Production method of amino metal precursor

Abstract

The invention discloses a production method of an amino metal precursor, and belongs to the technical field of semiconductor precursor materials, and the production method comprises the following steps: S1, mixing a metal oxide, an organic solvent, trialkyl halogenated silane and a protonic reactant, and carrying out a reaction to obtain a reaction liquid A1; s2, adding dialkylamine into the reaction liquid A1 for reaction to obtain reaction liquid A2; and S3, distilling or adding a cyclopentadiene monomer to react. According to the preparation method, a reaction route of the metal oxide, the trialkyl halogenated silane and the protonic reactant is adopted, so that the problems of high production cost, difficulty in raw material storage and production safety are fully solved, the cost expenditure is effectively controlled from the source, and a butyl lithium reagent which is commonly used in a traditional process but is extremely high in risk is successfully avoided; the safety of the whole process is greatly improved, the potential safety risk is reduced, the process efficiency is effectively improved, and the time consumed by the process is shortened.

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductor precursor materials, and in particular relates to a method for producing an amine-based metal precursor. Background Art

[0002] Tetrakis(dialkylamino)metal precursors and tris(dialkylamino)cyclopentadienylmetal precursors such as Hf(NMe2)4, Zr(NMe2)4, CpZr(NMeEt)4, CpTi(NMe2)3, CpHf(NMe2)3, CpZr(NMe2)3, etc. not only have good stability and high vapor pressure, but also show quite high reactivity. They are one of the best choices for preparing high dielectric constant (K) films. They can stably form high-quality metal element-containing films and have broad application potential in the semiconductor market.

[0003] The traditional process routes for preparing tetrakis(dialkylamino)metal precursors and tris(dialkylamino)cyclopentadienylmetal precursors are basically the same (except that the preparation of the latter requires the additional addition of Cp). For example, the existing preparation route of tris(dialkylamino)cyclopentadienylhafnium is: first react butyl lithium with dialkylamine to obtain dialkylamide lithium, then react it with hafnium tetrachloride to obtain tetrakis(dialkylamino)hafnium, and finally react tetrakis(dialkylamino)hafnium with cyclopentadiene to obtain tris(dialkylamino)cyclopentadienylhafnium. Another commonly used process route is: react hafnium halide HfX4 with cyclopentadienylmetal compound RCpM1 to prepare intermediate trihalocyclopentadienylhafnium RCpHfX3, and then react the intermediate with dialkylamide lithium LiNR 1 R 2 Reaction preparation R 3 CpHf(NR 1 R 2 )3. The butyl lithium / dialkyl lithium amide used in the traditional process route has extremely high reactivity and strong alkalinity, which not only makes the reaction degree difficult to control, but also requires a strictly water-free and oxygen-free reaction environment; in addition, the LiCl solid waste generated in the above route is difficult to filter; the above factors greatly increase the difficulty of experimental operation and the cost of raw material storage, and reduce the reaction efficiency.

[0004] Patent application with publication number CN117105991A discloses a method and device system for preparing tetrakis(dialkylamino)metal complexes and tris(dialkylamino)cyclopentadienylmetal complexes. The process synthesis route disclosed in the application is: (1) MX4+Me3SiNR 1 R 2 →M(NR 1 R 2 )4+Me3SiX; (2) M(NR1 R 2 )4+R 3 CpH→R 3 CpM(NR 1 R 2 )3+HNR 1 R 2 ; This application combines the regulation and control of reaction conditions to promote reactions that are beneficial to the formation of products, reduce the occurrence of side reactions, avoid the defect of using n-butyl lithium to introduce metal impurities, and avoid the production of lithium salts and other components that are not convenient for subsequent separation, thereby facilitating the purification of products. However, the reaction efficiency is low, time-consuming, and the raw material cost is high. Summary of the invention

[0005] The object of the present invention is to provide a method for producing an amine metal precursor to solve the problems of strict environmental requirements, low safety, low reaction efficiency and high process cost in producing an amine metal precursor.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A method for producing an amine metal precursor comprises the following steps: Step S1, mixing a metal oxide, an organic solvent, a trialkylsilane halide and a protic reactant and reacting them to obtain a reaction solution A1; the metal oxide is denoted as MO2; the trialkylsilane halide is denoted as SiR3X; Step S2, adding dialkylamine to the reaction solution A1 to obtain the reaction solution A2; the dialkylamine is denoted as NHR'R"; Step S3, distilling the reaction solution A2 to obtain a tetrakis(dialkylamino)metal precursor; or adding cyclopentadiene monomer to the reaction solution A2, reacting at room temperature, filtering, and distilling after the reaction to obtain a tris(dialkylamino)cyclopentadienylmetal precursor.

