Synthesis device of high-purity metal complex precursor

Abstract

The invention relates to the technical field of electronic materials, and provides a high-purity metal complex precursor synthesis device which is characterized in that a reaction kettle is arranged for reaction, and the reaction kettle is communicated with an n-hexane / tetrahydrofuran storage tank, an n-butyllithium storage tank and a DMSO storage tank; a hydrochloric acid aqueous solution dropwise adding tank, a cyclopentadiene / substituted cyclopentadiene dropwise adding tank, a bromopropane / liquefied dimethylamine dropwise adding tank and a solid feeder are used for adding raw materials, a reaction kettle is communicated with a barrel-cone type three-in-one filter for filtering, the barrel-cone type three-in-one filter is communicated with a distillation kettle / liquid separation kettle for distilling or liquid separation, the distillation kettle / liquid separation kettle is communicated with a rectifying tower for rectifying, and the rectifying tower is communicated with a rectifying tower for rectifying. The distillation kettle / liquid separation kettle is communicated with the reaction kettle for material returning; the distillation kettle / liquid separation kettle is communicated with a distillation condenser for distilling, condensing and recycling raw materials; according to the preparation method disclosed by the invention, the n-propyl cyclopentadiene can be firstly prepared, and then the n-propyl cyclopentadienyl zirconium trichloride is prepared; and finally, preparing to obtain the n-propyl cyclopentadienyl tri (dimethylamino) zirconium.

Description

Technical Field

[0001] The invention relates to the technical field of electronic materials, and in particular to a synthesis device for a high-purity metal complex precursor. Background Art

[0002] The application of high dielectric constant materials (High-K) in ultra-large-scale integrated circuits (ULSI) is very necessary. The reason is that when the device size is reduced, the planar structure area A is reduced accordingly. In order to ensure the capacitance, high dielectric constant materials are needed. Conventional high dielectric constant materials include oxides of Hf (hafnium), Zr (zirconium), Ta (tantalum), Ti (titanium), Y (yttrium), etc., as well as new materials such as titanates doped with alkaline earth metal materials, such as barium strontium titanate (BST), barium zirconate titanate (BZT), etc. Generally, precursor materials of elements such as Hf, Zr, Ta, Ti, and Y are used to obtain the above-mentioned high dielectric constant materials by atomic layer deposition (ALD) or chemical vapor deposition (CVD). Therefore, high-quality precursor materials are the key support for achieving High-K thin film deposition.

[0003] Zirconium dioxide film has a moderate dielectric constant (K~25) and is compatible with traditional silicon-based integrated circuit processes, so it is considered to be the most promising new gate dielectric material. Atomic layer deposition (ALD) technology, as a cutting-edge nanostructure manufacturing technology, forms smooth, uniform, controllable, high-quality films through orderly, self-limiting saturated chemical reactions on the substrate surface with good repeatability, making it widely used in microelectronics science, optical films, and nanotechnology. In ALD technology, the process of obtaining oxide films first introduces a gas-phase precursor, which then reacts chemically on the wafer surface to form the desired film structure.

[0004] When preparing ZrO2 thin films using atomic layer deposition (ALD) technology, commonly used precursor sources include tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium, tetrakis(methylethylamino)zirconium, cyclopentadienyltris(dimethylamino)zirconium, etc. These high-purity precursor sources are expensive and most of them need to be imported from abroad. In addition, when using tetrakis(dimethylamino)zirconium, tetrakis(diethylamino)zirconium, and tetrakis(methylethylamino)zirconium as precursors to deposit zirconium oxide films, although the film growth rate reaches 0.1nm / cycle, this rate still cannot fully meet the demand. Therefore, the development of a source material with a faster deposition rate, a simple synthesis process, and stable properties is extremely important for improving production efficiency and reducing costs.

[0005] Prior art CN119143814A discloses a method and device for synthesizing metal precursor organic carbonyl cobalt compounds, wherein the device includes a reactor on which a collecting and distributing mechanism is arranged, the collecting and distributing mechanism includes a rotating shaft and a collecting and distributing blade movably arranged at the first end of the rotating shaft, the collecting and distributing blade is driven to rotate forward to collect filtered solids, and reverse to diffuse the filtered solids in the collecting and distributing blade. A filter plate is arranged at the first end of the collecting and distributing blade, a uniform dispersing opening is provided on one side of the collecting and distributing blade, the collecting and distributing blade is driven to rotate forward to collect the filtered solids on the filter plate through the uniform dispersing opening; an arc portion is arranged on the other side of the collecting and distributing blade, a guide angle is arranged at the first end of the collecting and distributing blade, the collecting and distributing blade is driven to reverse to guide the liquid to flow along the guide angle, and flow rapidly along the two ends of the uniform dispersing opening to form a fast flow zone; a dripping mechanism is arranged on the reactor, the dripping mechanism includes a dripping head, a hollow cavity is provided on the rotating shaft, and the hollow cavity An annular groove is provided on the cavity, and the droplet head sprays out a fast and a slow droplet alternately, and the two droplets collide in the annular groove to diffuse the droplets to the fast flow area; the collecting and distributing blade is slidably connected to the first end of the rotating shaft, and the two collecting and distributing blades are mutually attached to each other and maintained in an inclined state as the rotating shaft is lifted, and the two collecting and distributing blades are attached to the bottom of the reactor as the rotating shaft is lowered to maintain a horizontal state; preferably, a rotating chute is provided on the rotating shaft, and a flip connecting plate arranged on the collecting and distributing blade is slidably connected in the rotating chute. Then this patent is a synthesis of metal precursor organic carbonyl cobalt compounds, but currently it is necessary to synthesize n-propylcyclopentadienyl tris(dimethylamino) zirconium, and it is necessary to synthesize n-propylcyclopentadiene first, and then synthesize n-propylcyclopentadiene zirconium trichloride, and it is best to synthesize n-propylcyclopentadienyl tris(dimethylamino) zirconium, so a device that meets this synthesis route is needed. Summary of the invention

