilane further comprises: and (3) rectifying and purifying a product system of the coordination reaction to obtain a tower bottom product and a tower top product, wherein the tower bottom product is a crude product of the tri (dimethylamino) silane. The tris (dimethylamino) silane product system may contain solvent, unreacted raw material dimethylamino chloride, metal ions formed by a chlorine acceptor and the like besides crude tris (dimethylamino) silane. The crude product of the tri (dimethylamino) silane can be separated from the tower bottom through the rectification purification process, and the solvent with low boiling point and the chlorodimethylamine are discharged from the tower top, thereby realizing the primary purification process. In order to further improve the extraction rate of the crude tris (dimethylamino) silane product, preferably, the pressure of a tower kettle in the rectification and purification process is 100-150 Kpa, the temperature of the tower top is 145-148 ℃, the reflux feed ratio is 15-20, and the number of theoretical plates is 80-120.
In a preferred embodiment, the temperature of the substitution reaction is 80-90 ℃, and the reaction pressure is 50-80 KPa. The synthesis reaction of the tri (dimethylamino) silane is an exothermic reaction, and the temperature and the pressure of the coordination reaction are limited in the range, so that the heat released by the reaction can be fully utilized, the reaction can be promoted to be carried out towards the direction of generating the tri (dimethylamino) silane, and the conversion rate of the tri (dimethylamino) silane can be further improved; on the other hand, the risk of influencing the stability of the reaction temperature due to the outgassing of the reaction solvent or chloromethylamine can be reduced.
In a preferred embodiment, the purification process comprises: performing complex reaction on the crude tris (dimethylamino) silane product and a complexing agent to obtain mixed gas containing the complex product; removing impurities in the mixed gas to obtain the electronic grade tri (dimethylamino) silane. In the process of carrying out complex reaction on the crude product of the tris (dimethylamino) silane and the complexing agent, metal ions formed by the chlorine receiver are combined with the complexing agent to form a complex which only has a coordination bond and does not have a covalent bond, or a chelate which has both the coordination bond and the covalent bond is formed and exists in a reaction system in a solid state. And then removed through an impurity removal step, which is beneficial to further improving the purification degree of the target product.
The complexing agent used in the above-mentioned complexing reaction may be formed using a complexing agent commonly used in the art. Preferably, the complexing agent includes, but is not limited to, one or more of the group consisting of organophosphates, amino hydroxy acids and hydroxyamino hydroxy acids. Compared with the existing complexing agent, the metal complexing agent has stronger coordination capacity with metal ions, so that the adoption of the complexing agent is beneficial to further improving the removal capacity of the metal ions formed by the chlorine acceptor and improving the cleanliness of a target product. More preferably, the organic phosphate includes, but is not limited to, one or more of the group consisting of sodium ethylene diamine tetra methylene phosphonate, diethylene triamine penta methylene phosphonate, and amino trimethylene phosphonate; amino hydroxy acids include, but are not limited to, one or more of the group consisting of sodium nitrilotriacetate, ethylenediaminetetraacetic acid, ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid, or diethylenetriaminepentaacetate; hydroxyaminohydroxy acids include, but are not limited to, one or more of the group consisting of hydroxyethylenediaminetetraacetic acid, ethylene glycol bis (. beta. -diaminoethyl) ethyl ether-N, N, N ', N' tetra-acetic acid, and dihydroxyglycine.
According to the actual requirement of the purification degree of the tri (dimethylamino) silane, the purification capability of the purification process to the crude tri (dimethylamino) silane can be further enhanced. In a preferred embodiment, before the step of removing the impurities in the mixed gas containing the complex product, the purification process further comprises: reboiling a product system of the complex reaction to obtain reboiled gas; and adsorbing the heavy boiling gas by adopting an adsorbent to obtain a purified product. The complex product system comprises a complex product in a solid state and tris (dimethylamino) silane in a liquid state. The liquid material can escape in a gaseous state through the reboiling process, and the separation of the solid material and the liquid material is realized. Then the escaped gas phase product is treated by adsorption to remove non-metallic impurities such as B, P and compounds thereof. Thus, a further purification process can be realized by the above-mentioned reboiling process and adsorption treatment.