[0007] In some embodiments, the metal oxide MO2 is selected from one of TiO2, ZrO2, and HfO2; and / or the organic solvent is one of alkanes, aromatic hydrocarbons, chlorinated alkanes, ether solvents and mixtures thereof; and / or the protic reactant is at least one of water, alcohol and phenol; and / or R in the SiR3X is a straight or branched alkyl group of C1-C6; X is one of Cl, Br, and I.

[0008] In some implementations, the protic reactant is an alcohol, which can be selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, n-hexanol, etc., preferably at least one of methanol, ethanol, and isopropanol.

[0009] In some implementations, the protic reactant is phenol, and optional ones include phenol, hydroquinone, and the like.

[0010] In some embodiments, the SiR3X includes but is not limited to at least one of trimethylchlorosilane, ethyldimethylchlorosilane, propyldimethylchlorosilane, diethylisopropylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, trimethylbromosilane, and triethylbromosilane; preferably at least one of trimethylchlorosilane, triethylchlorosilane, and triisopropylchlorosilane; more preferably trimethylchlorosilane.

[0011] In some embodiments, R' and R" in NHR'R" are independently selected from C1-C5 alkyl, further independently selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, and tert-butyl, and are preferably independently any one of methyl, ethyl, and isopropyl.

[0012] In some implementations, the organic solvent is an alkane, which may be selected from at least one of n-pentane, isopentane, n-hexane, tert-butyl methane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and dodecane, preferably n-hexane.

[0013] In some implementations, the organic solvent is an aromatic hydrocarbon, which may be at least one of benzene, toluene, xylene, and ethylbenzene.

[0014] In some implementations, the organic solvent is a chlorinated alkane, which may be selected from at least one of dichloromethane, chloroform, carbon tetrachloride, and 1-chlorooctane.

[0015] In some implementations, the organic solvent is an ether solvent, which can be selected from at least one of diethyl ether, isopropyl ether, tert-butyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, triethylene glycol monobutyl ether, propylene glycol methyl ether, and tetrahydrofuran, preferably tetrahydrofuran.

[0016] In some implementations, the equivalent ratio of SiR3X to MO2 is 8-20:1, and can be selected from 8:1, 8.2:1, 8.5:1, 9:1, 9.3:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12.0:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1, 15. 5:1, 16:1, 16.5:1, 17:1, 17.5:1, 18:1, 18.5:1, 19:1, 19.5:1, 20:1, etc., preferably 8-12:1, more preferably 8-9:1; and / or, the equivalent ratio of the protic reactant to MO2 is 0.01-4:1, such as 0.01:1, 0.03:1, 0.05:1, 0.07:1 , 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.5:1, 2.0:1, 2.5:1, 3.0:1, 3.5:1, 4.0:1, etc., preferably 0.05-2:1, more preferably 0.08-1:1; And / or, the equivalent ratio of NHR'R" to MO2 is 5-15:1, and can be selected from 5:1, 6:1, 7:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1, etc., preferably 8-12:1.

[0017] The mass ratio of the organic solvent to MO2 is 1:1-100.

[0018] In some implementations, the reaction time of adding the protic reactant in step S1 is 12-24 hours; In step S2, when the temperature is 0 Next, NHR'R" is added to the reaction solution A1, preferably at a temperature of -20 to 0 Under the conditions, NHR'R" was added to the reaction solution A1; The reaction temperature of the reaction solution A2 in step S2 is 60 ~100 .

[0019] In some implementations, the tetrakis(dialkylamino)metal precursor is denoted as M(NR'R")4, where M is Ti, Zr, or Hf, and R' and R" are as defined above.

[0020] In some implementations, the tris(dialkylamino)cyclopentadienyl metal precursor is denoted as CpM(NR'R")3, the cyclopentadiene monomer is denoted as Cp, and M, R' and R" are all as defined above.

