CN111303197A - Continuous production method of transition metal amino complex - Google Patents
Continuous production method of transition metal amino complex Download PDFInfo
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- CN111303197A CN111303197A CN202010324679.5A CN202010324679A CN111303197A CN 111303197 A CN111303197 A CN 111303197A CN 202010324679 A CN202010324679 A CN 202010324679A CN 111303197 A CN111303197 A CN 111303197A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/005—Compounds of elements of Group 5 of the Periodic System without metal-carbon linkages
Abstract
The invention provides a continuous production method of a transition metal amino complex, which comprises the steps of respectively cooling liquid A prepared by taking a metal alkyl compound and a solvent as main components in proportion and liquid B prepared by taking organic amine and the solvent as main components in proportion to the temperature required by the reaction, injecting the cooled liquid B into a continuous flow reactor for reaction, and allowing generated intermediate mixed liquid containing a solid product to flow out of the continuous flow reactor and then enter a dynamic tubular reactor; cooling the solution C prepared by taking a raw material containing transition metal and a solvent as main components in proportion to the temperature required by the reaction, entering a dynamic tubular reactor to react with the intermediate mixed solution to generate a product mixed solution containing solids, filtering and distilling. Compared with a reaction kettle for stirring reaction, the invention has the advantages of higher yield, higher conversion rate and higher production efficiency, and meanwhile, the production device composed of a specific mixing structure, a heat exchange system and a pressure-resistant material has higher stability and higher safety.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of semiconductor electronic chemicals, and particularly relates to a continuous production method of a transition metal amino complex.
[ background of the invention ]
The precursor is a main raw material of a semiconductor film deposition process, and refers to a substance which is applied to a semiconductor production manufacturing process, carries a target element, is in a gaseous state or a volatile liquid state, has chemical thermal stability and simultaneously has corresponding reaction activity or physical properties. In semiconductor manufacturing processes including thin film, photolithography, interconnect, doping techniques, and the like, precursors are mainly used in vapor deposition (including physical deposition PVD, chemical vapor deposition CVD, and atomic vapor deposition ALD) to form various thin film layers that meet semiconductor manufacturing requirements. In addition, the precursor can also be used for semiconductor epitaxial growth, etching, ion implantation doping, cleaning and the like, and is one of core materials in semiconductor manufacturing.
The transition metal amino complex is the best choice for preparing high dielectric constant (k) films at present as a representative precursor for generating capacitors and gates, is also suitable for an ALD process, and has wide market potential. However, the raw materials and products of the material are extremely sensitive to air, the exothermic amount of the reaction is large, the reaction is difficult to accurately control, the solid-solid and solid-liquid reactions are involved, the reaction efficiency is low, and the flash point of the raw materials is low, so that the material brings great pressure to the safe production. Thus, the preparation of such products of high purity is very difficult. At present, the synthesis of the materials is still mainly based on a laboratory preparation process, and most of the materials are prepared by batch reaction in a kettle and are mixed and reacted by stirring. The batch reaction has low reaction efficiency, low heat exchange efficiency and poor safety, and has higher risk of exposing and scrapping materials.
Such as tetrakis (methylethylamino) hafnium (TEMAH, tetramethylethylenediamine) hafnium, also known as tetrakis (methylethylamino) hafnium or tetrakis (methylethylamino) hafnium), is a key raw material for producing hafnium nitride or hafnium oxide by Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD) processes. CN103601750A discloses a preparation method of tetrakis (methylethylamino) hafnium, which is as follows: under an inert atmosphere, adding methylethylamine and an alkane solvent into a three-necked bottle, mechanically stirring, placing the reaction bottle at-10 to-80 ℃, dropwise adding n-hexane solution of n-butyllithium, stirring and reacting for 5 to 12 hours after dropwise adding, then adding hafnium tetrachloride into the reaction system, stirring and reacting for 18 to 30 hours under the protection of inert gas at the temperature of not higher than 60 ℃, then removing the solvent under normal pressure, and carrying out reduced pressure distillation to obtain TEMAH; CN106916178A discloses another method for industrially producing tetra (methylamino) hafnium, which comprises the steps of adding N-butyl lithium-alkane solution into a reactor protected by inert atmosphere, dropwise adding N-methylethylamine under the conditions of 0-30 ℃ and stirring for reaction, keeping the temperature of 0-30 ℃ for 8-12 hours of reaction, then adding hafnium tetrachloride in batches, keeping the temperature of 0-30 ℃ for reaction for 8-12 hours, keeping reflux for reaction for 4-8 hours, removing by-product lithium chloride through a centrifugal solid-liquid separator after cooling, transferring the solution to a distiller, and carrying out reduced pressure distillation to obtain TEMAH.
For another example, tetrakis (dimethylamino) zirconium (TDMAZ) is a precursor used to obtain high-k zirconium oxide thin films by CVD or ALD and is receiving increasing attention. CN103910640A discloses a method for synthesizing tetrakis (dimethylamino) zirconium as follows: adding dimethylamine and n-hexane into a three-necked bottle according to a ratio under argon atmosphere, uniformly stirring, placing the reaction bottle between-20 ℃ and-60 ℃, dropwise adding n-butyllithium solution into the reaction bottle, stirring and reacting for 10 hours after dropwise adding, then adding zirconium tetrachloride into the reaction system, keeping the temperature of the reaction system between-20 ℃ and 0 ℃, stirring and reacting for 24-30 hours under the protection of inert gas, then removing the solvent at normal pressure, and distilling under reduced pressure to obtain TDMAZ.
