Heterogeneous synthesis method of cyclopentadiene-based metal precursor

Abstract

The invention discloses a heterogeneous synthesis method of a cyclopentadiene-based metal precursor, and belongs to the technical field of semiconductor deposition materials. The structure of the cyclopentadienyl metal precursor is represented as RzCpM (NRxRy) 3, M is selected from Ti, Zr and Hf, Cp is a cyclopentadienyl group, R, Rx and Ry are independently selected from C1-C5 alkyl groups, and z is an integer of 0-5; the heterogeneous synthesis method comprises the following steps: mixing lithium dialkylamino, a metal halide and a heterogeneous reaction catalyst for reaction, and then adding a cyclopentadiene monomer for reaction. By introducing the specific heterogeneous reaction catalyst and optimizing the reaction condition parameters such as the raw material equivalence ratio, the material adding sequence, the reaction temperature and the reaction time, the reaction yield and the product quality can be effectively improved, and the defects of low yield and unstable process in the traditional heterogeneous synthesis route are well overcome; the method can be applied to industrial production and manufacturing of the cyclopentadienyl titanium / zirconium / hafnium precursor.

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductor deposition materials, and in particular relates to a heterogeneous synthesis method of a cyclopentadienyl metal precursor. Background Art

[0002] The oxide film of Group IV B metals has high dielectric (i.e. high K) properties and has been widely used in logic chips, memory chips and other semiconductor components. It is an ideal substitute for traditional silicon dioxide film. There are a series of difficulties in the application of precursor materials for preparing Group IV B metal oxide films in CVD / ALD: for example, metal chloride precursors (for example: HfCl 4 、ZrCl 4 ) produces HCl as a byproduct, which leads to equipment corrosion and reduced film purity; another example is tetra(dialkylamino)metal precursors (example: Hf(NMe 2 ) 4 、Zr(NEtMe) 4 ) are prone to condensation at low temperatures, resulting in poor precursor utilization and reduced process repeatability; in addition, some precursors are insufficiently reactive at low temperatures and cannot meet the ALD process requirements for flexible electronic devices.

[0003] Tris(dialkylamino)cyclopentadienyl metal precursors such as CpZr(NMe 2 ) 3 、CpZr(NMeEt) 3 、CpTi(NMe 2 ) 3 、CpHf(NMe 2 ) 3 、CpHf(NMeEt) 3 Not only do they have good stability and high vapor pressure, but they also exhibit quite high reactivity. They are one of the best choices for preparing high-K films. They can stably form high-quality films containing metal elements and have broad application potential in the semiconductor market.

[0004] The synthesis of tri(dialkylamino)cyclopentadienyl metal precursors is usually carried out using dialkylamide lithium LiNR 1 R 2, metal halide and cyclopentadiene monomer RCpH as raw materials; for example, Japanese patent JP2012201652A discloses a method for manufacturing amino zirconium compounds, and Example 1 of the patent discloses that after zirconium tetrachloride and dimethylamine are mixed, n-butyl lithium is added thereto for reaction, and then cyclopentadiene monomer is added thereto for reaction to obtain tris(dimethylamino)cyclopentadienyl hafnium, and the yield is only about 7%. Another example is Chinese patent CN107188908A discloses a method for preparing tris(dimethylamino)cyclopentadienyl zirconium, specifically, dimethylamino lithium and zirconium tetrachloride react to generate tetra(dimethylamino) zirconium, and cyclopentadiene monomer is added thereto to generate tris(dimethylamino)cyclopentadienyl zirconium. The process is a "one-pot" synthesis, which can simplify the operation steps, but the process yield is only 31-35%.

[0005] Although the above process is a relatively mature synthesis route, the raw material dialkylamine in the process is gaseous or liquid, dialkylamide lithium is solid, some metal halides are solid, and cyclopentadiene monomer is liquid. There are multiple raw materials in different states in the reaction system. In the actual scale-up production operation, this multiphase reaction will not only cause problems such as insufficient material reaction and low process yield, but also cause the defect of poor process repeatability, resulting in the inability to stably obtain the ideal product. Summary of the invention

[0006] In order to solve the above defects of the prior art, the purpose of the present invention is to provide a heterogeneous synthesis method of a cyclopentadienyl metal precursor, which can solve the problems of low yield and unstable process in the traditional multiphase synthesis route.

