Preparation method and device system of dialkylamino metal complex and triguanidinyl metal complex

Abstract

The present invention relates to a method and device system for preparing a dialkylamino metal complex and a triguanidine metal complex. The preparation method provided by the present invention combines the regulation and control of reaction conditions to promote reactions that are favorable for product generation, reduce the occurrence of side reactions, avoid the defect of introducing metal impurities using n-butyl lithium, and avoid the generation of components such as lithium salts that are inconvenient for subsequent separation, thereby facilitating product purification. Moreover, the dialkylamino metal complex and triguanidine metal complex prepared by the present invention meet the purity requirements for precursor materials in integrated circuit manufacturing.

Description

Technical Field

[0001] The present invention belongs to the technical field of semiconductor precursor materials, relates to the preparation of a precursor material, and in particular to a preparation method and device system of a dialkylamino metal complex and a triguanidine metal complex. Background Art

[0002] Oxides of elements such as lanthanum and yttrium have the advantages of wide band gap, low lattice energy and high dielectric constant. They have higher thermodynamic stability than ZrO2 and HfO2 and are candidate materials to replace SiO2 insulator materials.

[0003] La2O3 thin films can be prepared using methods such as chemical vapor deposition, sputtering, and atomic layer deposition. Because metal-nitrogen bonds have lower bond energies than metal-chlorine and metal-oxygen bonds, react rapidly with water, and produce fewer impurities than metal-carbon bonds, lanthanum complexes with alkylamino, amidino, or guanidino ligands (such as tris(dialkylamino)lanthanum and triguanidino lanthanum complexes) are more suitable for ALD deposition of La2O3 thin films. Yttrium oxide (Y2O3) can be deposited using similar complexes with yttrium replacing lanthanum.

[0004] Taking lanthanum as an example, La(NR 1 R 2 )3 is synthesized by using lithium dialkylamide LiNR 1 R 2 , Preparation process using halide LaX3 as raw material:

[0005] LaX3+LiNR 1 R 2 →La(NR 1 R 2 )3+LiX

[0006] Taking tris(dimethylamino)lanthanum La(NMe2)3 as an example, the unreacted LaCl3 and LiNMe2 mixture in this method can explode or undergo a highly exothermic reaction during separation, increasing the safety risks of the process. Furthermore, the reaction inevitably involves the use of alkyl lithium, and the reaction conditions are relatively harsh. The use of such metal reagents can easily introduce difficult-to-separate metallic impurities, affecting the purity of the final product. Furthermore, the generation of solid wastes such as lithium halide during the reaction further complicates separation.

[0007] The synthesis of lanthanum triguanide may be carried out in the following two ways:

[0008] The first method is to use LiNR first 1 R 2 The intermediate product tri(dialkylamino)lanthanum La(NR 1 R 2)3, and then with an excess of dialkylcarbodiimide R 3 -N=C=NR 3 Perform ligand reaction to prepare triguanidinyl lanthanum:

[0009] LaX3+LiNR 1 R 2 →La(NR 1 R 2 )3+LiX

[0010]

[0011] The second method is to first prepare guanidinolithium, and then react it with LaX3 to prepare triguanidinolanthana:

[0012]

[0013] or

[0014]

[0015] In the second method, guanidinolithium can be prepared by lithium amide and dialkylcarbodiimide, or directly prepared by n-butyl lithium and guanidine ligand. 1 R 2 )3, both methods inevitably use alkyl lithium, the conditions are relatively harsh, and it is easy to introduce difficult-to-separate metal impurities, affecting the purity of the final product; solid wastes such as lithium halide generated during the reaction increase the difficulty of separation.

[0016] Therefore, in order to meet the purity requirements of precursor materials in the integrated circuit manufacturing process, it is necessary to develop a preparation method and device system for dialkylamino metal complexes and triguanidine metal complexes that are suitable for industrial production with easy reaction control, simple separation and convenient operation. Summary of the Invention

[0017] The present invention aims to provide a method and apparatus system for preparing a dialkylamino metal complex and a triguanidine metal complex. The preparation method can reduce the occurrence of side reactions, avoid the defect of introducing metal impurities when using n-butyl lithium, and avoid the production of components such as lithium salts that are inconvenient for subsequent separation, thereby facilitating product purification. Moreover, the prepared dialkylamino metal complex and triguanidine metal complex meet the purity requirements for precursor materials in integrated circuit manufacturing.

[0018] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0019] In a first aspect, the present invention provides a method for preparing a dialkylamino metal complex, the preparation method comprising the following steps:

[0020] Under protective atmosphere, the halide MX3 reacts with excess trimethylsilyldialkylamine Me3SiNR in an inert solvent. 1 R 2 The reaction yields dialkylamino metal complex M(NR 1 R 2 )3, the reaction formula is as follows:

[0021] MX3+Me3SiNR 1 R 2 →M(NR 1 R 2 )3+Me3SiX;

[0022] The M is a lanthanide element and / or yttrium;

[0023] Said X is a halogen;

[0024] The R 1 With R 2 are independently alkyl, the N is amino nitrogen, and the Me is methyl.