For another example, CN106008224A discloses a method for synthesizing tetrakis (methylamino) vanadium, which comprises the following steps: adding a mixture of methylethylamine and ether or aromatic hydrocarbon or alkane into a reactor in an inert atmosphere, keeping the temperature of the system at 60-30 ℃, dropwise adding n-butyllithium, stirring at 30-0 ℃ for 8-12 hours after dropwise adding, dropwise adding vanadium tetrachloride at 60-30 ℃, reacting at 30-0 ℃ for 4-10 hours after dropwise adding, returning to room temperature, performing reflux reaction for 28 hours, evaporating a reaction solvent at normal pressure, and evaporating a product under reduced pressure.
For another example, CN106916072A discloses a method for synthesizing pentakis (dimethylamino) tantalum, comprising the following steps: adding a mixture of tantalum pentachloride and alkane into a reactor protected by inert atmosphere, adding dimethylamine under the stirring condition for reaction, keeping the temperature of a reaction system at 0-30 ℃, and keeping the temperature at 0-30 ℃ for reaction for 8-12 hours after dropwise addition; dropwise adding n-butyllithium-alkane solution, keeping the temperature of 0-30 ℃ for reacting for 4-20 hours, keeping the reflux reaction for 4-12 hours, decompressing and evaporating alkane solvent to dryness, transferring the solvent into a sublimator, and decompressing to obtain the product.
From the above, it can be seen that the transition metal amino complex is prepared by stirring, mixing and batch reaction, the reaction time is usually several hours to several tens hours, the reaction speed is slow, the reaction efficiency is low, and the requirement of industrial continuous production cannot be met.
[ summary of the invention ]
The invention provides a continuous production method of a transition metal amino complex, which can realize continuous production of the transition metal amino complex and improve the production efficiency.
The technical solution of the invention is as follows:
a continuous production method of a transition metal amino complex is characterized in that a liquid A prepared by taking a metal alkyl compound and a solvent as main components in proportion and a liquid B prepared by taking an organic amine and the solvent as main components in proportion are respectively cooled to the temperature required by the reaction and then are simultaneously injected into a continuous flow reactor for reaction, and an intermediate mixed liquid containing a solid product is generated and flows out of the continuous flow reactor and then enters a dynamic tubular reactor; cooling the solution C prepared by taking a raw material containing transition metal and a solvent as main components in proportion to the temperature required by the reaction, entering a dynamic tubular reactor to react with the intermediate mixed solution to generate a product mixed solution containing solids, filtering and distilling to obtain the liquid with the product purity of 95-96%.
Further, the continuous production method of the transition metal amino complex is characterized by comprising the following steps:
1) preparing a metal alkyl compound and a solvent into a solution A in proportion, preparing organic amine and the solvent into a solution B in proportion, and preparing a raw material containing transition metal and the solvent into a solution C in proportion;
2) respectively cooling the solution A and the solution B to the temperature required by the reaction after passing through a plunger pump and a precooler, and simultaneously injecting the solution A and the solution B into a continuous flow reactor with the temperature of-30-10 ℃ at a certain flow rate to perform the reaction for 5-30s to generate intermediate mixed solution containing solid products;
3) the intermediate mixed liquor flows out of the outlet of the continuous flow reactor and enters a dynamic tubular reactor with the temperature of 0-40 ℃; simultaneously, cooling the uniformly mixed solution C to the temperature required by the reaction through a precooler, and feeding the solution C into a dynamic tubular reactor at a certain flow rate; the intermediate mixed solution and the solution C stay in the dynamic tubular reactor for reaction for 20-60min to generate a product mixed solution containing solids;
4) the product mixture flows into a filter, after being filtered by the filter, clear liquid is filtered out from the bottom of the filter, and solids are intercepted in a filter cylinder by a filter element;
5) and (3) distilling the clarified liquid in a distilling device, and distilling off the solvent to obtain liquid with the product purity of more than or equal to 95%.
Further, the step 5) is followed by the following steps:
6) and (3) feeding the liquid with the product purity of more than or equal to 95% into a rectifying device for rectifying and purifying until the product purity reaches more than 99.99%.
Further, the metal alkyl compound is methyllithium, ethyllithium, isopropyllithium, n-butyllithium or t-butyllithium.
Further, the organic amine is NR1R2Wherein R is1、R2Is methyl, ethyl, isopropyl, sec-butyl or tert-butyl.
Further, the above continuous production method further comprises the steps of: and cooling the solution D prepared from the reaction monomer to the temperature required by the reaction through a precooler, and simultaneously entering the dynamic tubular reactor together with the solution C.
Further, the liquid C is prepared by uniformly mixing a solid raw material containing transition metal and a solvent under the stirring state, and then entering the dynamic tubular reactor from the upper part of the top end of the dynamic tubular reactor to participate in the reaction through a metering type peristaltic pump.
Further, the temperature of the dynamic tubular reactor is regulated and controlled by a heat transfer medium (preferably heat transfer oil, water or glycol); the temperature of the continuous flow reactor is controlled by a heat transfer medium, preferably a cooling liquid.
Furthermore, the materials in the dynamic tubular reactor are uniformly mixed by a mixing mechanism in the dynamic tubular reactor and flow to the rear end in the horizontal direction.
Further, the continuous flow reactor comprises an inner hollow tube, an outer jacket layer and two micro channels which are positioned between the inner hollow tube and the outer jacket layer and are mutually communicated through convection holes and are stacked up and down, the width of each micro channel is 1-10 mm, the optimal width of each micro channel is 1.5-3 mm, the liquid A and the liquid B are uniformly mixed through the micro channels, and the inner hollow tube and the outer jacket layer are filled with heat transfer media.