[0006] In view of this, the purpose of the present invention is to provide a synthesis device for a high-purity metal complex precursor to solve the problems arising from the background technology.

[0007] Based on the above purpose, the present invention provides a synthesis device of a high-purity metal complex precursor, comprising a reactor, wherein a plurality of feeding ports are arranged on the top of the reactor, and the plurality of feeding ports are respectively connected to a n-hexane / tetrahydrofuran storage tank, an n-butyl lithium storage tank, a DMSO storage tank, a hydrochloric acid aqueous solution dropping tank, a cyclopentadiene / substituted cyclopentadiene dropping tank, a bromopropane / liquefied dimethylamine dropping tank and a solid feeder through pipelines; a discharge port at the bottom of the reactor is connected to a cylindrical-conical three-in-one filter through a pipeline, a distillation kettle / liquid separation kettle is connected to the bottom of the cylindrical-conical three-in-one filter through a pipeline, and a distillation kettle / liquid separation kettle is connected to the reactor through a pipeline at the bottom of the distillation kettle / liquid separation kettle. The bottom of the still / liquid separator is connected to a distillation tower through a pipeline, the bottom of the still / liquid separator is also connected to a solid feeding device through a pipeline, the top of the still / liquid separator is connected to a distillation condenser through a pipeline, the bottom of the distillation condenser is respectively connected to a DMSO / normal hexane recovery tank and a substituted cyclopentadiene recovery tank through two pipelines, the bottom of the DMSO / normal hexane recovery tank is respectively connected to a normal hexane / tetrahydrofuran storage tank and a DMSO storage tank through two pipelines, the substituted cyclopentadiene recovery tank is connected to a cyclopentadiene / substituted cyclopentadiene dropping tank through a pipeline, and the top of the cyclopentadiene / substituted cyclopentadiene dropping tank is also connected to a cracking device for preparing cyclopentadiene through a pipeline.

[0008] Preferably, the n-hexane / tetrahydrofuran storage tank, n-butyl lithium storage tank, DMSO storage tank, solid feeder and the top of the distillation kettle / liquid separator are all connected to the nitrogen tank through a pipeline, and the pipelines connecting the n-hexane / tetrahydrofuran storage tank, n-butyl lithium storage tank, DMSO storage tank, solid feeder and the distillation kettle / liquid separator are respectively provided with valve thirty-nine, valve thirty-four, valve one, valve four and valve seven.

[0009] Preferably, the n-hexane / tetrahydrofuran storage tank and the n-butyl lithium storage tank are connected to the reactor through a common pipeline 1, a valve 38 is provided near one end of the pipeline 1 near the reactor, the n-hexane / tetrahydrofuran storage tank and the n-butyl lithium storage tank are connected to the pipeline 1 through pipeline 2 and pipeline 3 respectively, valve 41 and valve 37 are provided at both ends of the pipeline 2 respectively, and valve 35 and valve 36 are provided at both ends of the pipeline 2 respectively; The two ends of the pipeline connecting the DMSO storage tank to the reactor are respectively provided with valve 2 and valve 3.

[0010] Preferably, a valve five is provided on the pipeline connecting the solid feeder to the reactor; The two ends of the pipeline connecting the reactor to the cylindrical-conical three-in-one filter are respectively provided with valve 11 and valve 12; The two ends of the pipeline connecting the cylindrical-conical three-in-one filter to the distillation kettle / liquid separation kettle are respectively provided with valves 14 and 16, and a pipeline sight glass 1 is provided on the pipeline between valves 14 and 16; The bottom of the cylindrical-conical three-in-one filter is connected to the filter residue quenching treatment device through a pipeline, and a valve thirteen is arranged on the pipeline connecting the cylindrical-conical three-in-one filter to the filter residue quenching treatment device.