[0025] In the preparation method of the dialkylamino metal complex provided by the present invention, trimethylsilyldialkylamine Me3SiNR 1 R 2 As a reactant, it provides a dialkylamino ligand on the one hand, and can also serve as a dehalogenation agent for the halide MX3 on the other hand. The dehalogenation product Me3SiX escapes in the form of gas during the reaction, which is conducive to the forward progress of the reaction. Therefore, the boiling point of Me3SiX is particularly important to promote the forward progress of the entire reaction. According to the generation rate of Me3SiX, in order to make the reaction proceed in the forward direction, trimethylsilyldialkylamine Me3SiNR 1 R 2 It can be added in batches or by dropwise addition.

[0026] Preferably, M is lanthanum and / or yttrium.

[0027] For example, the melting and boiling points of trimethylsilyl halide Me3SiX are as follows: the melting point of Me3SiF is -74°C and the boiling point is 16°C; the melting point of Me3SiCl is -40°C and the boiling point is 57°C; the melting point of Me3SiBr is -43°C and the boiling point is 79°C; the melting point of Me3SiI is <0°C and the boiling point is 106°C. When the by-product Me3SiX escapes in the form of gas during the reaction, the reactant trimethylsilyldialkylamine as a dehalogenating agent is preferably retained in the system to continue the reaction. Therefore, trimethylsilyldialkylamine Me3SiNR is preferred. 1 R 2 The boiling point of the by-product trimethylsilyl halide is higher than that of the by-product trimethylsilyl halide.

[0028] For example, when trimethylsilyldialkylamine Me3SiNR 1 R 2 When Me3SiNMe2 (boiling point 84 ° C), the boiling point of the released trimethylsilyl halide below 84 ° C is conducive to the forward reaction. At this time, the preferred halide is MF3 and / or MCl3; when trimethylsilyldialkylamine Me3SiNR 1 R 2 When the trimethylsilyl halide is Me3SiNEt2 (Et is ethyl, boiling point 125°C to 126°C), the boiling point of the released trimethylsilyl halide is below 125°C, which is conducive to the forward reaction. Considering the boiling point of the halide and the metal element content in the halide, the halide is preferably MF3 and / or MCl3;

[0029] Therefore, the halide MX3 is preferably MF3 and / or MCl3.

[0030] Preferably, the R 1 With R 2 are each independently a methyl group and / or an ethyl group.

[0031] Correspondingly, the trimethylsilyldialkylamine Me3SiNR 1 R 2 Preferred is any one of trimethylsilyldimethylamine, trimethylsilyldiethylamine or trimethylsilylmethylethylamine, or a combination of at least two thereof.

[0032] Preferably, the trimethylsilyldialkylamine Me3SiNR 1 R 2 The molar ratio of the feed to the halide MX3 is ≥3:1. In order to ensure the efficiency of the product generation, trimethylsilyldialkylamine Me3SiNR 1 R 2 The molar ratio of the halide MX3 to the halide MX3 is 3:1 to 9:1, for example, 3:1, 4:1, 6:1, 8:1, 9:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] In the present invention, trimethylsilyldialkylamine Me3SiNR 1 R 2 The molar ratio of MX3 to halide is 3:1 to 9:1, which can ensure that MX3 is completely converted into M(NR 1 R 2 )3. Reduce the formation of partially dehalogenated complexes.

[0034] Preferably, the feed mass ratio of the halide MX3 to the inert solvent is 1:4 to 1:40, for example, it can be 1:4, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35 or 1:40, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] The inert solvent in the present invention has a great influence on the MX3 and Me3SiNR 1 R 2 It plays the role of dispersion and dissolution.

[0036] Preferably, the inert solvent includes a hydrocarbon solvent that does not participate in the reaction.

[0037] The boiling point of the inert solvent selected in the present invention is higher than that of trimethylhalosilane Me3SiX, so as to avoid taking away too much inert solvent when removing Me3SiX; further, in order to reduce the evaporation of the solvent during the purification process, the inert solvent is preferably a solvent having a boiling point higher than that of Me3SiNR 1 R 2 A hydrocarbon solvent having a boiling point of 10°C or higher is used; and to facilitate removal of the solvent after the reaction, the boiling point of the inert solvent needs to be controlled to not exceed 150°C. Further preferably, the inert solvent is a hydrocarbon solvent having a boiling point of 60°C to 150°C, for example, 60°C, 70°C, 80°C, 90°C, 100°C, 120°C, or 150°C, but is not limited to the values ​​listed above, and other values ​​not listed within the numerical range are also applicable.

[0038] Preferably, the inert solvent includes any one of n-hexane (boiling point 68.9°C), n-heptane (boiling point 98°C), n-octane (boiling point 125°C), n-nonane (boiling point 151°C), n-decane (boiling point 174°C), toluene (boiling point 110°C), xylene or trimethylbenzene, or a combination of at least two thereof.

[0039] The xylene described in the present invention includes any one of p-xylene, m-xylene or o-xylene, or a combination of at least two of them. Typical but non-limiting combinations include a combination of p-xylene and m-xylene, a combination of m-xylene and o-xylene, a combination of p-xylene and o-xylene, or a combination of p-xylene, m-xylene and o-xylene.