Further, the dynamic tubular reactor comprises an inner hollow tube, an outer jacket layer and a middle chamber which is positioned between the inner hollow tube and the outer jacket layer and used for mixing materials, wherein the middle chamber is provided with a winding tube which surrounds the inner hollow tube and is controlled by a motor, and the inner hollow tube and the outer jacket layer are filled with heat transfer media; the reaction temperature of the step 3) is controlled by heating or cooling a heat transfer medium through temperature control equipment matched with the dynamic tubular reactor.
Further, the filter is at least two sets of parallel filters which can be switched between open and closed.
Furthermore, the filter is a metal filter medium which is internally provided with a back flushing system and has micron-sized filtering precision.
Further, the transition metal amino complex includes: (i) m1(NR1R2)4Or R3CpM1(NR1R2)3Wherein M is1Is V, Ti, Zr or Hf; r1、R2Is methyl, ethyl, isopropyl, sec-butyl or tert-butyl, Cp is cyclopentadienyl, R3Is H, methyl, ethyl, isopropyl, sec-butyl or tert-butyl; (ii) m2(NR1R2)5Or R3CpM2(NR1R2)4Wherein M is2Is V, Nb or Ta, R1、R2Is methyl, ethyl, isopropyl, sec-butyl or tert-butyl, etc., Cp is cyclopentadienyl, R3Is H, methyl, ethyl, isopropyl, sec-butyl or tert-butyl.
The invention has the following general beneficial effects:
compared with a reaction kettle for stirring reaction, the invention has the advantages of higher yield, higher conversion rate and higher production efficiency, and meanwhile, the production device composed of a specific mixing structure, a heat exchange system and a pressure-resistant material has higher stability and higher safety.
In particular, the invention
(1) The mixing efficiency is high: compared with the mixing of the stirring paddle of the existing reaction kettle, the internal three-dimensional structure of the continuous flow reactor, the channel and the hierarchical structure which are specially designed for mixing, ensures that the mixing efficiency of materials in the reactor is higher.
(2) The conversion rate is high: through more reasonable temperature control, heat transfer and mixing effects, the conversion rate of the invention can reach 82% -90%, which is far higher than the conversion rate (70-80%) of the stirring batch reaction of the existing reaction kettle.
(3) The reaction time is short: compared with the reaction kettle stirring reaction batch reaction time of more than 20h, the reaction time of the continuous flow preparation method is within 60min, and the reaction time is greatly shortened.
(4) The yield is high: taking the stirring reaction of a 5L kettle in a laboratory for preparing the tetra (methyl ethylamino) hafnium, the yield of 24 hours of reaction is not more than 250g, while the yield of 24 hours of the invention is 3288g, which is 13 times of the stirring reaction of the 5L kettle, and the continuous flow preparation method can realize 24 hours of uninterrupted reaction in one day, and has great advantages compared with the batch production of the stirring reaction.
(5) The stability and the safety are good: the stirring reaction of the reaction kettle has common stirring and mixing efficiency and limited temperature control effect due to the design of the kettle body, so the stability of the reaction is generally controlled, and the safety is also general; the whole system is a sealed system, has a good mixing structure, a heat exchange system and a pressure-resistant material, and can accurately control the temperature (0.1 ℃) and the feeding speed (the precision is mL/min) of the reaction, so that the reaction device can achieve ideal stability and safety.
[ description of the drawings ]
FIG. 1 is a simplified continuous production apparatus according to the present invention;
FIG. 2 is a schematic diagram of the internal structure of a continuous flow reactor of the present invention;
FIG. 3 is a schematic view of the internal structure of the dynamic tube reactor of the present invention.
Note, 10, liquid phase feed tank; 20, a liquid-solid feed tank; 30, a pump; 40, a precooler; 50, a continuous flow reactor; 60, a dynamic tubular reactor; 70, a filter; 80, a distillation device; 90, a rectification device; 91, a condenser; 100, micro flow channels; 100a, upper microchannel; 100b, a lower microchannel; 200, convection holes; 501, a first agent inlet; 502, a second inlet; and 7, a liquid outlet.
[ detailed description ] embodiments
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
The continuous production device mainly comprises a feeding system (comprising an advection pump, a peristaltic pump and a stirrer), a precooler, a continuous flow reactor, a dynamic tubular reactor, a filter, a distillation device and a rectification device.
Wherein, the liquid feeding pump is preferably an advection pump or a diaphragm pump, the solid-liquid (namely dispersion liquid containing solids) feeding is preferably a peristaltic pump, and the solid-liquid is uniformly mixed by a stirrer; the precooler is a heat exchanger, and the raw materials are respectively cooled to the temperature required by the reaction so as to reduce the influence on the temperature required by the reaction.
The continuous flow reactor is designed with a unique internal structure as shown in fig. 2. The inside 3 layers of three-dimensional layout structures that set up of continuous flow reactor, including inboard hollow tube, outside jacket layer and lie in two through the mutual upper and lower range upon range of miniflow channels that set up of convection current hole between inboard hollow tube, the outside jacket layer, inboard hollow tube, outside jacket in situ packing have heat transfer medium. The micro flow channel mark 100a on the upper part, the micro flow channel mark 100b on the upper part, which is positioned at the inflection point of the upper layer 100a, is communicated with the end part of the lower layer 100b through a convection hole 200; the turning point of the lower layer 100b is communicated with the end of the upper layer 100a through a pair of flow holes 200, so that the fluid in the two micro-channels can be mixed back and forth and crosswise, and the mixing process is extremely short. The two fluids respectively flow in from the first agent inlet 501 and the second agent inlet 502, and after several tens of times of mixing within a period of several seconds to minutes, the two fluids can achieve the purpose of fully mixing and reacting, and finally flow out from the liquid outlet 7, and the more detailed structural description thereof is referred to patent application CN 108854891A; it should be noted that, the continuous production apparatus of the present invention is suitable for liquid-solid mixing, and therefore, a conventional micro flow channel is severely blocked and cannot be used, and in view of the problem, the width of the micro flow channel of the continuous flow reactor of the present invention is preferably 1 to 10mm, and more preferably 1.5 to 3 mm.