[0011] Preferably, the reactor and the rectifying tower are connected to the distillation kettle / liquid separation kettle through a common pipeline 4, valves 17 and 19 are respectively provided at both ends of the pipeline 4, a pipeline sight glass 2 is provided between the valves 17 and 19 on the pipeline 4, the pipeline 4 is located between the valves 19 and the pipeline sight glass 2 and is connected to the solid feeding device through the pipeline, and a valve 43 is provided on the pipeline connecting the solid feeding device to the pipeline 4; The reaction kettle and the distillation tower are connected to the pipeline 4 through the pipeline 5 and the pipeline 6 respectively. The two ends of the pipeline 5 are respectively provided with valves 21 and 22. The pipeline 6 is provided with a valve 44. A valve 23 is provided on the pipeline connecting the distillation kettle / liquid separation kettle to the distillation condenser, a pipeline 7 is connected to the bottom of the distillation condenser, a pipeline sight glass 3 is provided on the pipeline 7, the pipeline 7 is connected to the DMSO / n-hexane recovery tank and the substituted cyclopentadiene recovery tank through the pipeline 8 and the pipeline 9 respectively, a valve 26 is provided on the pipeline 8, and a valve 25 is provided on the pipeline 9; The distillation condenser is connected to a vacuum pump through a pipeline, and a valve twenty-seven is arranged on the pipeline connecting the distillation condenser to the vacuum pump.

[0012] Preferably, the bottom of the DMSO / n-hexane recovery tank is connected to pipeline 10, and valve 28 is provided on pipeline 10. Pipeline 10 is connected to the n-hexane / tetrahydrofuran storage tank and the DMSO storage tank through pipeline 11 and pipeline 12 respectively, and valve 40 and valve 42 are provided at both ends of pipeline 11, and valve 31 and valve 30 are provided at both ends of pipeline 12; The bottom of the substituted cyclopentadiene recovery tank is connected to pipeline 13, valves 29 and 32 are respectively provided at both ends of pipeline 13, pipeline 13 is connected to pipeline 14, pipeline 14 is connected to the cyclopentadiene / substituted cyclopentadiene dropping tank, valve 33 is provided on pipeline 14, pipeline 14 is connected to the cracking cyclopentadiene production device through pipeline 15, and valve 6 is provided on pipeline 15; The pipelines connecting the hydrochloric acid aqueous solution dropping tank, the cyclopentadiene / substituted cyclopentadiene dropping tank, and the bromopropane / liquefied dimethylamine dropping tank to the feeding port of the reaction kettle are respectively provided with valve ten, valve eight and valve nine.

[0013] Preferably, the reaction kettle, the cylindrical-conical three-in-one filter and the distillation kettle / liquid separation kettle are respectively provided with a stirrer 1, a stirrer 2 and a stirrer 3.

[0014] Beneficial effects of the present invention: The present invention adopts the method of setting a reaction kettle for reaction, the reaction kettle is connected to a n-hexane / tetrahydrofuran storage tank, an n-butyl lithium storage tank, a DMSO storage tank, a hydrochloric acid aqueous solution dropping tank, a cyclopentadiene / substituted cyclopentadiene dropping tank, a bromopropane / liquefied dimethylamine dropping tank and a solid feeder for raw material addition, the reaction kettle is connected to a cylindrical cone type three-in-one filter for filtering, the cylindrical cone type three-in-one filter is connected to a distillation kettle / liquid separation kettle for distillation or liquid separation, the distillation kettle / liquid separation kettle is connected to a distillation tower for distillation, and the distillation kettle / liquid separation kettle is connected to a distillation tower for distillation. The reaction kettle is used for recycling; the distillation kettle / liquid separation kettle is connected to the distillation condenser for distillation and condensation to recover the raw materials; the present invention can first prepare n-propyl cyclopentadiene through DMSO, sodium hydroxide solid, cyclopentadiene, propyl bromide, acid aqueous solution drops and anhydrous sodium sulfate, and then prepare n-propyl cyclopentadiene with n-butyl lithium, n-hexane, tetrahydrofuran and zirconium tetrachloride to obtain n-propyl cyclopentadienyl zirconium trichloride; finally, the n-propyl cyclopentadienyl zirconium trichloride is prepared together with n-hexane and liquefied dimethylamine to obtain n-propyl cyclopentadienyl tris dimethylamino zirconium. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only for the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0016] Figure 1 It is a schematic diagram of the overall device of the present invention; The markings in the figure are: 1. Valve 1; 2. Valve 2; 3. Valve 3; 4. Valve 4; 5. Valve 5; 6. Valve 6; 7. Valve 7; 8. Valve 8; 9. Valve 9; 10. Valve 10; 11. Valve 11; 12. Valve 12; 13. Valve 13; 14. Valve 14; 15. Pipeline sight glass 1; 16. Valve 16; 17. Valve 17; 18. Pipeline sight glass 2; 19. Valve 19; 20. Vacuum pump; 21. Valve 21; 22. Valve 22; 23. Valve 23; 24. Pipeline sight glass 3; 25. Valve 25; 26. Valve 26; 27. Valve 27; 28. Valve 28; 29. ​​Valve 29; 30. Valve 30; 31. Valve 31; 32. Valve 32; 33. Valve 33; 34. Valve 34; 35. Valve 35; 36. Valve 36; 37. Valve 37 ; 38. Valve 38; 39. Valve 39; 40. Valve 40; 41. Valve 41; 42. Valve 42; 43. Valve 43; 44. Valve 44; 45. Reactor; 46. n-Hexane / tetrahydrofuran storage tank; 47. n-Butyl lithium storage tank; 48. DMSO storage tank; 49. Hydrochloric acid aqueous solution dropping tank; 50. Cyclopentadiene / substituted cyclopentadiene dropping tank; 51. Propane bromide / liquefied dimethylamine Dropping tank; 52. Solid feeder; 53. Cylindrical-conical three-in-one filter; 54. Distillation kettle / liquid separation kettle; 55. Agitator three; 56. Distillation tower; 57. Distillation condenser; 58. DMSO / n-hexane recovery tank; 59. Substituted cyclopentadiene recovery tank; 60. Cyclopentadiene cracking device; 61. Nitrogen tank; 62. Agitator one; 63. Agitator two; 64. Solid feeding device; 65. Filter residue quenching treatment device. DETAILED DESCRIPTION