[0021] In some implementations, the equivalent ratio of Cp to MO2 is 0.8-2:1, optionally including but not limited to 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, etc., preferably 1.0-1.4:1; and / or, the dropwise addition temperature of Cp added to the reaction solution A2 is 25 ~50 .

[0022] In some implementations, Cp is substituted or unsubstituted cyclopentadiene, and the substituent in the substituted cyclopentadiene is one of C1-C5 alkyl, C1-C5 alkoxy, silicon, and siliconoxy, and the number of the substituents is 1-5.

[0023] Beneficial effects of the present invention: (1) The present invention takes full account of production costs and production safety. Metal oxides, which are cheaper and easier to store, are selected as starting materials for the reaction. Compared with the high-cost and difficult-to-store metal halide raw materials in the existing process, metal oxides are in sufficient supply in the market and have a high cost-effectiveness, which effectively controls cost expenditure from the source.

[0024] (2) The present invention designs a process route for preparing intermediates by reacting metal oxides, trialkylsilane halides and protic reactants. This innovative industrial reaction route successfully avoids the butyl lithium reagent commonly used in traditional processes but extremely dangerous. Butyl lithium is extremely active in chemical properties and flammable when exposed to air. There are many safety hazards during storage, transportation and use. The method of the present invention greatly improves the safety of the entire process and reduces potential safety risks. In addition, it avoids the production of lithium salts in the reaction, saves a lot of process time consumed by filtering lithium salts, and significantly improves the reaction / process efficiency.

[0025] (3) The process of the present invention achieves a significant improvement in raw material utilization. By optimizing the reaction conditions, steps and various links, the raw materials are more fully utilized in the entire reaction route, avoiding unnecessary waste. This improvement in raw material utilization not only reduces the consumption of raw materials, but also reduces the subsequent processing costs, making the process of the present invention have higher economic benefits and industrial application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The present invention will be further described below in conjunction with the accompanying drawings.

[0027] Figure 1 is the H NMR spectrum of the product CpHf(NMe2)3 in Example 1 of the present invention; Figure 2 is the H NMR spectrum of the product CpZr(NMe2)3 in Example 5 of the present invention; Figure 3 is the H NMR spectrum of the product Hf(NMe2)4 in Example 7 of the present invention; Figure 4 is the H NMR spectrum of the product Zr(NMeEt)4 in Example 8 of the present invention; Figure 5 This is the hydrogen NMR spectrum of the product Ti(NMe2)4 in Example 9 of the present invention. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] The present application provides a method for producing an amine metal precursor, comprising the following steps: Step S1, mixing a metal oxide (MO2), an organic solvent, a trialkylsilane halide (SiR3X) and a protic reactant and reacting the mixture to obtain a reaction solution A1; Step S2: at a temperature of ≤0 Under the following conditions, dialkylamine (NHR'R") is added to the reaction solution A1 to carry out a reaction to obtain a reaction solution A2; Step S3, distilling the reaction solution A2 to obtain a tetrakis(dialkylamino)metal precursor; or adding cyclopentadiene monomer to the reaction solution A2, reacting at room temperature, filtering, and distilling after the reaction to obtain a tris(dialkylamino)cyclopentadienylmetal precursor.

[0030] In some embodiments, the reaction time of adding the protic reactant in step S1 is 12-24 hours; In step S2, at a temperature of -20 ~0 Under the conditions, dialkylamine (NHR'R") is added to the reaction solution A1; The reaction temperature of the reaction solution A2 in step S2 is 60 ~100 .

[0031] In some embodiments, the MO2 is selected from one of TiO2, ZrO2, and HfO2.

[0032] In some embodiments, the organic solvent is an alkane, an aromatic hydrocarbon, a chlorinated alkane, an ether solvent or a mixture thereof; the mass ratio of the organic solvent to MO2 is 1:1-100.

[0033] In some embodiments, the protic reactant is one of water, alcohol, and phenol. Preferably, the protic reactant is at least one of methanol, ethanol, and isopropanol, more preferably ethanol.