The adsorbent may be of a kind commonly used in the art, and includes, but is not limited to, one or more of the group consisting of silica gel, alumina, activated carbon, polyamide, diatomaceous earth, activated carbon, and molecular sieves, and preferably, the above adsorbent is a molecular sieve. According to the difference of the molecular diameter in the components to be treated, a molecular sieve with a certain aperture is selected for adsorption, and an adsorption product with higher purity can be obtained. The molecular sieve can be used in a single pore size or in a mixture of multiple pore sizes. When a single-aperture molecular sieve is used, the molecular sieve with the aperture only smaller than that of the tris (dimethylamino) silane is selected, so that the molecular sieve has better adsorption capacity on all impurity compounds; when the molecular sieves with various apertures are selected and mixed, proper molecular sieves are selected according to the distribution condition of the molecular diameters of impurity compounds in the components, and impurities with different molecular diameters are adsorbed in stages (the order is small first and then large). Before the molecular sieve is used for adsorption, activation treatment is needed, for example, under the protection of inert gas, drying treatment is carried out on the molecular sieve at 300-380 ℃, and the inert gas can be nitrogen, argon or helium. In order to further improve the removal rate of impurities, the height-diameter ratio of an adsorption column adopted in the adsorption process is 5-15, the adsorption temperature is 20-60 ℃, the adsorption column is made of 316L stainless steel, and the inner wall of the adsorption column is subjected to electrolytic polishing treatment.
In a preferred embodiment, after the step of treating the heavy boiling gas with the adsorbent, the purification process further comprises: performing sub-boiling rectification on the purified product to obtain a tower top product; removing impurities in the tower top product to obtain the electronic grade tri (dimethylamino) silane. In the sub-boiling rectification process, when the liquid to be purified is heated to a temperature lower than the boiling point by 5 ℃, the material is basically in a molecular state because the boiling point of a target object is not reached, so that metal ions and solid particles are not entrained in steam. Therefore, the gas phase product discharged in the adsorption treatment process is subjected to sub-boiling rectification, metal ions and solid particles contained in the gas phase product can be further removed, and the impurity content in the target product is reduced. Preferably, the ratio of height to diameter of an evaporation device adopted in the sub-boiling rectification process is 3-7, and the temperature is 135-140 ℃. The temperature of the sub-boiling rectification process and the height-diameter ratio of the evaporation device are limited in the range, so that the separation rate of the tri (dimethylamino) silane can be further improved on the basis of ensuring that metal ions and solid particles are not entrained, and the yield and the purification degree of a target product are improved.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
A novel aminosilane and a preparation method thereof, comprising the following stepsThe method comprises the following steps: first, in N2Under protection, 16.25g (0.25mol) of zinc powder, 30ml of n-heptane and 23.85g (0.3mol) of chlorodimethylamine solution are added into a stirred bed reaction kettle, mechanical stirring is started for 15min, 13.6g (0.1mol) of trichlorosilane is slowly dripped under vigorous stirring, the stirring reaction is continued, the temperature is controlled to be 85 +/-2 ℃, the pressure in the kettle is 65KPa, after 2h of reaction, the mixture is sequentially filtered (manufacturer: JHDS series filter model of Nicotine Jianghai filtration equipment Limited), primary rectification (tower kettle pressure is 125KPa, tower top temperature is 145-148 ℃, reflux feed ratio is 17, theoretical plate number is 115), combined adsorption (industrial grade ethylene diamine tetra methylene phosphonic acid sodium with purity of 99% produced by Hubei Yuansheng Seisai Limited company), and molecular sieve is 13X type molecular sieve produced by Gallery open-dimensional chemical engineering Limited company, pore diameter is 0.9nm, silicon-aluminum ratio is 3.0, and processing is carried out at 350℃, Separating and purifying reaction products by procedures of sub-boiling rectification (the height-diameter ratio is 6, the temperature is 138 ℃), fine filtration (a steam filter with the filtration precision of 0.02 mu m produced by Shanghai Min Sanshi petrochemical equipment Co., Ltd.) and the like, and further obtaining the electronic grade tri (dimethylamino) silane, wherein under the process condition, the product yield reaches 86%, and the purity of the obtained tri (dimethylamino) silane can reach 99.999%.