[0017] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0018] It should be noted that, unless otherwise defined, the technical terms or scientific terms used in the present invention should be understood by people with ordinary skills in the field to which the present invention belongs. The "first", "second" and similar words used in the present invention do not indicate any order, quantity or importance, but are only used to distinguish different components. "Include" or "comprise" and similar words mean that the elements or objects appearing before the word include the elements or objects listed after the word and their equivalents, without excluding other elements or objects. "Connect" or "connected" and similar words are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "Up", "down", "left", "right" and the like are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0019] like Figure 1 As shown, this embodiment provides a synthesis device for a high-purity metal complex precursor, including a reaction kettle 45, wherein a plurality of feeding ports are arranged on the top of the reaction kettle 45, and the plurality of feeding ports are respectively connected to a n-hexane / tetrahydrofuran storage tank 46, an n-butyl lithium storage tank 47, a DMSO storage tank 48, a hydrochloric acid aqueous solution dropping tank 49, a cyclopentadiene / substituted cyclopentadiene dropping tank 50, a bromopropane / liquefied dimethylamine dropping tank 51 and a solid feeder 52 through pipelines; The n-hexane / tetrahydrofuran storage tank 46 and the n-butyl lithium storage tank 47 are connected to the reactor 45 by a common pipeline 1, and a valve 38 38 is arranged at one end of the pipeline 1 near the reactor 45. The n-hexane / tetrahydrofuran storage tank 46 and the n-butyl lithium storage tank 47 are connected to the pipeline 1 through pipeline 2 and pipeline 3 respectively, and valve 41 41 and valve 37 37 are arranged at both ends of the pipeline 2 respectively, and valve 35 35 and valve 36 36 are arranged at both ends of the pipeline 2 respectively; The two ends of the pipeline connecting the DMSO storage tank 48 to the reactor 45 are respectively provided with valve two 2 and valve three 3; the pipeline connecting the solid feeder 52 to the reactor 45 is provided with valve five 5.

[0020] The bottom discharge port of the reactor 45 is connected to a cylindrical-conical three-in-one filter 53 through a pipeline, the bottom of the cylindrical-conical three-in-one filter 53 is connected to a distillation kettle / liquid separator 54 through a pipeline, the bottom of the distillation kettle / liquid separator 54 is connected to the reactor 45 through a pipeline, and the two ends of the pipeline connecting the reactor 45 to the cylindrical-conical three-in-one filter 53 are respectively provided with a valve 11 and a valve 12; The two ends of the pipeline connecting the cylindrical cone type three-in-one filter 53 to the distillation kettle / liquid separation kettle 54 are respectively provided with valve 14 14 and valve 16 16, and a pipeline sight glass 15 is provided on the pipeline between the valve 14 14 and the valve 16 16; The bottom of the cylindrical-conical three-in-one filter 53 is connected to the filter residue quenching treatment device 65 through a pipeline, and a valve thirteen 13 is provided on the pipeline connecting the cylindrical-conical three-in-one filter 53 to the filter residue quenching treatment device 65.