[0007] Firstly, the present invention provides a heterogeneous synthesis method of a cyclopentadienyl metal precursor, comprising the following steps: mixing a dialkyl amide lithium, a metal halide and a heterogeneous reaction catalyst for reaction, and then adding a cyclopentadiene monomer for reaction.

[0008] Further, the structure of the cyclopentadienyl metal precursor is represented by R z CpM(NR x R y ) 3 , wherein M is selected from Ti, Zr, Hf, Cp is cyclopentadienyl, R, R x and R y The alkyl groups are independently selected from C1-C5 groups, and z is an integer of 0-5.

[0009] Furthermore, R x and R y Independently selected from methyl or ethyl.

[0010] Further, exemplary hafnium cyclopentadienyl precursors include: CpHf(NMe 2 ) 3、CpHf(NMeEt) 3 , CpHf(NEt 2 ) 3 、(MeCp)Hf(NMe 2 ) 3 、(MeCp)Hf(NMeEt) 3 、(MeCp)Hf(NEt 2 ) 3 、(Me 2 Cp)Hf(NMe 2 ) 3 、(Me 2 Cp)Hf(NMeEt) 3 、(Me 2 Cp)Hf(NEt 2 ) 3 、(Me 5 Cp)Hf(NMe 2 ) 3 、(Me 5 Cp)Hf(NMeEt) 3 、(Me 5 Cp)Hf(NEt 2 ) 3 wait.

[0011] Further, exemplary cyclopentadienyl zirconium precursors include: CpZr(NMe 2 ) 3 、CpZr(NMeEt) 3 、CpZr(NEt 2 ) 3 、(MeCp)Zr(NMe 2 ) 3 、(MeCp)Zr(NMeEt) 3 、(MeCp)Zr(NEt 2 ) 3 、(Me 2 Cp)Zr(NMe 2 ) 3 、(Me 2 Cp)Zr(NMeEt) 3 、(Me 2 Cp)Zr(NEt 2 ) 3 、(Me 5 Cp)Zr(NMe 2 ) 3 、(Me 5 Cp)Zr(NMeEt) 3 、(Me 5 Cp)Zr(NEt 2 )3 wait.

[0012] Further, exemplary cyclopentadienyl titanium precursors are: CpTi(NMe 2 ) 3 、CpTi(NMeEt) 3 、CpTi(NEt 2 ) 3 、(MeCp)Ti(NMe 2 ) 3 、(MeCp)Ti(NMeEt) 3 、(MeCp)Ti(NEt 2 ) 3 、(Me 2 Cp)Ti(NMe 2 ) 3 、(Me 2 Cp)Ti(NMeEt) 3 、(Me 2 Cp)Ti(NEt 2 ) 3 、(Me 5 Cp)Ti(NMe 2 ) 3 、(Me 5 Cp)Ti(NMeEt) 3 、(Me 5 Cp)Ti(NEt 2 ) 3 wait.

[0013] Furthermore, the structure of lithium dialkylamide is represented by LiN(R x R y ) 2 , R x and R y As defined above.

[0014] Furthermore, the structure of the metal halide is represented by MY 4 , M is selected from Ti, Zr, Hf, Y represents a halogen, and the metal halide includes at least one of fluoride, chloride, bromide, and iodide, preferably chloride or bromide.

[0015] Furthermore, the molar equivalent ratio of the metal halide to the dialkylamide lithium is 1:4-6.

[0016] Furthermore, the heterogeneous reaction catalyst has the following structure: ; Among them, R 1 is a C2-C6 alkenyl or C2-C6 alkynyl, R 2is a substituted or unsubstituted phenyl group, R 3 is any one of H, C1-C5 straight chain or branched alkyl, X is Cl or Br, and n is 0 or 1.

[0017] Furthermore, R 1 It is any of vinyl, propenyl, allyl, butenyl and ethynyl, and is preferably vinyl.