Example 2
A novel aminosilane and a preparation method thereof comprise the following steps: first, in N2Adding 7.8g (0.3mol) of aluminum powder, 40ml of n-heptane and 27.83g (0.35mol) of chlorodimethylamine solution into a stirred bed reaction kettle under protection, starting mechanical stirring for 15min, slowly dropwise adding 13.6g (0.1mol) of trichlorosilane under vigorous stirring, continuously stirring for reaction, controlling the temperature to be 85 +/-2 ℃, controlling the pressure in the kettle to be 70KPa, reacting for 2h, sequentially filtering (manufacturer: JHDS series filter of Nicotine Jianghai filtration equipment Limited company), performing primary rectification (tower kettle pressure of 125KPa, tower top temperature of 145-148 ℃, reflux feed ratio of 17, theoretical plate number of 115), performing combined adsorption (industrial grade sodium ethylene diamine tetra methylene phosphonate with purity of 99% produced by Hubei Seiyisai Seisai Limited company), and performing combined adsorption (complexing agent is 13X type molecular sieve produced by Sudoku Korea Seisakung Kangwei chemical engineering Limited company, aperture of 0.9nm and silicon-aluminum ratio of 0.93.0 treatment at 350 ℃), sub-boiling rectification (aspect ratio 6, temperature 138 ℃), fine filtration (manufacturer: steam filter with filtering precision of 0.02 μm produced by shanghai Min cheng petrochemical equipment limited), and the like, to further obtain electronic grade tris (dimethylamino) silane, wherein under the process conditions, the product yield reaches 89%, and the purity of the obtained tris (dimethylamino) silane can reach 99.999%.
Example 3
A novel aminosilane and a preparation method thereof comprise the following steps: first, in N2Under protection, 9.1g (0.35mol) of aluminum powder, 50ml of n-heptane and 31.8g (0.4mol) of chlorodimethylamine solution are added into a stirred bed reaction kettle, mechanical stirring is started for 15min, 13.6g (0.1mol) of trichlorosilane is slowly dripped under vigorous stirring, the stirring reaction is continued, the temperature is controlled to be 85 +/-2 ℃, the pressure in the kettle is 70KPa, after 2h of reaction, the mixture is sequentially filtered (manufacturer: JHDS series filter of Nicotine Jianghai filtration equipment Limited company), primary rectification (tower kettle pressure is 125KPa, tower top temperature is 145-148 ℃, reflux feed ratio is 17, theoretical plate number is 115), combined adsorption (industrial grade ethylene diamine tetra methylene phosphonic acid sodium with purity of 99% produced by Hubei Yuansheng Seisai Limited company), and molecular sieve is 13X type molecular sieve produced by Gallery open-dimensional chemical engineering Limited company, pore diameter is 0.9nm, silicon-aluminum ratio is 3.0, and processing is carried out at 350℃, Separating and purifying reaction products by sub-boiling rectification (the height-diameter ratio is 6, the temperature is 138 ℃), fine filtration (a steam filter with the filtration precision of 0.02 mu m produced by Shanghai Min Sanshi Equipment Co., Ltd.) and other procedures to obtain the electronic grade tri (dimethylamino) silane, wherein under the process conditions, the product yield reaches 85%, and the purity of the obtained tri (dimethylamino) silane can reach 99.999%.
Example 4
The differences from example 3 are: the molar ratio of the trichlorosilane to the chlorine receiving agent to the chlorinated dimethyl ammonia is 1:3.5: 3.
The yield of the product is 76%, and the purity is 99.997%.
Example 5
The differences from example 3 are: the molar ratio of the trichlorosilane to the chlorine receiving agent to the chlorinated dimethyl ammonia is 1:2.5: 4.5.
The yield of the product is 79 percent, and the purity is 99.999 percent.
Example 6
The differences from example 3 are: the molar ratio of the trichlorosilane to the chlorine receiving agent to the chlorinated dimethyl ammonia is 1:2: 6.