[0021] The bottom of the still / liquid separator 54 is connected to a distillation tower 56 through a pipeline, the bottom of the still / liquid separator 54 is also connected to a solid feeding device 64 through a pipeline, the top of the still / liquid separator 54 is connected to a distillation condenser 57 through a pipeline, the bottom of the distillation condenser 57 is respectively connected to a DMSO / n-hexane recovery tank 58 and a substituted cyclopentadiene recovery tank 59 through two pipelines, the bottom of the DMSO / n-hexane recovery tank 58 is respectively connected to a n-hexane / tetrahydrofuran storage tank 46 and a DMSO storage tank 48 through two pipelines, the substituted cyclopentadiene recovery tank 59 is connected to a cyclopentadiene / substituted cyclopentadiene dropping tank 50 through a pipeline, and the top of the cyclopentadiene / substituted cyclopentadiene dropping tank 50 is also connected to a cracking device for preparing cyclopentadiene 60 through a pipeline; The reaction kettle 45 and the rectifying tower 56 are connected to the distillation kettle / liquid separation kettle 54 and share a pipeline 4, and valve 17 17 and valve 19 19 are respectively provided at both ends of the pipeline 4, and a pipeline sight glass 2 18 is provided on the pipeline 4 between the valve 17 17 and the valve 19 19, and the pipeline 4 is connected to the solid feeding device 64 through the pipeline between the valve 19 19 and the pipeline sight glass 2 18, and a valve 43 43 is provided on the pipeline connecting the solid feeding device 64 to the pipeline 4; The reaction kettle 45 and the distillation tower 56 are connected to the pipeline 4 through the pipeline 5 and the pipeline 6 respectively. The two ends of the pipeline 5 are respectively provided with a valve 21 and a valve 22 22. The pipeline 6 is provided with a valve 44 44. A valve 23 is provided on the pipeline connecting the distillation kettle / liquid separation kettle 54 to the distillation condenser 57. The bottom of the distillation condenser 57 is connected with a pipeline 7, and a pipeline sight glass 3 24 is arranged on the pipeline 7. The pipeline 7 is connected with the DMSO / normal hexane recovery tank 58 and the substituted cyclopentadiene recovery tank 59 through the pipeline 8 and the pipeline 9 respectively. The pipeline 8 is provided with a valve 26 26, and the pipeline 9 is provided with a valve 25 25; The distillation condenser 57 is connected to the vacuum pump 20 through a pipeline, and a valve 27 is provided on the pipeline connecting the distillation condenser 57 to the vacuum pump 20; The bottom of the DMSO / n-hexane recovery tank 58 is connected to pipeline ten, and a valve twenty-eight 28 is provided on pipeline ten. Pipeline ten is connected to the n-hexane / tetrahydrofuran storage tank 46 and the DMSO storage tank 48 through pipeline eleven and pipeline twelve respectively. Valve forty 40 and valve forty-two 42 are respectively provided at both ends of pipeline eleven, and valve thirty-one 31 and valve thirty 30 are respectively provided at both ends of pipeline twelve; The bottom of the substituted cyclopentadiene recovery tank 59 is connected to the pipeline 13, and valves 29 29 and 32 32 are respectively provided at both ends of the pipeline 13. The pipeline 13 is connected to the pipeline 14, and the pipeline 14 is connected to the cyclopentadiene / substituted cyclopentadiene dropping tank 50. The pipeline 14 is provided with a valve 33 33. The pipeline 14 is connected to the cracking cyclopentadiene production device 60 through the pipeline 15, and the pipeline 15 is provided with a valve 66; The pipelines connecting the hydrochloric acid aqueous solution dropping tank 49, the cyclopentadiene / substituted cyclopentadiene dropping tank 50, and the bromopropane / liquefied dimethylamine dropping tank 51 to the feeding port of the reaction kettle 45 are respectively provided with valve ten 10, valve eight 8 and valve nine 9.

[0022] The tops of the n-hexane / tetrahydrofuran storage tank 46, the n-butyl lithium storage tank 47, the DMSO storage tank 48, the solid feeder 52 and the distillation kettle / liquid separator 54 are all connected to the nitrogen tank 61 through pipelines, and the pipelines connecting the n-hexane / tetrahydrofuran storage tank 46, the n-butyl lithium storage tank 47, the DMSO storage tank 48, the solid feeder 52 and the distillation kettle / liquid separator 54 to the nitrogen tank 61 are respectively provided with valve thirty-nine 39, valve thirty-four 34, valve one 1, valve four 4 and valve seven 7. The n-hexane / tetrahydrofuran storage tank 46 and the n-butyl lithium storage tank 47 are connected to the reactor 45 by a common pipeline 1, and a valve 38 38 is arranged at one end of the pipeline 1 near the reactor 45. The n-hexane / tetrahydrofuran storage tank 46 and the n-butyl lithium storage tank 47 are connected to the pipeline 1 through pipeline 2 and pipeline 3 respectively, and valve 41 41 and valve 37 37 are arranged at both ends of the pipeline 2 respectively, and valve 35 35 and valve 36 36 are arranged at both ends of the pipeline 2 respectively; The reaction kettle 45, the cylindrical-conical three-in-one filter 53 and the distillation kettle / liquid separation kettle 54 are respectively provided with a stirrer 1 62, a stirrer 2 63 and a stirrer 3 55.