A stirrer is arranged in the dynamic tubular reactor, as shown in fig. 3, the stirrer comprises an inner hollow tube, an outer jacket layer and an intermediate chamber which is arranged between the inner hollow tube and the outer jacket layer and used for mixing materials, the intermediate chamber is provided with a winding tube which surrounds the inner hollow tube and is controlled by a motor, a certain rotating speed is controlled under the driving of the motor, the solid materials and the liquid materials are fully mixed and contacted under the disturbance and stirring action of the winding tube in the reactor, the sedimentation phenomenon cannot be generated, the solid materials and the liquid materials are always in a uniform mixing state, the back mixing phenomenon is not obvious, the materials flow towards the discharge hole under the driving of feeding, the reaction residence time can be accurately controlled through the control of the feeding flow, and the materials flow towards the discharge hole under the driving of feeding; the inner hollow tube and the outer jacket layer are filled with heat transfer media, and the reaction temperature is controlled by heating or cooling the heat transfer media through temperature control equipment matched with the dynamic tubular reactor.
The filter is a metal sintered filter with the filtering precision reaching the micron level and is provided with a back flushing system, and the two filters are arranged, one is opened and the other is prepared; the rectifying device can be a filler rectifying tower.
The flow description of the invention is exemplified as follows:
the prepared A and B liquids (or materials can be metered and proportioned by a metering pump), the flow rate is set, the A and B liquids are simultaneously pumped into a continuous flow reactor for reaction after passing through a plunger pump and a precooler, and the temperature of the reactor is controlled by cooling liquid (preferably glycol); after 5-30s of reaction, generating a solid product as an intermediate, wherein an intermediate mixed solution flows out from an outlet of the continuous flow reactor and enters the dynamic tubular reactor from a side feed inlet at the top end of the dynamic tubular reactor to participate in the reaction; the liquid C is prepared by uniformly mixing a solid raw material and a solvent under the stirring state, and then entering the dynamic tubular reactor from the upper part of the top end of the dynamic tubular reactor to participate in the reaction through a metering type peristaltic pump; the intermediate mixed liquid and the liquid C are simultaneously conveyed into the dynamic tubular reactor for reaction, the temperature of the reactor is controlled by a heat-conducting oil temperature controller, the two materials are fully and uniformly mixed by a mixing mechanism inside the dynamic tubular reactor in the reactor, the two materials are in a state of slowly flowing towards the rear end in the horizontal direction, and the back mixing degree is very small; the reaction product stays in the dynamic tubular reactor for 20-60min, the generated product mixed liquor finally flows out from the lower part of the tail end of the reactor, the flowing-out solution is a solid-liquid mixture, the solid-liquid mixture flows into a filter, after the fine filtration of the filter, clear liquor is filtered out from the bottom of the filter, and the solid is intercepted in a filter cartridge by a filter element. And (3) distilling the clear liquid in a distilling device, wherein most of the solvent is evaporated out and recycled by the distilling device, and the purity of the product in the distilled solution reaches 95-96%. And (4) the crude product enters a rectifying device for rectification and purification to obtain an electronic grade product.
The method can increase reactants and add the reactants into the dynamic tubular reactor to participate in reaction in a treatment method equivalent to that of the liquid C.
The process takes place in the general reaction:
wherein R is1～R2May be methyl (-CH)3) Ethyl (-C)2H5) Isopropyl (-iPr), sec-butyl (-sec-Bu), tert-butyl (-tBu), etc., n is a natural number, X is a halogen, and M is a transition metal.
When reactants are added (e.g., cyclopentadienyl ligands), the process occurs with the general reaction:
wherein R is3Is H, methyl, ethyl, isopropyl, sec-butyl or tert-butyl.
The operation steps of a preferred embodiment of the present invention are as follows:
1. debugging
Calibrating and testing a plunger pump, a peristaltic pump, temperature and pressure and the like respectively to ensure the accuracy of the instrument and the metering accuracy of the plunger pump and the peristaltic pump;
2. system purging replacement pressure maintaining
The individual pieces of equipment and piping should have been cleaned and dried prior to original assembly. And after the system is assembled, purging and replacing the system, and cleaning and discharging impurities, water and the like in the system. And replacing and maintaining the pressure of the system, detecting the air tightness of the system to ensure that the system has good air tightness, and replacing air in the system with high-purity nitrogen to ensure an oxygen-free and water-free state.
3. Continuous flow reaction
(1) Reducing the temperature of the reactor to-30-10 ℃;
(2) filling the solutions A and B for the plunger pump to discharge gas in the inlet pipe, and reducing the temperature of the precooler to-30-10 ℃;
(3) when the temperature of the precooler and the reactor is reduced to the set temperature, the plunger pumps A and B are started to feed the continuous flow reactor simultaneously. After the A and the B are mixed and reacted in the reactor, the temperature of the reactor tends to rise, the temperature setting of the cooling liquid is well controlled, and the temperature in the reactor is maintained at the set temperature; the solution A and the solution B stay in the reactor for 5 to 30 seconds, and are fully mixed and reacted to generate a solid product which is an intermediate, and the solid intermediate and the solvent form a flowable solid-liquid mixed solution. And discharging the solid mixed liquid from a discharge hole at the bottom of the tail end of the reactor.