[0018] Furthermore, the R 2 It is any one of phenyl, benzyl, phenethyl, and phenyl substituted with 1 to 5 methyl groups.

[0019] Furthermore, the R 3 Including but not limited to any one of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, and tert-butyl.

[0020] In one embodiment, the R 1 For vinyl, R 3 is H, n is 0.

[0021] In one embodiment, the R 1 For vinyl, R 2 is phenyl, R 3 is H, X is Cl, and n is 1.

[0022] In one embodiment, the R 1 For vinyl, R 2 is benzyl, R 3 is H, X is Cl, and n is 1.

[0023] In one embodiment, the R 1 For vinyl, R 2 is a dimethyl-substituted phenyl group, R 3 is H, X is Br, and n is 1.

[0024] In one embodiment, the R 1 For vinyl, R 2 is a phenyl group substituted with a methyl group, R 3 is methyl, X is Br, and n is 1.

[0025] Furthermore, the heterogeneous reaction catalyst is used in an amount of 0.1%-10% of the molar equivalent of the metal halide, such as but not limited to 0.1%, 0.5%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, etc.

[0026] Further, the structure of cyclopentadiene monomer is represented by R zCp, R and z have the same meanings as defined above.

[0027] Furthermore, the molar equivalent ratio of the metal halide to the cyclopentadiene monomer is 1:1-2.

[0028] Furthermore, a solvent is added to the heterogeneous synthesis method, and the solvent is selected from at least one of an alkane organic solvent and an aromatic hydrocarbon organic solvent; the alkane organic solvent includes but is not limited to at least one of n-pentane, n-hexane, and n-octane, and the aromatic hydrocarbon organic solvent includes but is not limited to at least one of benzene, toluene, and ethylbenzene; the mass volume ratio of the metal halide to the solvent is 0.05-0.2:1 kg / L.

[0029] Furthermore, the dialkylamide lithium can be commercially available, or can be prepared by reacting dialkylamine and alkyllithium.

[0030] In some embodiments, the heterogeneous synthesis method of the cyclopentadienyl metal precursor comprises the following steps:

[0031] S1, adding solvent, dialkylamine and alkyl lithium into a reaction kettle for mixed reaction;

[0032] S2, adding a heterogeneous reaction catalyst and a metal halide to react;

[0033] S3, adding cyclopentadiene monomer to react;

[0034] S4, filtering and distilling out the cyclopentadienyl metal precursor product.

[0035] Further, the structure of the dialkylamine is represented by HNR x R y , R x and R y The dialkylamine has the same definition as above and can be introduced into the reaction in the form of a liquid or solution or in the form of a gas.

[0036] Furthermore, the molar equivalent ratio of the dialkylamine to the metal halide is 4-6:1.

[0037] Furthermore, the alkyl lithium is selected from at least one of methyl lithium, n-butyl lithium, tert-butyl lithium and phenyl lithium.

[0038] Furthermore, the molar equivalent ratio of the alkyl lithium to the metal halide is 4-6:1.

[0039] Furthermore, the feeding temperature in S1 is controlled to be lower than -15°C, the temperature of the mixed reaction in S1 is -30~30°C, and the reaction time is 1-24h.

[0040] Furthermore, the reaction temperature in S2 is 30-50°C, preferably 40-45°C; and the reaction time is 4-24h.

[0041] Furthermore, in S3, the reaction temperature is adjusted to 20-28°C and cyclopentadiene monomer is added. After the addition is completed, the reaction temperature is adjusted to 30-50°C, preferably 40-45°C for reaction, and the reaction time is 8-24h.

[0042] Beneficial effects of the present invention:

[0043] (1) The present application uses a suitable heterogeneous reaction catalyst to solve the many defects of the traditional multiphase synthesis process of cyclopentadienyl metal precursors, and obtains a higher reaction yield and a more stable synthesis effect in the kilogram-level reaction scale-up process, effectively improving the process efficiency and saving the process cost.

[0044] (2) The present application controls the relative amounts of raw materials such as equivalent ratio, material addition sequence, reaction temperature and reaction time, which can further improve the reaction yield and product quality, and enhance process reliability and safety.