[0023] Open valve 1, valve 2, valve 3, and valve 4 to transfer 6 L of DMSO in DMSO storage tank 48 to reactor 45 by nitrogen pressure, open valve 5, transfer 416 g of sodium hydroxide solid in solid feeder 52 to reactor 45, start agitator 62 of reactor 45, and cool the materials in reactor 45 to 0°C, then open valve 8, slowly drop 767 g of cyclopentadiene in cyclopentadiene / substituted cyclopentadiene dropping tank 50 to reactor 45, after the dropwise addition is completed, slowly return to room temperature and continue stirring for 3 h, then open valve 9, slowly drop 1230 g of bromopropane in bromopropane / liquefied dimethylamine dropping tank 51 to reactor 45, after the dropwise addition is completed, continue stirring for 12 h, then open valve 10, drop 120 mL of HCl and 1600 g of aqueous hydrochloric acid in dropping tank 49, and add 100 mL of HCl and 1600 g of bromopropane to reactor 45. mL water mixture is added dropwise to the reaction kettle 45. After the addition is completed, valve 11, valve 12, valve 14, valve 16, valve 17, valve 18, valve 19, valve 21, valve 22, valve 23, valve 24, valve 25, valve 26, valve 27, valve 28, valve 29, valve 30, valve 31, valve 32, valve 33, valve 34, valve 35, valve 36, valve 37, valve 38, valve 39, valve 40, valve 41, valve 42, valve 43, valve 44, valve 45, valve 46, valve 47, valve 48, valve 49, valve 50, valve 51, valve 52, valve 53, valve 54, valve 55, valve 56, valve 57, valve 58, valve 59, valve 60, valve 61, valve 62, valve 63, valve 64, valve 65, valve 66, valve 67, valve 68, valve 69, valve 70, valve 71, valve 72, valve 73, valve 74, valve 75, valve 76, valve 77, valve 78, valve 79, valve 80, valve 81, valve 82, valve 83, valve 84, valve 85, valve 86, valve 87, valve 88, valve 89, valve 90, valve 91, valve 92, valve 93, valve 94, valve 95, valve 96, valve 97, valve 98, valve 99, valve 100, valve 101, valve 102, valve 103, valve 104, The liquid separation surface of the organic phase and the aqueous phase is obtained, and then anhydrous sodium sulfate is added into the reactor 45 through the solid feeder 52, and the organic phase is dried and dehydrated. After the dehydration is completed, the mixed material of the organic phase and the anhydrous sodium sulfate is transferred to the cylindrical cone type three-in-one filter 53 for filtration, and the filtrate enters the distillation kettle / liquid separation kettle 54, and the valve twenty-three 23 and the valve twenty-five 25 are opened. DMSO is separated by vacuum distillation into the DMSO / n-hexane recovery tank 58, and then the valve twenty-five 25 is closed, and the valve twenty-six 26 is opened. The vacuum distillation method is used to control the vacuum degree to 13-15 torr, and 681.5 g of the fraction with an internal temperature of 26 ℃ is collected into the substituted cyclopentadiene recovery tank 59. The purity of n-propylcyclopentadiene is 97% and the yield is 63% when detected by gas chromatography.

[0024] Open valve thirty-four 34, valve thirty-five 35, valve thirty-six 36, valve thirty-eight 38, use nitrogen to press material to quantitatively transfer 1680 mL of n-butyl lithium in n-butyl lithium storage tank 47 to reactor 45, then close valve thirty-four 34, valve thirty-five 35, valve thirty-six 36, open valve thirty-nine 39, valve forty-one 41, valve thirty-seven 37, use nitrogen to press material to quantitatively transfer 2 L of n-hexane in n-hexane / tetrahydrofuran storage tank 46 to reactor 45, then cool reactor 45 to 0 ℃, open valve twenty-nine 29, valve thirty-two 32, valve thirty-three 33, use nitrogen to press material to transfer n-propyl cyclopentadiene in substituted cyclopentadiene recovery tank 59 to cyclopentadiene / substituted cyclopentadiene dropping tank 50, then quantitatively and slowly add 433 of n-propyl cyclopentadiene in cyclopentadiene / substituted cyclopentadiene dropping tank 50 g to the reaction kettle 45. After the dropwise addition is completed, the reaction is continued for 2 h. Then, valve thirty-nine 39, valve forty-one 41, valve thirty-seven 37 and valve thirty-eight 38 are opened in sequence. 0.8 L of tetrahydrofuran in the n-hexane / tetrahydrofuran storage tank 46 is quantitatively transferred to the reaction kettle 45 by nitrogen pressure. Then, 886 g of zirconium tetrachloride in the solid feeder 52 is added to the reaction kettle 45 in two batches. Then, the temperature is slowly restored to room temperature. The reaction is continued to be stirred for 12 h. Then, the material in the reaction kettle 45 is transferred to the cylindrical-conical three-in-one filter 53 for filtration. The filtrate enters the distillation kettle / liquid separation kettle 54. After the solvent is drained, valve seventeen 17 and valve forty-three 43 are opened to obtain 868.4 g of n-propylcyclopentadiene zirconium trichloride with a yield of 75%.