4. Dynamic tubular reaction
(1) Controlling the temperature of the reactor at 0-40 ℃;
(2) the solution C is filled into the peristaltic pump to discharge gas in the inlet pipe, and the temperature of the precooler is reduced to the reaction temperature;
(3) and (3) reducing the temperature of the precooler and the reactor to the reaction temperature, stirring and opening the solution C, and uniformly stirring the solution C to form a suspension.
(4) When the intermediate solid mixed liquid flows out from the outlet of the continuous flow reactor, a peristaltic pump is immediately started to feed the raw material solution C into the dynamic tubular reactor. The two materials are fully and uniformly mixed by a mixing mechanism in the dynamic tubular reactor in the reactor, and the materials flow slowly towards the rear end in the horizontal direction, and the back mixing degree is very small; the reaction is carried out for 20min-60min in the dynamic tubular reactor, the temperature tends to rise in the reaction process, the setting of a heat-conducting oil temperature controller is well controlled, and the temperature in the reactor is maintained within the reaction temperature range; finally, a liquid product and a solid byproduct are generated, and the solid product is a solid-liquid mixed solution. The resultant product mixture finally flows out from the lower part of the end of the reactor, and the flowing-out solution is a solid-liquid mixture.
5. Filtration
After the solid-liquid mixed liquid enters the filter, the solid-liquid mixed liquid is subjected to precise filtration by the filter under the action of a certain pressure difference, the solid-liquid mixed liquid is subjected to solid-liquid separation, clear liquid is filtered out from the bottom of the filter, and the solid is intercepted in the filter cartridge by the filter element. The filter is one-open one for standby, and after the amount of the filtered solid reaches a certain amount, the filter needs to be switched to ensure the continuity of the system.
6. Distillation
After the filtered clear liquid enters a distillation device, most of the solvent is evaporated out by using a normal pressure distillation device and is recycled. After the solvent is recovered by distillation, the product concentration in the solution reaches about 95 percent.
7. Rectification and purification
The distilled solution enters a rectifying device, a full heat and mass transfer process is carried out in a rectifying tower by utilizing a reduced pressure rectifying method, finally, all substance components form balanced distribution in the rectifying tower, and then the product is extracted from the side line of the rectifying tower. The solution at the top of the tower contains part of light components, the solution at the bottom of the tower contains part of heavy components, the purity of the product extracted at the side line is detected by ICP-MS, and the content of metal impurities can reach less than 1 ppm.
The following examples are not provided to limit the scope of the present invention, nor are the steps described to limit the order of execution, and the directions described are limited to the drawings. Modifications of the invention which are obvious to those skilled in the art in view of the prior art are also within the scope of the invention as claimed.
Example one
The continuous production method of the tetra (ethylmethylamino) hafnium comprises the following steps:
1) mixing n-butyllithium and n-hexane according to a proportion to prepare a solution A, wherein the mass concentration of the n-butyllithium is 15%; mixing ethylmethylamine (purity is more than or equal to 99%) and n-hexane to prepare a solution B, wherein the volume concentration of the ethylmethylamine is 15%; mixing hafnium chloride (the purity is more than or equal to 99%) and n-hexane to prepare a solution C, wherein the mass concentration of the hafnium chloride is 23%;
2) respectively cooling the solution A and the solution B to-15 ℃ through a plunger pump and a precooler, and simultaneously pumping the solution A and the solution B into a continuous flow reactor with the temperature of-15 ℃ at a certain flow rate for reaction for 5-30s to generate intermediate mixed liquor containing solid products; the flow ratio of the solution A to the solution B is preferably 1:1, and more preferably 40-50 mL/min;
3) the intermediate mixed liquor flows out of the outlet of the continuous flow reactor and enters a dynamic tubular reactor with the temperature of minus 10 ℃; simultaneously, cooling the uniformly mixed solution C to-10 ℃ through a precooler, and feeding the solution C into a dynamic tubular reactor at a certain flow rate; the intermediate mixed solution and the solution C stay in the dynamic tubular reactor for reaction for 20-60min to generate a product mixed solution containing solids; the flow rates of the intermediate mixed liquid and the solution C are respectively preferably 10mL/min and 10 mL/min;
4) the product mixture flows into a filter, after being filtered by the filter, clear liquid is filtered out from the bottom of the filter, and solids are intercepted in a filter cylinder by a filter element;
5) the clear liquid enters a distillation device to evaporate the solvent, and then is subjected to reduced pressure distillation to obtain tetra (ethylmethylamino) hafnium with the purity of more than or equal to 95 percent, the yield can reach 411g of tetra (ethylmethylamino) hafnium in 180min, and the conversion rate can reach 90 percent;
6) the distilled solution enters a rectifying device, a full heat and mass transfer process is carried out in a rectifying tower by utilizing a reduced pressure rectifying method, finally, all substance components form balanced distribution in the rectifying tower, and then products are extracted from the side line of the rectifying tower; the solution at the top of the tower contains part of light components, the solution at the bottom of the tower contains part of heavy components, the purity of the product extracted at the side line is detected by ICP-MS, and the content of metal impurities is less than 1 ppm.