[0045] (3) The heterogeneous synthesis method of the present application has high industrial application value and can be used in the industrial production of cyclopentadienyl titanium / zirconium / hafnium precursors. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 : The heterogeneous reaction catalyst of Example 1 1 H NMR characterization chart.

[0047] Figure 2 : Example 1 The obtained product CpHf(NMe 2 ) 3 of 1 H NMR characterization chart.

[0048] Figure 3 : The heterogeneous reaction catalyst of Example 2 1 H NMR characterization chart.

[0049] Figure 4 : The heterogeneous reaction catalyst of Example 3 1 H NMR characterization chart.

[0050] Figure 5 Example 4: Product CpZr(NMe 2 ) 3 of 1 H NMR characterization chart. DETAILED DESCRIPTION

[0051] 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.

[0052] Example 1

[0053] This embodiment provides a cyclopentadienyl metal precursor - CpHf (NMe 2 ) 3 The heterogeneous synthesis method comprises the following steps:

[0054] S1. Add 18 L of n-hexane to a 50 L reactor. After the temperature in the reactor is cooled to -18 °C, 1.58 kg (35.15 mol, 4.5 eq) of dimethylamine is introduced. After the addition of dimethylamine is completed, 9.00 kg (32.80 mol, 4.2 eq) of n-butyl lithium solution is slowly added dropwise. The reaction temperature is maintained at about -15 °C during the addition. After the addition is completed, the temperature is naturally raised to room temperature (25 ± 3 °C) and the reaction is carried out for 1 hour.

[0055] S2, add 0.011kg (0.39mol, 0.05eq) of heterogeneous reaction catalyst, then add 2.5kg (7.81mol, 1.0eq) of hafnium tetrachloride, maintain the reaction temperature between 40℃-45℃ during the addition process, and react at 45℃ for 4h after the addition. The heterogeneous reaction catalyst (CAS: 118-10-5) has the following structure: The HNMR characterization spectrum of the heterogeneous reaction catalyst is shown in the attached Figure 1 , the characterization data is 1 HNMR (400 MHz, CDCl 3 ): δ 8.88 (d, J = 4.5 Hz, 1H), 8.12 (d, J = 8.4 Hz, 1H), 7.98(d, J = 8.5 Hz, 1H), 7.72 – 7.64 (m, 1H), 7.60 (d, J = 4.5 Hz, 1H), 7.48 (dd, J =11.2, 4.1 Hz, 1H), 5.99 (ddd, J = 16.4, 11.1, 7.6 Hz, 1H), 5.69 (t, J= 5.6 Hz,1H), 5.04 (s, 1H), 5.01 (d, J = 6.7 Hz, 1H), 3.29 – 3.20 (m, 1H), 3.09 (td, J =9.3, 4.6 Hz, 1H), 2.96 – 2.83 (m, 2H), 2.75 (dt, J = 13.1, 8.8 Hz, 1H), 2.22(dd, J = 16.6, 8.1 Hz, 1H), 1.99 (dd, J = 12.1, 10.3 Hz, 1H), 1.50 (dd, J = 19.0,10.7 Hz, 2H), 1.35 – 1.13 (m, 2H), 0.87 (dd, J = 14.6, 6.9 Hz, 1H).

[0056] S3. After the reactor was cooled to 25°C, 0.72 kg (10.93 mol, 1.4 eq) of cyclopentadiene monomer was added dropwise. After the addition was completed, the mixture was reacted at 45°C for 12 h. The mixture was filtered, and the filtrate was distilled to remove the solvent. Then, 2.49 kg of the product was distilled under reduced pressure, and the calculated yield was 85.0%.

[0057] The product structure was characterized by HNMR (see Appendix Figure 2 ), the characterization data is: 1 HNMR (C 6 D 6 ): δ2.96 (S,18H,N(CH 3 ) 2 ), 6.03(S,5H,C 5 H 5 ).