The yield of the product is 63%, and the purity is 99.990%.
Example 7
The differences from example 3 are: the molar ratio of the trichlorosilane to the chlorine receiving agent to the chlorinated dimethyl ammonia is 1:4: 2.
The yield of the product was 52% and the purity was 99.991%.
Example 8
The differences from example 3 are: the chlorine receiver is metallic zinc.
The yield of the product is 86 percent, and the purity is 99.996 percent.
Example 9
The differences from example 3 are: the chlorine receiver is metallic copper.
The yield of the product is 83 percent, and the purity is 99.997 percent.
Example 10
The differences from example 3 are: the temperature of the substitution reaction was 80 ℃ and the pressure was 80 KPa.
The yield of the product is 84.6%, and the purity is 99.998%.
Example 11
The differences from example 3 are: the temperature of the substitution reaction was 90 ℃ and the pressure was 50 KPa.
The yield of the product is 84.8%, and the purity is 99.999%.
Example 12
The differences from example 3 are: the temperature of the substitution reaction was 70 ℃ and the pressure was 40 KPa.
The yield of the product was 51% and the purity was 99.992%.
Example 13
The differences from example 3 are: the temperature of the substitution reaction was 10 ℃ and the pressure was 90 KPa.
The yield of the product was 47% and the purity was 98.991%.
Example 14
The differences from example 3 are: the reaction process is to mix the chlorine receiving agent, dimethylamine chloride and trichlorosilane and then input the mixture into the reaction unit 200 for reaction. The purification procedure was as in example 3.
The yield of the product was 57% and the purity was 98.994%.
Example 15
The differences from example 3 are: in the combined adsorption process, the complexing agent is ethylenediamine tetraacetic acid with the purity of 99% produced by Shandong Longhui chemical Co., Ltd, the molecular sieve is a 10X molecular sieve produced by Shanghai cloud-cloud environment-friendly new material Co., Ltd, the pore diameter is 0.9nm, and the silica-alumina ratio is 2.8.
The yield of the product is 85.1%, and the purity is 99.996%.
Example 16
The differences from example 3 are: in the combined adsorption process, the complexing agent is dihydroxy glycine with the purity of 99 percent produced by chemical company Limited Wande Hubei, and the molecular sieve is 10X.
The yield of the product was 84.2% and the purity was 99.996%.
Comparative example 1
The differences from example 3 are: the reaction process is to mix the chlorine receiving agent, dimethylamine chloride and trichlorosilane and then input the mixture into the reaction unit 200 for reaction, and the reaction process is carried out under normal pressure. The purification procedure was as in example 3.
The yield of the product was 42.6% and the purity was 98.321%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
it is seen from comparison of examples 3 to 7 that limiting the molar ratio of trichlorosilane, chlorine acceptor and chlorinated dimethylamine to the preferred range of the present application is beneficial for further improving the yield and purity of electronic grade tris (dimethylamino) silane.
Comparing examples 3, 8 and 9, it is seen that the yield is higher when electronic grade tris (dimethylamino) silane is prepared using the preferred chlorine acceptor of the present application.
Comparing examples 3, 10 to 13, it is seen that limiting the temperature and pressure of the substitution reaction to the preferred ranges herein is beneficial in increasing the yield and purity of electronic grade tris (dimethylamino) silane.
Comparing examples 3, 14, 15, and 16, it can be seen that the mixing manner of the raw materials and the type of the adsorbent in the combined adsorption process can affect the yield and purity of the finally obtained electronic grade tris (dimethylamino) silane.
Comparing examples 1 to 3 and comparative example 1, it can be seen that the yield and purity of electronic grade tris (dimethylamino) silane can be greatly improved by the process provided herein.