Example two
The continuous production method of the pentakis (diethylamino) tantalum comprises the following steps:
1) preparing solution A from tert-butyl lithium and n-hexane in proportion, wherein the mass concentration of tert-butyl lithium is 12%; mixing diethylamine (the purity is more than or equal to 99%) and n-hexane to prepare a solution B, wherein the volume concentration of the diethylamine is 12%; mixing tantalum pentachloride (the purity is more than or equal to 99%) and n-hexane to prepare a solution C, wherein the mass concentration of the tantalum pentachloride is 20.6%;
2) respectively cooling the solution A and the solution B to-10 ℃ through a plunger pump and a precooler, and simultaneously pumping the solution A and the solution B into a continuous flow reactor with the temperature of-10 ℃ at a certain flow rate for reaction for 5-30s to generate intermediate mixed liquor containing solid products; the flow ratio of the solution A to the solution B is preferably 1:1, and more preferably 40-50 mL/min;
3) the intermediate mixed liquor flows out of the outlet of the continuous flow reactor and enters a dynamic tubular reactor with the temperature of 0 ℃; simultaneously, cooling the uniformly mixed solution C to 0 ℃ through a precooler, and feeding the solution C into a dynamic tubular reactor at a certain flow rate; the intermediate mixed solution and the solution C stay in the dynamic tubular reactor for reaction for 20-60min to generate a product mixed solution containing solids; the flow rates of the intermediate mixture liquid and the solution C are preferably 15.6mL/min and 10mL/min, respectively.
4) The product mixture flows into a filter, after being filtered by the filter, clear liquid is filtered out from the bottom of the filter, and solids are intercepted in a filter cylinder by a filter element;
5) the clear liquid enters a distillation device, the solvent is evaporated out, and then reduced pressure distillation is carried out, so that pentakis (diethylamine) tantalum with the purity of more than or equal to 95% can be obtained, the yield of 180min can reach 397g pentakis (diethylamine) tantalum, and the conversion rate can reach 86%;
6) the distilled solution enters a rectifying device, a full heat and mass transfer process is carried out in a rectifying tower by utilizing a reduced pressure rectifying method, finally, all substance components form balanced distribution in the rectifying tower, and then products are extracted from the side line of the rectifying tower; the solution at the top of the tower contains part of light components, the solution at the bottom of the tower contains part of heavy components, the purity of the product extracted at the side line is detected by ICP-MS, and the content of metal impurities is less than 1 ppm.
EXAMPLE III
The continuous production method of the tetra (ethyl methyl amino) zirconium comprises the following steps:
1) mixing n-butyllithium and an n-hexane solvent according to a proportion to prepare a solution A, wherein the mass concentration of the n-butyllithium is 15%; mixing ethyl methylamine (the purity is more than or equal to 99%) and n-hexane to prepare a solution B, wherein the volume concentration of the ethyl methylamine is 13%; ZrCl4(the purity is more than or equal to 99 percent) and n-hexane are mixed to prepare solution C, ZrCl4The mass concentration is 16.7%;
2) respectively cooling the solution A and the solution B to-15 ℃ through a plunger pump and a precooler, and simultaneously pumping the solution A and the solution B into a continuous flow reactor with the temperature of-15 ℃ at a certain flow rate for reaction for 5-30s to generate intermediate mixed liquor containing solid products; the flow ratio of the solution A to the solution B is preferably 1:1, and more preferably 40-50 mL/min;
3) the intermediate mixed liquor flows out of the outlet of the continuous flow reactor and enters a dynamic tubular reactor with the temperature of minus 5 ℃; simultaneously, cooling the uniformly mixed solution C to-5 ℃ through a precooler, and feeding the solution C into a dynamic tubular reactor at a certain flow rate; the intermediate mixed solution and the solution C stay in the dynamic tubular reactor for reaction for 20-60min to generate a product mixed solution containing solids; the flow rates of the intermediate mixed liquid and the solution C are respectively preferably 11.5mL/min and 10mL/min (temperature recommended replacement);
4) the product mixture flows into a filter, after being filtered by the filter, clear liquid is filtered out from the bottom of the filter, and solids are intercepted in a filter cylinder by a filter element;
5) the clear liquid enters a distillation device to evaporate the solvent, and then is subjected to reduced pressure distillation to obtain tetra (ethylmethylamino) zirconium with the purity of more than or equal to 95 percent, the yield of 180min can reach 280g of tetra (ethylmethylamino) zirconium, and the conversion rate can reach 85 percent;
6) the distilled solution enters a rectifying device, a full heat and mass transfer process is carried out in a rectifying tower by utilizing a reduced pressure rectifying method, finally, all substance components form balanced distribution in the rectifying tower, and then products are extracted from the side line of the rectifying tower; the solution at the top of the tower contains part of light components, the solution at the bottom of the tower contains part of heavy components, the purity of the product extracted at the side line is detected by ICP-MS, and the content of metal impurities is less than 1 ppm.
Example four
The continuous production method of the tris (dimethylamino) cyclopentadienyl zirconium comprises the following steps:
1) mixing n-butyllithium and n-hexane according to a proportion to prepare a solution A, wherein the mass concentration of the n-butyllithium is 15%; mixing dimethylamine (the purity is more than or equal to 99%) and n-hexane to prepare a solution B, wherein the mass fraction of the dimethylamine is 20%; ZrCl4(the purity is more than or equal to 99 percent) and n-hexane are mixed to prepare solution C, ZrCl4The mass concentration is 16.7%; mixing cyclopentadiene monomer and n-hexane to prepare solution D, wherein the mass concentration of the cyclopentadiene monomer is 6.7%;
2) respectively cooling the solution A and the solution B to-5 ℃ through a plunger pump and a precooler, and simultaneously pumping the solution A and the solution B into a continuous flow reactor with the temperature of-5 ℃ at a certain flow rate for reaction for 5-30s to generate intermediate mixed liquor containing solid products; the flow ratio of the solution A to the solution B is preferably 1:1, and more preferably 40-50 mL/min;
3) the intermediate mixed liquor flows out of the outlet of the continuous flow reactor and enters a dynamic tubular reactor with the temperature of minus 5 ℃; simultaneously, respectively cooling the uniformly mixed solution C and solution D to-5 ℃ through a precooler, and feeding the solution C and the solution D into a dynamic tubular reactor at a certain flow rate; the intermediate mixed solution, the solution C and the solution D stay in the dynamic tubular reactor for reaction for 20-60min to generate a product mixed solution containing solids; the flow rates of the intermediate mixed liquid, the solution C and the solution D are respectively preferably 10mL/min, 10mL/min and 10 mL/min;
4) the product mixture flows into a filter, after being filtered by the filter, clear liquid is filtered out from the bottom of the filter, and solids are intercepted in a filter cylinder by a filter element;
5) the clear liquid enters a distillation device, the solvent is evaporated, and then reduced pressure distillation is carried out, so that tris (dimethylamino) cyclopentadienyl zirconium with the purity of more than or equal to 95 percent can be obtained, the yield can reach 245g of tris (dimethylamino) cyclopentadienyl zirconium in 180min, and the conversion rate can reach 82 percent;
6) the distilled solution enters a rectifying device, a full heat and mass transfer process is carried out in a rectifying tower by utilizing a reduced pressure rectifying method, finally, all substance components form balanced distribution in the rectifying tower, and then products are extracted from the side line of the rectifying tower; the solution at the top of the tower contains part of light components, the solution at the bottom of the tower contains part of heavy components, the purity of the product extracted at the side line is detected by ICP-MS, and the content of metal impurities is less than 1 ppm.