[0058] Example 2

[0059] This embodiment provides a cyclopentadienyl metal precursor - CpHf (NMe 2 ) 3 The heterogeneous synthesis method comprises the following steps:

[0060] S1. Add 18 L of n-hexane to a 50 L reactor. After the temperature in the reactor is cooled to -15°C, add 1.58 kg (35.15 mol, 4.5 eq) of dimethylamine. After the addition of dimethylamine is completed, slowly add 9.00 kg (32.80 mol, 4.2 eq) of n-butyl lithium solution dropwise. During the addition, the reaction temperature is maintained at about -10°C. After the addition is completed, the temperature is naturally raised to room temperature (25±3°C) and the reaction is allowed to react for 1 hour.

[0061] S2. Add 0.011 kg (0.39 mol, 0.05 eq) of heterogeneous reaction catalyst, and then add 2.5 kg (7.81 mol, 1.0 eq) of hafnium tetrachloride. During the addition process, the reaction temperature is maintained between 40°C and 45°C. After the addition is completed, react at 45°C for 4 hours. The heterogeneous reaction catalyst (CAS: 485-71-2) has the following structure: The HNMR characterization spectrum of the heterogeneous reaction catalyst is shown in the attached Figure 3 The characterization data is 1 HNMR (400 MHz, CDCl 3 ): δ 8.86 (d, J = 4.5 Hz, 1H), 8.12 (d, J = 8.5 Hz, 1H), 8.03(d, J = 8.4 Hz, 1H), 7.69 (t, J = 7.6 Hz,1H), 7.58 (d, J = 4.4 Hz, 1H), 7.50 (t, J =7.6 Hz, 1H), 5.75 (ddd, J = 17.7, 10.2, 7.7 Hz, 1H), 5.65 (d, J = 4.1 Hz, 1H), 4.98 (s, 0.5H), 4.94 (d, J = 2.2 Hz, 1H), 4.90 (s, 0.5H), 3.47 – 3.36 (m, 1H), 3.19 – 3.02 (m, 2H), 2.72 – 2.58 (m, 2H), 2.27 (s, 1H), 1.83 (d, J = 14.9 Hz,1H), 1.62 – 1.42 (m, 2H), 1.30 – 1.15 (m, 2H), 0.92 – 0.77 (m, 1H).

[0062] S3. After the reactor was cooled to 25°C, 0.72 kg (10.93 mol, 1.4 eq) of cyclopentadiene monomer was added dropwise. After the addition was completed, the mixture was reacted at 45°C for 12 h. The filtrate was filtered, and the solvent was distilled off. Then, 2.44 kg of the product was distilled off under reduced pressure. The calculated yield was 83.20%.

[0063] Example 3

[0064] This embodiment provides a cyclopentadienyl metal precursor - CpHf (NMe 2 ) 3 The heterogeneous synthesis method comprises the following steps:

[0065] S1. Add 18 L of n-hexane to a 50 L reactor. After the temperature in the reactor is cooled to -15°C, 1.58 kg (35.15 mol, 4.5 eq) of dimethylamine is introduced. After the addition of dimethylamine is completed, 9.00 kg (32.80 mol, 4.2 eq) of n-butyl lithium solution is slowly added dropwise. The reaction temperature is maintained at about -15°C during the addition. After the addition is completed, the temperature is naturally raised to room temperature (25±3°C) and the reaction is allowed to react for 1 hour.