[0034] In some embodiments, R in the SiR3X is a C1-C6 straight or branched alkyl group, which may be at least one of trimethyl, triethyl, tripropyl, tri-n-butyl, tri-n-pentyl, tri-n-hexyl, methyl diethyl, dimethyl propyl, diethyl propyl, dimethyl butyl, etc.; X is a halogen selected from Cl, Br, I; In some embodiments, the SiR3X is trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane; more preferably trimethylchlorosilane.

[0035] In some embodiments, R' and R" in the NHR'R" are independently selected from C1-C5 alkyl.

[0036] In some embodiments, the equivalent ratio of SiR3X to MO2 is 8-20:1; preferably, the equivalent ratio of SiR3X to MO2 is 8-12:1, at which a more suitable production cost and a higher yield can be obtained; more preferably, the equivalent ratio of SiR3X to MO2 is 8-9:1.

[0037] In some embodiments, the equivalent ratio of the protic reactant to MO2 is 0.01-4:1, preferably the equivalent ratio of the protic reactant to MO2 is 0.05-2:1, further preferably 0.08-1:1, and more preferably the equivalent ratio of the protic reactant to MO2 is 0.1:1.

[0038] In some embodiments, the equivalent ratio of NHR'R" to MO2 is 5-15:1, preferably 8-12:1. Too much NHR'R" may cause side reactions.

[0039] In some embodiments, the reaction solution A2 is distilled to obtain a tetrakis(dialkylamino)metal precursor (M(NR'R")4, M is Ti, Zr, Hf, R' and R" are as defined above). An exemplary reaction principle is as follows:

[0040] In some embodiments, cyclopentadiene monomer (Cp) is added to reaction solution A2, reacted at room temperature, filtered, and distilled out tris(dialkylamino)cyclopentadienyl metal precursor (CpM(NR'R")3, M is Ti, Zr, Hf, R', R" and Cp are as defined above) after the reaction. The exemplary reaction principle is as follows:

[0041] In some embodiments, the temperature at which cyclopentadiene monomer (Cp) is added to the reaction solution A2 is 25 ~50 .

[0042] In some embodiments, the equivalent ratio of cyclopentadiene monomer (Cp) to MO2 is 0.8-2:1, preferably, the equivalent ratio of cyclopentadiene monomer Cp to MO2 is 1.0-1.4:1.

[0043] The following describes the invention in conjunction with specific embodiments.

[0044] Example 1

[0045] This embodiment provides a method for producing an amine metal precursor, comprising the following steps: Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 1 L of solvent ethylene glycol dimethyl ether and trimethylsilyl chloride (439 g, 4.041 mol, 8.5 eq), stirring was started, and ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. During the addition of ethanol, the temperature did not exceed 60 After the ethanol was added, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1 g, 4.039 mol, 8.5 eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 70 The reaction was continued for 6 hours. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was completed, the reaction was carried out at room temperature for 12 hours. The reaction liquid was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 161.2 g of light yellow liquid (tris(dimethylamino)cyclopentadienyl hafnium, chemical formula CpHf(NMe2)3), with a yield of 90.3%.

[0046] The product hydrogen spectrum is as follows Figure 1 As shown: 1 HNMR(C6D6): δ2.96 (S,18H,N(CH3)2), 6.03(S,5H,C5H5).

[0047] After distillation, the CpHf(NMe2)3 product with a metal purity of 99.9999% can be obtained.

[0048] Example 2

[0049] This embodiment provides a method for producing an amine metal precursor, comprising the following steps: Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 1.1 L of solvent ethylene glycol dimethyl ether and triethylchlorosilane (588.5 g, 3.905 mol, 8.2 eq), stirring was started, and ethanol (4.4 g, 0.1 mol, 0.2 eq) was added dropwise at room temperature. During the addition of ethanol, the temperature did not exceed 60 After the ethanol was added, the reaction was continued at room temperature for 14 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (214.5 g, 4.758 mol, 10 eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 60 The reaction was continued for 5.5 hours. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was completed, the reaction was carried out at room temperature for 12 hours. The reaction liquid was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 152.6 g of light yellow liquid (tris(dimethylamino)cyclopentadienyl hafnium, chemical formula CpHf(NMe2)3), with a yield of 85.5%.

[0050] After distillation, the CpHf(NMe2)3 product with a metal purity of 99.9999% can be obtained.