Comparative example 1
The batch production method of the tetra (ethylmethylamino) hafnium comprises the following steps:
placing 1.68L of n-butyllithium n-hexane solution with the mass concentration of 15% in a reaction kettle, adding 2L of n-hexane, and cooling to-15 ℃; continuously stirring, slowly dropwise adding 172g of ethylmethylamine (the purity is more than or equal to 99%) into the reaction kettle, violently releasing heat in the reaction process, and continuously cooling to ensure that the temperature of the reaction kettle is kept at-15 ℃; after the dropwise addition is completed, stirring is continuously carried out for 2 hours, and the temperature of the system is slowly increased to 0 ℃; slowly adding 200g of hafnium chloride (the purity is more than or equal to 99 percent) into a reaction kettle, violently releasing heat in the reaction process, keeping the reaction temperature as far as possible by cooling, naturally heating the system to room temperature after the reaction is finished, and continuously stirring for 24 hours; after 24 hours, stopping stirring, carrying out suction filtration, evaporating the solvent, and then carrying out reduced pressure distillation to obtain the tetra (ethylmethylamino) hafnium with the purity of more than or equal to 95%, wherein the mass of the product is 192g, and the yield is 75%.
Comparative example No. two
The batch production method of the tris (dimethylamino) cyclopentadienyl zirconium comprises the following steps:
placing 1.54L of n-butyllithium n-hexane solution with the mass concentration of 15% in a reaction kettle, and cooling to-20 ℃; continuously stirring, slowly dripping 562g of a normal hexane solution (20%) of dimethylamine into the reaction kettle, violently releasing heat in the reaction process, and continuously cooling to ensure that the temperature of the reaction kettle is kept at-20 ℃; after the dropwise addition is completed, stirring is continuously carried out for 2 hours, and the temperature of the system is slowly increased to 0 ℃; adding 140g of zirconium chloride (the purity is more than or equal to 99%) slowly into a reaction kettle, releasing heat violently in the reaction process, keeping the reaction temperature as far as possible by cooling, naturally heating the system to room temperature after the reaction is finished, and continuously stirring for 24 hours; after 24 hours, cooling the reaction kettle to 0 ℃ again, slowly adding 52g of cyclopentadiene monomer into the reaction kettle, violently releasing heat in the reaction process, continuously cooling to keep the reaction temperature, after reacting for 2 hours, stopping stirring, filtering, evaporating the solvent, and then carrying out reduced pressure distillation to obtain the tris (dimethylamino) cyclopentadienyl zirconium with the purity of more than or equal to 95%, wherein the mass of the product is 126.5g, and the yield is 73%.
Claims (15)
1. A continuous production method of a transition metal amino complex is characterized in that a liquid A prepared by taking a metal alkyl compound and a solvent as main components in proportion and a liquid B prepared by taking an organic amine and the solvent as main components in proportion are respectively cooled to the temperature required by the reaction and then are simultaneously injected into a continuous flow reactor for reaction at the temperature of minus 30-10 ℃, and an intermediate mixed liquid containing a solid product is generated and enters a dynamic tubular reactor after flowing out of the continuous flow reactor; cooling the solution C prepared by taking a raw material containing transition metal and a solvent as main components in proportion to the temperature required by the reaction, allowing the solution C to enter a dynamic tubular reactor to react with the intermediate mixed solution at 0-40 ℃ to generate a product mixed solution containing solids, filtering and distilling to obtain the liquid with the product purity of more than or equal to 95%.
2. The continuous production method of a transition metal ammo complex according to claim 1, characterized by comprising the steps of:
1) preparing a metal alkyl compound and a solvent into a solution A in proportion, preparing organic amine and the solvent into a solution B in proportion, and preparing a raw material containing transition metal and the solvent into a solution C in proportion;
2) respectively cooling the solution A and the solution B to the temperature required by the reaction after passing through a plunger pump and a precooler, and simultaneously injecting the solution A and the solution B into a continuous flow reactor with the temperature of-30-10 ℃ at a certain flow rate to perform the reaction for 5-30s to generate intermediate mixed solution containing solid products;
3) the intermediate mixed liquor flows out of the outlet of the continuous flow reactor and enters a dynamic tubular reactor with the temperature of 0-40 ℃; simultaneously, cooling the uniformly mixed solution C to the temperature required by the reaction through a precooler, and feeding the solution C into a dynamic tubular reactor at a certain flow rate; the intermediate mixed solution and the solution C stay in the dynamic tubular reactor for reaction for 20-60min to generate a product mixed solution containing solids;
4) the product mixture flows into a filter, after being filtered by the filter, clear liquid is filtered out from the bottom of the filter, and solids are intercepted in a filter cylinder by a filter element;
5) and (3) distilling the clarified liquid in a distilling device, and distilling off the solvent to obtain liquid with the product purity of more than or equal to 95%.