[0066] S2. Add 0.016 kg (0.39 mol, 0.05 eq) of heterogeneous reaction catalyst, and then add 2.5 kg (7.81 mol, 1.0 eq) of hafnium tetrachloride. During the addition process, the reaction temperature is maintained between 40°C and 45°C. After the addition is completed, the reaction is carried out at 45°C for 4 hours. The heterogeneous reaction catalyst (CAS: 69257-04-1) has the following structure: The HNMR characterization spectrum of the heterogeneous reaction catalyst is shown in the attached Figure 4 , the characterization data is 1 H NMR (400 MHz, CDCl 3 ): δ 8.81 (d, J = 4.4 Hz, 1H), 8.11 (d, J = 7.8 Hz,1H), 7.82 (d, J = 4.4 Hz, 1H), 7.73 (d, J = 7.7 Hz, 1H), 7.66 (d, J = 7.3 Hz, 2H),7.46 (d, J = 6.1 Hz, 1H), 7.26 – 7.23 (m, 2H), 7.19 (t, J = 7.4 Hz, 2H), 6.54 (d, J = 4.3 Hz, 1H), 5.71 (q,J = 12.0 Hz, 2H), 5.42 (ddd, J = 16.9, 10.4, 6.3 Hz,1H), 5.24 (s, 1H), 5.19 (s, 0.5H), 4.94 (d, J = 10.4 Hz, 1H), 4.74 (s, 1H), 4.01 (t, J = 9.0 Hz, 1H), 3.64 (d, J = 12.7 Hz, 1H), 3.13 (dt, J = 12.1, 9.6 Hz,2H), 2.48 (s, 1H), 2.13 (t, J = 11.7 Hz, 1H), 1.99 – 1.89 (m, 2H), 1.61 (s, 1H), 1.08 (s, 1H), 0.87 (d, J = 6.8 Hz, 0.5H).

[0067] S3. After the reactor was cooled to 25°C, 0.72 kg (10.93 mol, 1.4 eq) of cyclopentadiene monomer was added dropwise. After the addition was completed, the mixture was reacted at 45°C for 12 h. The filtrate was filtered and the solvent was distilled off. Then, 2.68 kg of the product was distilled off under reduced pressure. The calculated yield was 91.20%.

[0068] Example 4

[0069] This embodiment provides a cyclopentadienyl metal precursor, CpZr(NMe 2 ) 3 The heterogeneous synthesis method comprises the following steps:

[0070] S1. Add 18 L of n-hexane to a 50 L reactor. After the temperature in the reactor is cooled to -20 °C, add 1.58 kg (35.15 mol, 4.5 eq) of dimethylamine. After the addition of dimethylamine is completed, slowly add 9.00 kg (32.80 mol, 4.2 eq) of n-butyl lithium solution dropwise. During the addition, the reaction temperature is maintained at about -5 °C. After the addition is completed, the temperature is naturally raised to room temperature (25 ± 3 °C) and the reaction is carried out for 1 hour.

[0071] S2, add 0.016kg (0.39mol, 0.05eq) of heterogeneous reaction catalyst, then add 1.82kg (7.81mol, 1.0eq) of zirconium tetrachloride, maintain the reaction temperature between 40℃-45℃ during the addition process, and react at 45℃ for 4h after the addition. The heterogeneous reaction catalyst (CAS: 69257-04-1) has the following structure: .

[0072] S3. After the reactor was cooled to 25°C, 0.72 kg (10.93 mol, 1.4 eq) of cyclopentadiene monomer was added dropwise. After the addition was completed, the mixture was reacted at 45°C for 12 h. The filtrate was filtered and the solvent was distilled off. Then, 2.02 kg of the product was distilled off under reduced pressure. The calculated yield was 89.70%.

[0073] The product structure was characterized by HNMR (see Appendix Figure 5 ), the characterization data is 1 H NMR (C 6 D 6 ): δ2.92(S,18H,N(CH 3 ) 2 ), 6.06(S,5H,C 5 H 5 ).

[0074] Comparative Example 1

[0075] This comparative example provides a cyclopentadienyl metal precursor - CpHf (NMe 2 ) 3 The heterogeneous synthesis method comprises the following steps:

[0076] S1. Add 18 L of n-hexane to a 50 L reactor. After the temperature in the reactor is cooled to -18 °C, 1.58 kg (35.15 mol, 4.5 eq) of dimethylamine is introduced. After the addition of dimethylamine is completed, 9.00 kg (32.80 mol, 4.2 eq) of n-butyl lithium solution is slowly added dropwise. The reaction temperature is maintained at about -15 °C during the addition. After the addition is completed, the temperature is naturally raised to room temperature (25 ± 3 °C) and the reaction is carried out for 1 hour.

[0077] S2. Add 2.5 kg (7.81 mol, 1.0 eq) of hafnium tetrachloride. During the addition, maintain the reaction temperature between 40°C and 45°C. After the addition is completed, react at 45°C for 4 hours.