[0025] 487.6 g of n-propylcyclopentadienylzirconium trichloride was transferred into the solid feeder 52 through the solid feeder device 64 .

[0026] Open valve thirty-four 34, valve thirty-five 35, valve thirty-six 36, valve thirty-eight 38, use nitrogen to press material to quantitatively transfer 1985 mL of n-butyl lithium in n-butyl lithium storage tank 47 to reactor 45, then close valve thirty-four 34, valve thirty-five 35, valve thirty-six 36, open valve thirty-nine 39, valve forty-one 41, valve thirty-seven 37, use nitrogen to press material to quantitatively transfer 2 L of n-hexane in n-hexane / tetrahydrofuran storage tank 46 to reactor 45, then cool reactor 45 to -10 ℃, then quantitatively add 252.8 g of liquefied dimethylamine in bromopropane / liquefied dimethylamine dropping tank 51 to reactor 45, after the addition is complete, continue the reaction for 2 h, then add 487.6 g of liquefied dimethylamine in solid feeder 52. g n-propylcyclopentadienylzirconium trichloride was added into the reaction kettle 45 in two batches, and then slowly restored to room temperature and reacted for 12 hours, and the materials in the reaction kettle 45 were transferred to the cylindrical cone three-in-one filter 53 for filtration, and the filtrate entered the distillation kettle / separation kettle 54 to drain the solvent, and then the valve seventeen 17, valve nineteen 19, and valve forty-four 44 were opened, and the materials in the distillation kettle / separation kettle 54 were transferred to the distillation tower 56 for vacuum distillation to obtain 439 g of n-propylcyclopentadienyl tris(dimethylamino)zirconium with a yield of 83%.

[0027] It should be understood by those skilled in the art that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the present invention is limited to these examples; under the concept of the present invention, the technical features in the above embodiments or different embodiments may also be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity. Any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A synthesis device for a high-purity metal complex precursor, comprising a reaction vessel (45), characterized in that: The top of the reactor (45) is provided with a plurality of feeding ports, which are respectively connected to an n-hexane / tetrahydrofuran storage tank (46), an n-butyl lithium storage tank (47), a DMSO storage tank (48), a hydrochloric acid aqueous solution dropping tank (49), a cyclopentadiene / substituted cyclopentadiene dropping tank (50), a bromopropane / liquefied dimethylamine dropping tank (51) and a solid feeder (52) through pipelines; the bottom discharge port of the reactor (45) is connected to a cylindrical-conical three-in-one filter (53) through a pipeline, the bottom of the cylindrical-conical three-in-one filter (53) is connected to a distillation kettle / liquid separator (54) through a pipeline, the bottom of the distillation kettle / liquid separator (54) is connected to the reactor (45) through a pipeline, and the bottom of the distillation kettle / liquid separator (54) is connected to a rectification tower through a pipeline. (56), the bottom of the distillation kettle / liquid separator (54) is also connected to the solid feeding device (64) through a pipeline, the top of the distillation kettle / liquid separator (54) is connected to the distillation condenser (57) through a pipeline, the bottom of the distillation condenser (57) is respectively connected to the DMSO / n-hexane recovery tank (58) and the substituted cyclopentadiene recovery tank (59) through two pipelines, the bottom of the DMSO / n-hexane recovery tank (58) is respectively connected to the n-hexane / tetrahydrofuran storage tank (46) and the DMSO storage tank (48) through two pipelines, the substituted cyclopentadiene recovery tank (59) is connected to the cyclopentadiene / substituted cyclopentadiene dropping tank (50) through a pipeline, and the top of the cyclopentadiene / substituted cyclopentadiene dropping tank (50) is also connected to the cracking cyclopentadiene device (60) through a pipeline.

2. The synthesis device of the high-purity metal complex precursor according to claim 1, characterized in that: The tops of the n-hexane / tetrahydrofuran storage tank (46), the n-butyl lithium storage tank (47), the DMSO storage tank (48), the solid feeder (52) and the distillation kettle / liquid separator (54) are all connected to the nitrogen tank (61) via pipelines. The pipelines connecting the n-hexane / tetrahydrofuran storage tank (46), the n-butyl lithium storage tank (47), the DMSO storage tank (48), the solid feeder (52) and the distillation kettle / liquid separator (54) to the nitrogen tank (61) are respectively provided with valve thirty-nine (39), valve thirty-four (34), valve one (1), valve four (4) and valve seven (7).