3. The continuous production method of transition metal ammo-based complexes according to claim 1, characterized in that said step 5) is followed by the following steps:
6) and (3) feeding the liquid with the product purity of more than or equal to 95% into a rectifying device for rectifying and purifying until the product purity reaches more than 99.99%.
4. The continuous production method of a transition metal amino complex according to claim 1, 2 or 3, wherein the metal alkyl compound is methyllithium, ethyllithium, isopropyllithium, n-butyllithium or t-butyllithium.
5. Continuous process for the production of transition metal ammo complexes according to claim 1, 2 or 3 characterised in that the organic amine is NR1R2Wherein R is1、R2Is methyl, ethyl, isopropyl, sec-butyl or tert-butyl.
6. The continuous production method of a transition metal ammine complex as claimed in claim 1, 2 or 3, which further comprises cooling the solution D prepared from the reaction monomers to a temperature required for the reaction through a precooler, and feeding the solution D and the solution C into a dynamic tubular reactor simultaneously.
7. The continuous production method of a transition metal ammino complex as claimed in claim 1, 2 or 3, characterized in that the solution C is prepared by uniformly mixing a solid raw material containing a transition metal and a solvent under stirring, and then entering the dynamic tubular reactor from the upper part of the top end of the dynamic tubular reactor to participate in the reaction through a metering type peristaltic pump.
8. The continuous production method of a transition metal ammo complex according to claim 1, 2 or 3, characterized in that the temperature of the dynamic tube reactor is regulated by a heat transfer medium; the temperature of the continuous flow reactor is controlled by a heat transfer medium.
9. The continuous production method of a transition metal ammine complex as claimed in claim 1, 2 or 3, wherein the materials inside the dynamic tubular reactor are uniformly mixed by a mixing mechanism inside the dynamic tubular reactor and flow in a horizontal direction toward the rear end.
10. The continuous production method of the transition metal amino complex as claimed in claim 1, 2 or 3, wherein the continuous flow reactor comprises an inner hollow tube, an outer jacket layer and two micro channels which are positioned between the inner hollow tube and the outer jacket layer and are mutually communicated through convection holes and are stacked up and down, the width of the micro channels is 1-10 mm, the liquid A and the liquid B are uniformly mixed through the micro channels, and the inner hollow tube and the outer jacket layer are filled with a heat transfer medium.
11. The continuous production method of a transition metal ammine complex as claimed in claim 1, 2 or 3, wherein the width of the micro flow channel is 1.5 to 3 mm.
12. The continuous production method of a transition metal amino complex according to claim 1, 2 or 3, wherein the dynamic tube reactor comprises an inner hollow tube, an outer jacket layer, and an intermediate chamber for mixing materials between the inner hollow tube and the outer jacket layer, wherein the intermediate chamber is provided with a winding tube controlled by a motor and surrounding the inner hollow tube, and the inner hollow tube and the outer jacket layer are filled with a heat transfer medium; the reaction temperature of the step 3) is controlled by heating or cooling a heat transfer medium through temperature control equipment matched with the dynamic tubular reactor.
13. The continuous production method of a transition metal ammine complex according to claim 2 or 3, wherein the filter is at least two sets of parallel filters that can be switched between open and closed.
14. The continuous production method of transition metal ammo complex as claimed in claim 2 or 3, wherein the filter is a metal filter medium with a back-blowing system inside and with a filtering precision of micron order.
15. The continuous production method of a transition metal ammo-complex according to claim 1, wherein the transition metal ammo-complex comprises: (i) m1(NR1R2)4Or R3CpM1(NR1R2)3Wherein M is1Is V, Ti, Zr or Hf; r1、R2Is methyl, ethyl, isopropyl, sec-butyl or tert-butyl, Cp is cyclopentadienyl, R3Is H, methyl, ethyl, isopropyl, sec-butyl or tert-butyl; (ii) m2(NR1R2)5Or R3CpM2(NR1R2)4Wherein M is2Is V, Nb or Ta, R1、R2Is methyl, ethyl, isopropyl, sec-butyl or tert-butyl, etc., Cp is cyclopentadienyl, R3Is H, methyl, ethyl, isopropyl, sec-butyl or tert-butyl.
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| CN111171069A (en) * | 2020-01-15 | 2020-05-19 | 浙江硕而博化工有限公司 | Method and device for preparing hexamethyl disilazane lithium amide solution |
| CN111848438B (en) * | 2020-07-29 | 2023-05-23 | 浙江鼎龙科技股份有限公司 | Process for preparing 4, 6-diphenyl azo resorcinol and 4, 6-diamino resorcinol |
| CN113842658B (en) * | 2021-09-23 | 2023-05-23 | 苏州源展材料科技有限公司 | Refining method of liquid ALD precursor |
| CN113563207B (en) * | 2021-09-24 | 2021-12-07 | 苏州源展材料科技有限公司 | Process for preparing metal organic complexes |
| CN113999257A (en) * | 2021-11-26 | 2022-02-01 | 江苏南大光电材料股份有限公司 | Preparation method of semiconductor grade tetra (methylethylamino) zirconium |
| CN117603251B (en) * | 2024-01-23 | 2024-03-26 | 铜陵安德科铭电子材料科技有限公司 | Method for efficiently preparing high-k organometallic precursor |
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