It is noted that the terms first, second and the like in the description and in the claims of the present application 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 terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
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 (17)
1. An apparatus for synthesizing electronic grade tris (dimethylamino) silane, comprising:
a raw material premixing device (100), wherein the raw material premixing device (100) is provided with a chlorine receiving agent inlet (101), a dimethylamino chloride inlet (102), a solvent inlet (103) and a mixed liquid outlet (104);
the reaction unit (200) is provided with a trichlorosilane inlet (211), an inert atmosphere inlet (212), a mixed liquid inlet (213) and a crude product outlet (214), and the mixed liquid inlet (213) is communicated with the mixed liquid outlet (104);
a pressurizing device (300), the pressurizing device (300) being used for adjusting the pressure in the reaction unit (200); and
purification unit (400), purification unit (400) are provided with purification entry and bin outlet, the purification entry with coarse product export (214) sets up through coarse product conveying line intercommunication.
2. The apparatus for synthesizing electronic grade tris (dimethylamino) silane according to claim 1, wherein the reaction unit (200) comprises:
the reaction device (210) is provided with the mixed liquid inlet (213), the trichlorosilane inlet (211) and a synthesized product outlet;
the rectifying device (220), rectifying device (220) set up distillation entry (221), top of the tower product export (222) and coarse product export (214), distillation entry (221) with the synthetic product export intercommunication sets up.
3. The apparatus for synthesizing electronic grade tris (dimethylamino) silane according to claim 1 or 2, wherein the purification unit (400) comprises:
a complexing device (410), wherein the complexing device (410) is provided with a metal complexing agent inlet, the purification inlet and a complex product outlet, and the purification inlet is communicated with the crude product outlet (214); and
the device comprises an impurity removal device (420), wherein the impurity removal device (420) is provided with a filtering inlet and an electronic grade tri (dimethylamino) silane outlet, and the filtering inlet is communicated with the complexing product outlet through a complexing product conveying pipeline.
4. An electronic grade tris (dimethylamino) silane synthesizer according to claim 3, characterized in that the interior of the complexing device (410) is provided with a metal complexing agent layer (411), the metal complexing agent layer (411) being selected from an organic phosphate layer, an amino acid layer or a hydroxyamino acid layer.
5. The apparatus of claim 4, wherein the organic phosphate layer is selected from a sodium ethylenediamine tetramethylene phosphonate layer, a diethylenetriamine pentamethylene phosphonate layer, or an amino trimethylene phosphonate layer;
the amino hydroxy acid layer is selected from a nitrilotriacetic acid sodium layer, an ethylene diamine tetraacetic acid salt layer, diethylenetriamine pentaacetic acid or a diethylenetriamine pentaacetic acid salt layer;
the hydroxy amino hydroxy acid layer is selected from a hydroxy ethylene diamine tetraacetic acid layer, a glycol bis (beta-diaminoethyl) ethyl ether-N, N, N ', N' tetra acetic acid layer or a dihydroxy glycine layer.
6. The apparatus for synthesizing electronic grade tris (dimethylamino) silane according to claim 5, wherein the purification unit (400) further comprises:
the reboiling device (430), the reboiling device (430) is provided with a reboiling inlet and a reboiling gas outlet, and the reboiling inlet is communicated with the complexing product outlet; and
the adsorption device (440) is provided with a heavy boiling gas inlet and a gas phase product outlet, the heavy boiling gas inlet is communicated with the heavy boiling gas outlet, and the gas phase product outlet is communicated with the filtering inlet through a gas phase product conveying pipeline.
7. The apparatus for synthesizing electronic-grade tris (dimethylamino) silane according to claim 6, wherein the purification unit (400) further comprises a sub-boiling rectification apparatus (450), the sub-boiling rectification apparatus (450) being disposed on the gas-phase product transfer line.
8. The apparatus for synthesizing electronic grade tris (dimethylamino) silane according to claim 2, further comprising: the device comprises a solid slag filtering device (230) and a conveying device (240), wherein the solid slag filtering device (230) and the conveying device (240) are sequentially arranged on a crude product conveying pipeline between the reaction device (210) and the rectifying device (220) along the flowing direction of materials.
9. A method for synthesizing electronic grade tris (dimethylamino) silane, comprising:
under the conditions of solvent, inert atmosphere and pressurization, reacting a chlorine receiving agent, dimethylamine chloride and trichlorosilane to obtain a crude product of tris (dimethylamino) silane, wherein the chlorine receiving agent is a metal simple substance capable of coordinating with chlorine atoms; and
and purifying the crude product of the tri (dimethylamino) silane to obtain the electronic grade tri (dimethylamino) silane.