[0078] S3, after the reactor was cooled to 25°C, 0.72 kg (10.93 mol, 1.4 eq) of cyclopentadiene monomer was added dropwise, and the mixture was reacted at 45°C for 12 h. The mixture was filtered, and the filtrate was distilled to remove the solvent, and then 1.54 kg of the product was distilled under reduced pressure, with a yield of 52.5%.

[0079] Comparative Example 2

[0080] This comparative example provides a cyclopentadienyl metal precursor - CpHf (NMe 2 ) 3 The heterogeneous synthesis method comprises the following steps:

[0081] S1. Add 18 L of n-hexane to a 50 L reactor. After the temperature in the reactor is cooled to -15°C, 1.58 kg (35.15 mol, 4.5 eq) of dimethylamine is introduced. After the addition of dimethylamine is completed, 9.00 kg (32.80 mol, 4.2 eq) of n-butyl lithium solution is slowly added dropwise. The reaction temperature is maintained at about -15°C during the addition. After the addition is completed, the temperature is naturally raised to room temperature (25±3°C) and the reaction is allowed to react for 1 hour.

[0082] S2, add 3.29kg (7.81mol, 1.0eq) of heterogeneous reaction catalyst, then add 2.5kg (7.81mol, 1.0eq) of hafnium tetrachloride, maintain the reaction temperature between 40℃-45℃ during the addition process, and react at 45℃ for 4h after the addition. The heterogeneous reaction catalyst (CAS: 69257-04-1) has the following structure: .

[0083] S3, after the reactor was cooled to 25°C, 0.72 kg (10.93 mol, 1.4 eq) of cyclopentadiene monomer was added dropwise, and the mixture was reacted at 45°C for 12 h. The mixture was filtered, and the filtrate was distilled to remove the solvent, and then 1.83 kg of the product was distilled under reduced pressure, with a calculated yield of 62.3%.

[0084] Comparative Example 3

[0085] This comparative example provides a cyclopentadienyl metal precursor - CpHf (NMe 2 ) 3 The heterogeneous synthesis method comprises the following steps:

[0086] S1. Add 18 L of n-hexane to a 50 L reactor. After the temperature in the reactor is cooled to -18 °C, 1.58 kg (35.15 mol, 4.5 eq) of dimethylamine is introduced. After the addition of dimethylamine is completed, 9.00 kg (32.80 mol, 4.2 eq) of n-butyl lithium solution is slowly added dropwise. The reaction temperature is maintained at about -15 °C during the addition. After the addition is completed, the temperature is naturally raised to room temperature (25 ± 3 °C) and the reaction is carried out for 1 hour.

[0087] S2. Add 0.072 kg (0.39 mol, 0.05 eq) of heterogeneous reaction catalyst and 2.5 kg (7.81 mol, 1.0 eq) of hafnium tetrachloride. During the addition process, maintain the reaction temperature between 40°C and 45°C. After the addition is completed, react at 45°C for 4 hours. The heterogeneous reaction catalyst is trimethylbenzyl ammonium chloride (CAS: 56-93-9).

[0088] S3. After the reactor was cooled to 25°C, 0.72 kg (10.93 mol, 1.4 eq) of cyclopentadiene monomer was added dropwise. After the addition was completed, the mixture was reacted at 45°C for 12 h. The mixture was filtered, and the filtrate was distilled to remove the solvent. Then, 1.79 kg of the product was distilled under reduced pressure, with a yield of 61.0%.

[0089] Performance testing method:

[0090] 1. Yield: The calculation formula is (actual product mass / theoretical product mass)*100%.

[0091] 2. Process stability: Five batches of products were synthesized using the synthesis method of each embodiment, and the number of unqualified yields was calculated (yield ≥ 85% was qualified, and less than 85% was unqualified). The more unqualified yields, the worse the stability of the process. If the yields of the products synthesized in the five batches are all ≥ 85%, the process stability is better; the statistical results are shown in Table 1.