[0051] Example 3

[0052] This embodiment provides a method for producing an amine metal precursor, comprising the following steps: Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 1.6 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (464.5 g, 4.276 mol, 9 eq) as solvent, stirring was started, and methanol (5.3 g, 0.165 mol, 0.35 eq) was added dropwise at room temperature. During the addition of methanol, the temperature did not exceed 60 After the methanol was added, the reaction was continued at room temperature for 16 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (257.2 g, 5.705 mol, 12 eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 75 The reaction was continued for 6 hours. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was completed, the reaction was carried out at room temperature for 12 hours. The reaction liquid was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 157.4 g of light yellow liquid (tris(dimethylamino)cyclopentadienyl hafnium, chemical formula: CpHf(NMe2)3), with a yield of 88.2%.

[0053] After distillation, the CpHf(NMe2)3 product with a metal purity of 99.9999% can be obtained.

[0054] Example 4

[0055] This embodiment provides a method for producing an amine metal precursor, comprising the following steps: Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 1.2 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (464.5 g, 4.276 mol, 9 eq) as solvent, stirring was started, and ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. During the addition of ethanol, the temperature did not exceed 60 After the ethanol was added, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1 g, 4.039 mol, 8.5 eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 80 The reaction was continued for 6 hours. Finally, cyclopentadiene (31.4 g, 0.475 mol, 1.0 eq) was added dropwise at room temperature. After the addition was completed, the reaction was allowed to proceed at room temperature for 12 hours. The reaction solution was filtered, the filtrate was collected, and the filtrate was concentrated. The filtrate was distilled under reduced pressure to obtain 134.6 g of a light yellow liquid (cyclopentadienyl tris (dimethylamino) hafnium, chemical formula CpHf (NMe2) 3), with a yield of 79.4%. After distillation, a CpHf (NMe2) 3 product with a metal purity of 99.9999% was obtained.

[0056] Example 5

[0057] This embodiment provides a method for producing an amine metal precursor, comprising the following steps: Zirconium oxide (75.0 g, 0.609 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 2.0 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (665.0 g, 6.121 mol, 10.1 eq) as solvent, stirring was started, and ethanol (7.8 g, 0.169 mol, 0.28 eq) was added dropwise at room temperature. During the addition of ethanol, the temperature did not exceed 60 After the ethanol was added, the reaction was continued at room temperature for 12 h until the zirconium oxide was converted into zirconium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (400g, 8.873mol, 14.6eq), and the reaction temperature is not higher than 30 during the introduction of dimethylamine After the dimethylamine is introduced, 100 The mixture was heated under reflux and the reaction was continued for 6 hours. Finally, cyclopentadiene (80.0 g, 1.210 mol, 2.0 eq) was added dropwise at room temperature. After the addition was completed, the mixture was reacted at room temperature for 12 hours. The reaction liquid was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 135.7 g of a light yellow liquid (cyclopentadienyl tris(dimethylamino) zirconium, chemical formula: CpZr(NMe2)3), with a yield of 77.3%.

[0058] The product hydrogen spectrum is as follows Figure 2 As shown: 1 HNMR(C6D6): δ2.92 (S,18H,N(CH3)2), 6.06(S,5H,C5H5).

[0059] Example 6

[0060] This embodiment provides a method for producing an amine metal precursor, comprising the following steps: Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 1.8 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (620 g, 5.707 mol, 12 eq) as solvent, stirring was started, and ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. During the addition of ethanol, the temperature did not exceed 60 After the ethanol was added, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce methylethylamine gas (225 g, 3.806 mol, 8.0 eq), and the reaction temperature is not higher than 30 After the methylethylamine is introduced, 70 The reaction was continued for 6 hours. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was completed, the reaction was allowed to proceed at room temperature for 12 hours. The reaction solution was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 166.2 g of a light yellow liquid (cyclopentadienyltrimethylethylamino hafnium, chemical formula CpHf(NMeEt)3), with a yield of 83.7%. Product hydrogen spectrum data: 1 HNMR(C6D6): δ1.0 (t, 9H,CH3), 2.9 (s,9H, NCH3), 3.2 (q, 6H, NCH2), 6.1 (s, 5H, C5H5).