3. The synthesis device of the high-purity metal complex precursor according to claim 2, characterized in that: The n-hexane / tetrahydrofuran storage tank (46) and the n-butyl lithium storage tank (47) are connected to the reactor (45) through a common pipeline 1. A valve 38 (38) is provided at one end of the pipeline 1 close to the reactor (45). The n-hexane / tetrahydrofuran storage tank (46) and the n-butyl lithium storage tank (47) are connected to the pipeline 1 through pipeline 2 and pipeline 3 respectively. A valve 41 (41) and a valve 37 (37) are provided at both ends of the pipeline 2 respectively. A valve 35 (35) and a valve 36 (36) are provided at both ends of the pipeline 2 respectively. A valve 2 (2) and a valve 3 (3) are provided at both ends of the pipeline connecting the DMSO storage tank (48) to the reactor (45). A valve 5 (5) is provided on the pipeline connecting the solid feeder (52) to the reactor (45).

4. The synthesis device of the high-purity metal complex precursor according to claim 3, characterized in that: The two ends of the pipeline connecting the reaction kettle (45) to the cylindrical-conical three-in-one filter (53) are respectively provided with valve eleven (11) and valve twelve (12); the two ends of the pipeline connecting the cylindrical-conical three-in-one filter (53) to the distillation kettle / liquid separation kettle (54) are respectively provided with valve fourteen (14) and valve sixteen (16), and a pipeline sight glass one (15) is provided on the pipeline between valve fourteen (14) and valve sixteen (16); the bottom of the cylindrical-conical three-in-one filter (53) is connected to the filter residue quenching treatment device (65) through a pipeline, and a valve thirteen (13) is provided on the pipeline connecting the cylindrical-conical three-in-one filter (53) to the filter residue quenching treatment device (65).

5. The synthesis device of the high-purity metal complex precursor according to claim 4, characterized in that: The reaction kettle (45) and the distillation tower (56) are connected to the distillation kettle / liquid separation kettle (54) through a common pipeline 4, and valve 17 (17) and valve 19 (19) are respectively provided at both ends of the pipeline 4. A pipeline sight glass 2 (18) is provided on the pipeline 4 between valve 17 (17) and valve 19 (19). The pipeline 4 is connected to the solid feeding device (64) through a pipeline between valve 19 (19) and pipeline sight glass 2 (18). A valve 43 (43) is provided on the pipeline connecting the solid feeding device (64) to the pipeline 4. The reaction kettle (45) and the distillation tower (56) are connected to the pipeline 4 through pipeline 5 and pipeline 6 respectively. Valve 21 (21) and valve 22 (43) are respectively provided at both ends of the pipeline 5. 22), a valve forty-four (44) is provided on the pipeline six; a valve twenty-three (23) is provided on the pipeline connecting the distillation kettle / liquid separation kettle (54) to the distillation condenser (57); the bottom of the distillation condenser (57) is connected to a pipeline seven, a pipeline sight glass three (24) is provided on the pipeline seven, the pipeline seven is connected to the DMSO / n-hexane recovery tank (58) and the substituted cyclopentadiene recovery tank (59) through pipeline eight and pipeline nine respectively, a valve twenty-six (26) is provided on the pipeline eight, and a valve twenty-five (25) is provided on the pipeline nine; the distillation condenser (57) is connected to the vacuum pump (20) through a pipeline, and a valve twenty-seven (27) is provided on the pipeline connecting the distillation condenser (57) to the vacuum pump (20).

6. The synthesis device of the high-purity metal complex precursor according to claim 5, characterized in that: The bottom of the DMSO / n-hexane recovery tank (58) is connected to pipeline 10, on which a valve 28 (28) is provided. Pipeline 10 is connected to the n-hexane / tetrahydrofuran storage tank (46) and the DMSO storage tank (48) through pipeline 11 and pipeline 12, respectively. Both ends of pipeline 11 are provided with valve 40 (40) and valve 42 (42), and both ends of pipeline 12 are provided with valve 31 (31) and valve 30 (30). The bottom of the substituted cyclopentadiene recovery tank (59) is connected to pipeline 13, and both ends of pipeline 13 are provided with valve 29 (29) and valve 30. 2 (32), pipeline thirteen is connected to pipeline fourteen, pipeline fourteen is connected to the cyclopentadiene / substituted cyclopentadiene dropping tank (50), pipeline fourteen is provided with valve thirty-three (33), pipeline fourteen is connected to the cracking cyclopentadiene production device (60) through pipeline fifteen, and pipeline fifteen is provided with valve six (6); the pipelines connecting the hydrochloric acid aqueous solution dropping tank (49), the cyclopentadiene / substituted cyclopentadiene dropping tank (50), and the bromopropane / liquefied dimethylamine dropping tank (51) to the feed port of the reaction kettle (45) are respectively provided with valve ten (10), valve eight (8) and valve nine (9).

7. The synthesis device of the high-purity metal complex precursor according to claim 1, characterized in that: The reaction kettle (45), the cylindrical-conical three-in-one filter (53) and the distillation kettle / liquid separation kettle (54) are respectively provided with a stirrer 1 (62), a stirrer 2 (63) and a stirrer 3 (55).

Images