[0092] Table 1 Serial number Example 1 Example 2 Example 3 Example 4 Comparative Example 1 First batch yield 86.2% 89.0% 90.4% 87.5% 67.5% The second batch yield 85.8% 87.9% 88.0% 84.3% 45.0% The third batch yield 89.5% 85.1% 86.5% 85.0% 50.7% The fourth batch yield 85.0% 83.2% 91.2% 89.7% 52.5% The fifth batch yield 84.3% 84.8% 89.9% 90.3% 62.2%

[0093] Analysis: It can be seen from Table 1 that the synthesis method in Examples 1-4 with the addition of a heterogeneous reaction catalyst has a higher yield and process stability, while the multiphase synthesis process without the use of a heterogeneous reaction catalyst has not only a low yield but also poor process stability.

[0094] 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.

[0095] 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 heterogeneous synthesis method of a cyclopentadienyl metal precursor, characterized in that: The following steps are involved: After lithium dialkylamide, metal halide and heterogeneous reaction catalyst are mixed for reaction, cyclopentadiene monomer is added for reaction; the heterogeneous reaction catalyst has the following structure: ； Wherein, R1 is a C2-C6 alkenyl or a C2-C6 alkynyl, R2 is a substituted or unsubstituted phenyl, R3 is any one of H, a C1-C5 straight chain or branched alkyl, X is Cl or Br, and n is 0 or 1; The structure of the metal halide is represented by MY4, where M is selected from Ti, Zr, and Hf, and Y represents a halogen.

2. The heterogeneous synthesis method according to claim 1, characterized in that R1 is any one of vinyl, propenyl, allyl, butenyl, and ethynyl; and / or, R2 is any one of phenyl, benzyl, phenethyl, and phenyl substituted with 1 to 5 methyl groups; and / or, R3 includes any one of H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, and tert-butyl.

3. The heterogeneous synthesis method according to claim 1, characterized in that The amount of the heterogeneous reaction catalyst used is 0.1%-10% of the molar equivalent of the metal halide.

4. The heterogeneous synthesis method according to claim 1, characterized in that R1 is vinyl, R3 is H, and n is 0.

5. The heterogeneous synthesis method according to claim 1, characterized in that R1 is vinyl, R2 is phenyl, R3 is H, X is Cl, and n is 1.

6. The heterogeneous synthesis method according to claim 1, characterized in that R1 is vinyl, R2 is benzyl, R3 is H, X is Cl, and n is 1.

7. The heterogeneous synthesis method according to claim 1, characterized in that The molar equivalent ratio of the metal halide to the lithium dialkylamide is 1:4-6, and the molar equivalent ratio of the metal halide to the cyclopentadiene monomer is 1:1-2.

8. The heterogeneous synthesis method according to claim 1, characterized in that The heterogeneous synthesis method of the cyclopentadienyl metal precursor comprises the following steps: S1, adding solvent, dialkylamine and alkyl lithium into a reaction kettle for mixed reaction; S2, adding a heterogeneous reaction catalyst and a metal halide to react; S3, adding cyclopentadiene monomer to react; S4, filtering and distilling out the cyclopentadienyl metal precursor product; The structure of the cyclopentadienyl metal precursor is represented by R z CpM(NR x R y )3, wherein M is selected from Ti, Zr, Hf, Cp is cyclopentadienyl, R, R x and R y An alkyl group is independently selected from C1-C5, and z is an integer of 0-5.

9. The heterogeneous synthesis method according to claim 8, characterized in that: The molar equivalent ratio of dialkylamine to metal halide is 4-6:1; and / or, the alkyl lithium is selected from at least one of methyl lithium, n-butyl lithium, tert-butyl lithium, and phenyl lithium; and / or, the molar equivalent ratio of alkyl lithium to metal halide is 4-6:

1.

10. The heterogeneous synthesis method according to claim 8 or 9, characterized in that: The temperature of the mixed reaction in S1 is -30°C to 30°C, and the reaction time is 1-24h; and / or, the reaction temperature in S2 is 30-50° C. and the reaction time is 4-24 h; And / or, in S3, the reaction temperature is adjusted to 20-28° C. and then cyclopentadiene monomer is added. After the addition is completed, the reaction temperature is adjusted to 30-50° C. for reaction, and the reaction time is 8-24 hours.

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