[0061] Example 7

[0062] This embodiment provides a method for producing an amine metal precursor, comprising the following steps: Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 1 L of solvent ethylene glycol dimethyl ether and trimethylsilyl chloride (439 g, 4.041 mol, 8.5 eq), stirring was started, and ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. During the addition of ethanol, the temperature did not exceed 60 After the ethanol was added, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1 g, 4.039 mol, 8.5 eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 70 The reaction was continued for 6 h, the reaction solution was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 156.5 g of a low melting point solid (tetrakis(dimethylamino)hafnium, chemical formula: Hf(NMe2)4) with a yield of 92.8%.

[0063] The product hydrogen spectrum is as follows Figure 3 As shown: 1 HNMR(C6D6): δ2.99 (S,24H,N(CH3)2).

[0064] Example 8

[0065] Zirconium oxide (75.0 g, 0.609 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 2.0 L of ethylene glycol dimethyl ether and trimethylsilyl chloride (665.0 g, 6.121 mol, 10.1 eq) as solvent, stirring was started, and ethanol (7.8 g, 0.169 mol, 0.28 eq) was added dropwise at room temperature. During the addition of ethanol, the temperature did not exceed 60 After the ethanol was added, the reaction was continued at room temperature for 12 h until the zirconium oxide was converted into zirconium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce methylethylamine gas (400g, 6.767mol, 11.1eq), and the reaction temperature is not higher than 30 during the introduction of methylethylamine After the methylethylamine is introduced, 90 The reaction was continued under reflux for 6 hours. Finally, the reaction solution was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 168.2 g of yellow liquid (tetrakis(methylethylamino)zirconium, chemical formula: Zr(NMeEt)4) with a yield of 85.3%.

[0066] The product hydrogen spectrum is as follows Figure 4 As shown: 1 HNMR(C6D6): δ1.17 (t, 9H,CH3), 2.99 (s,9H, NCH3), 3.25 (q, 6H, NCH2).

[0067] Example 9

[0068] Titanium oxide (37.9 g, 0.475 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 1 L of solvent ethylene glycol dimethyl ether and trimethylsilyl chloride (439 g, 4.041 mol, 8.5 eq), stirring was started, and ethanol (2.2 g, 0.048 mol, 0.1 eq) was added dropwise at room temperature. During the addition of ethanol, the temperature did not exceed 60 After the ethanol was added, the reaction was continued at room temperature for 12 h until the titanium oxide was converted into titanium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1 g, 4.039 mol, 8.5 eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 60 The reaction was continued for 6 h, the reaction solution was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 90.6 g of yellow liquid (tetrakis(dimethylamino)titanium, chemical formula: Ti(NMe2)4) with a yield of 85.1%.

[0069] The product hydrogen spectrum is as follows Figure 5 As shown: 1 HNMR(C6D6): δ3.11 (S,24H,N(CH3)2).

[0070] Comparative Example 1

[0071] Hafnium oxide (100.0 g, 0.475 mol, 1.0 eq) was added to the reaction flask, and the inert gas N2 was replaced three times. After adding 1 L of solvent ethylene glycol dimethyl ether and trimethylsilyl chloride (361.3 g, 3.325 mol, 7 eq), stirring was started, and methanol (1.5 g, 0.047 mol, 0.1 eq) was added dropwise at room temperature. During the addition of methanol, the temperature did not exceed 60 After the methanol was added, the reaction was continued at room temperature for 12 h until hafnium oxide was converted into hafnium tetrachloride. The temperature of the reaction system was lowered to 0 , slowly introduce dimethylamine gas (182.1 g, 4.039 mol, 8.5 eq), and the reaction temperature is not higher than 30 After the dimethylamine is introduced, 70 The reaction was continued for 6 hours. Finally, cyclopentadiene (44.0 g, 0.665 mol, 1.4 eq) was added dropwise at room temperature. After the addition was completed, the reaction was carried out at room temperature for 12 hours. The reaction liquid was filtered, the filtrate was collected, and the filtrate was concentrated and distilled under reduced pressure to obtain 111.5 g of light yellow liquid with a yield of 62.5%.

[0072] Comparative Example 2

[0073] The reaction was basically the same as Example 3, except that the amount of trimethylsilyl chloride added was 310 g (2.853 mol, 6 eq). 75.2 g of crude product was obtained, with a yield of 42.1%.