10. The method of synthesizing electronic grade tris (dimethylamino) silane of claim 9, wherein the chlorine acceptor is selected from one or more of the group consisting of metallic zinc, metallic aluminum, and metallic copper;
preferably, the molar ratio of the trichlorosilane to the chlorine acceptor to the dimethylamino chloride is 1 (2.5-3.5):
(3.0～4.5)。
11. the method of synthesizing electronic grade tris (dimethylamino) silane according to claim 9 or 10, wherein the reaction process comprises:
carrying out a coordination reaction on the chlorine receiving agent and the dimethylamine chloride to obtain a product system of the coordination reaction;
carrying out substitution reaction on the product system of the coordination reaction and the trichlorosilane to obtain a product system of the substitution reaction;
and rectifying and purifying the product system of the substitution reaction to obtain a tower bottom product and a tower top product, wherein the tower bottom product is the crude product of the tri (dimethylamino) silane.
12. The method for synthesizing electronic grade tris (dimethylamino) silane according to claim 11, wherein the pressure of a tower kettle in the rectification and purification process is 100-150 Kpa, the temperature of the tower top is 145-148 ℃, the reflux-feed ratio is 15-20, and the theoretical plate number is 80-120.
13. The method for synthesizing electronic grade tris (dimethylamino) silane according to claim 11, wherein the temperature of the substitution reaction is 80 to 90 ℃ and the reaction pressure is 50 to 80 KPa.
14. The method of synthesizing electronic grade tris (dimethylamino) silane according to any of claims 9 to 13, wherein the purification process comprises:
carrying out a complexing reaction on the crude tris (dimethylamino) silane product and a complexing agent to obtain a mixed gas containing a complexing product;
and removing impurities in the mixed gas to obtain the electronic grade tri (dimethylamino) silane.
15. The method of synthesizing electronic grade tris (dimethylamino) silane of claim 14, wherein the complexing agent is selected from one or more of an organophosphate, an amino hydroxy acid, and a hydroxy amino hydroxy acid;
preferably, the organic phosphate is selected from one or more of the group consisting of sodium ethylene diamine tetra methylene phosphonate, diethylene triamine penta methylene phosphonate and amino trimethylene phosphonate;
the amino hydroxy acid is selected from one or more of sodium nitrilotriacetate, ethylene diamine tetraacetic acid salt, diethylenetriamine pentaacetic acid or diethylenetriamine pentaacetic acid salt;
the hydroxy amino carboxylic acid is selected from one or more of the group consisting of hydroxy ethylene diamine tetraacetic acid, ethylene glycol bis (beta-diaminoethyl) ethyl ether-N, N, N ', N' tetra acetic acid and dihydroxy glycine.
16. The method of synthesizing electronic grade tris (dimethylamino) silane of claim 15, wherein prior to the step of removing impurities from the gas mixture containing complexed products, the purification process further comprises:
reboiling the mixed gas containing the complex product to obtain reboiled gas; and
adsorbing the heavy boiling gas by adopting an adsorbent to obtain a purified product;
preferably, the adsorbent is selected from one or more of the group consisting of silica gel, alumina, activated carbon, polyamide, diatomaceous earth, activated carbon, and molecular sieves.
17. The method of synthesizing electronic grade tris (dimethylamino) silane of claim 16, wherein after the step of treating the reboiled gas with an adsorbent, the purification process further comprises:
performing sub-boiling rectification on the purified product to obtain a tower top product;
removing impurities in the tower top product to obtain the electronic grade tri (dimethylamino) silane;
preferably, the ratio of height to diameter of an evaporation device adopted in the sub-boiling rectification process is 3-7, and the temperature is 135-140 ℃.
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| CN115591272A (en) * | 2022-10-27 | 2023-01-13 | 大连科利德光电子材料有限公司（Cn） | Method and system for purifying silicon-based precursor |
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| CN115591272B (en) * | 2022-10-27 | 2023-04-07 | 大连科利德光电子材料有限公司 | Method and system for purifying silicon-based precursor |
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