[0074] Comparative Example 3

[0075] The reaction was basically the same as Example 1, except that the amount of dimethylamine added was 91 g (2.018 mol, 4.2 eq). 46.2 g of crude product was obtained, with a yield of 25.9%.

[0076] Comparative Example 4: Reference is made to Comparative Example 2 in CN111303197A. The yield is 73%.

[0077] Comparative Example 5: Reference is made to Comparative Example 1 in CN111303197A. Yield: 75%.

[0078] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0079] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for producing an amine metal precursor, characterized in that: The steps include: Step S1, mixing a metal oxide, an organic solvent, a trialkylsilane halide and a protic reactant and reacting them to obtain a reaction solution A1; Step S2, adding dialkylamine to the reaction solution A1 to obtain the reaction solution A2; Step S3, distilling the reaction solution A2 to obtain a tetrakis(dialkylamino)metal precursor; or adding cyclopentadiene monomer to the reaction solution A2, reacting at room temperature, filtering, and distilling after the reaction to obtain a tris(dialkylamino)cyclopentadienylmetal precursor.

2. The method for producing an amine metal precursor according to claim 1, characterized in that: The metal oxide is selected from one of TiO2, ZrO2 and HfO2; and / or, the organic solvent is one of alkanes, aromatic hydrocarbons, chloroalkanes, ether solvents and mixtures thereof; and / or, the protic reactant is at least one of water, alcohol and phenol; and / or, the trialkylsilane halide is denoted as SiR3X; in the SiR3X, R is a straight or branched alkyl group of C1-C6; and X is one of Cl, Br and I.

3. The method for producing an amine metal precursor according to claim 1, characterized in that: The protic reactant is an alcohol selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol and n-hexanol; and / or the trialkylsilyl halide is selected from at least one of trimethylsilyl chloride, triethylsilyl chloride and triisopropylsilyl chloride.

4. The method for producing an amine metal precursor according to claim 1, characterized in that: The dialkylamine is denoted as NHR'R", wherein R' and R" in the NHR'R" are independently selected from C1-C5 alkyl groups.

5. The method for producing an amine metal precursor according to claim 1, characterized in that: The equivalent ratio of the trialkylsilane halide to the metal oxide is 8-20:1; and / or the equivalent ratio of the protic reactant to the metal oxide is 0.01-4:1; and / or the equivalent ratio of the dialkylamine to the metal oxide is 5-15:

1.

6. The method for producing an amine metal precursor according to claim 1, characterized in that: The equivalent ratio of the trialkylsilane halide to the metal oxide is 8-12:1; and / or the equivalent ratio of the protic reactant to the metal oxide is 0.05-2:1; and / or the equivalent ratio of the dialkylamine to the metal oxide is 8-12:

1.

7. The method for producing an amine metal precursor according to claim 1, characterized in that: The reaction time of adding the protic reactant in step S1 is 12-24 hours; In step S2, a dialkylamine is added to the reaction solution A1 at a temperature below 0°C; The reaction temperature for obtaining the reaction solution A2 in step S2 is 60°C to 100°C.

8. The method for producing an amine metal precursor according to claim 1, characterized in that: The tetrakis(dialkylamino)metal precursor is denoted as M(NR'R")4, where M is Ti, Zr, or Hf, and R' and R" are independently selected from C1-C5 alkyl groups.

9. The method for producing an amine metal precursor according to claim 1, characterized in that: The tris(dialkylamino)cyclopentadienyl metal precursor is denoted as CpM(NR'R")3, where M is Ti, Zr, or Hf, R' and R" are independently selected from C1-C5 alkyl groups, Cp is substituted or unsubstituted cyclopentadiene, and the substituent in the substituted cyclopentadiene is one of a C1-C5 alkyl group, a C1-C5 alkoxy group, a silicon group, or a siliconoxy group, and the number of the substituents is 1-5.

10. The method for producing an amine metal precursor according to claim 9, characterized in that: The dropwise addition temperature of the cyclopentadiene monomer into the reaction solution A2 is 25° C. to 50° C.; and / or the equivalent ratio of the cyclopentadiene monomer to the metal oxide is 0.8-2:1.

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