[0040] The trimethylbenzene described in the present invention includes any one of mesitylene, unsymmetrical trimethylbenzene or chrysene, or a combination of at least two of them. Typical but non-limiting combinations include a combination of mesitylene and unsymmetrical trimethylbenzene, a combination of unsymmetrical trimethylbenzene and chrysene, a combination of mesitylene and chrysene, or a combination of mesitylene, unsymmetrical trimethylbenzene and chrysene.

[0041] Preferably, the protective atmosphere comprises nitrogen and / or an inert gas.

[0042] The reaction temperature in the first aspect of the present invention is preferably lower than that of trimethylsilyldialkylamine Me3SiNR 1 R 2 The boiling point of Me3SiNR is higher than that of trimethylsilane Me3SiX. 1 R 2 The precipitation in an inert solvent enables the reaction to proceed in the forward direction and avoids the formation of Me3SiNR 1 R 2 Volatile escape, preferably, the reaction temperature is 0°C to 150°C, for example, it can be 0°C, 20°C, 30°C, 50°C, 60°C, 80°C, 100°C, 120°C or 150°C, but is not limited to the listed values, other unlisted values ​​within the numerical range are also applicable, preferably 20°C to 120°C.

[0043] For example, when trimethylsilyldialkylamine Me3SiNR 1 R 2 When it is Me3SiNMe2, the reaction temperature should not exceed 84°C. If MF3 is selected as the metal source, the reaction temperature is preferably above 16°C and not more than 84°C; if MCl3 is selected as the metal source, the reaction temperature is preferably above 57°C and not more than 84°C.

[0044] For example, when trimethylsilyldialkylamine Me3SiNR 1 R 2 When it is Me3SiNEt2, the reaction temperature should not exceed 125°C. If MF3 is selected as the metal source, the reaction temperature is preferably above 16°C and not more than 125°C; if MCl3 is selected as the metal source, the reaction temperature is preferably above 57°C and not more than 125°C; if MBr3 is selected as the metal source, the reaction temperature is preferably above 79°C and not more than 84°C.

[0045] Preferably, the reaction time is 3 h to 30 h, for example, 3 h, 5 h, 8 h, 10 h, 12 h, 15 h, 16 h, 18 h, 20 h, 24 h, 25 h, 28 h or 30 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0046] Preferably, the reaction is carried out under stirring conditions.

[0047] Preferably, the stirring speed of the stirring condition is 30 rpm to 150 rpm, for example, it can be 30 rpm, 40 rpm, 50 rpm, 60 rpm, 80 rpm, 100 rpm, 120 rpm or 150 rpm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0048] In a second aspect, the present invention provides a device system for preparing the dialkylamino metal complex described in the first aspect, wherein the device system comprises a reaction unit, a pretreatment unit, a filtration unit, a purification unit, and a nitrogen supply unit;

[0049] The reaction unit includes a reaction device, a trimethylsilyldialkylamine supply device and a halide supply device; the trimethylsilyldialkylamine supply device and the halide supply device are independently connected to the reaction device through feed pipelines;

[0050] The nitrogen supply pipeline of the nitrogen supply unit is connected to the feed pipeline of the trimethylsilyldialkylamine supply device and the feed pipeline of the halide supply device respectively;

[0051] The pre-treatment unit includes a condensing device and a first vacuum generating device connected in sequence; the condensing device includes at least one condenser connected in series, and the bottom discharge port of the last condenser is connected to the light phase storage tank; the first vacuum generating device is used to control the vacuum degree of the condensing device;

[0052] The purification unit includes a sublimator, a fractionating device, a second vacuum generating device, a first crystallization device and a third vacuum generating device; the light phase outlet of the sublimator is connected to the fractionating device; the second vacuum generating device is used to control the vacuum degree of the fractionating device; the sublimator is also connected to the first crystallization device; the third vacuum generating device is used to control the vacuum degree of the first crystallization device.

[0053] The discharge port of the reaction device and the feed port of the sublimator are independently connected to the filtering unit respectively.

[0054] The preparation device system provided in the second aspect is used to prepare the dialkylamino metal complex M(NR 1 R 2 ) 3 when preparing:

[0055] (a) nitrogen replacement is performed on each unit and connecting pipeline involved in the preparation device system, and an inert solvent, a halide, and trimethylsilyldialkylamine are prepared according to the feed amount;

[0056] (b) mixing an inert solvent, a halide, and trimethylsilyldialkylamine in a reaction apparatus, and controlling the temperature in the reaction apparatus to allow the reaction to proceed;

[0057] (c) After the low-boiling point components are removed by distillation in the reaction unit, the product solution is filtered through a filtration unit and then enters a sublimator;

[0058] (d) controlling the temperature and pressure of the sublimator to perform vacuum distillation and sublimation, wherein the inert solvent enters the fractionation device through the light phase outlet above the sublimator and is collected in the heavy phase storage tank below the fractionation column; the dialkylamino metal complex enters the first crystallization device after vacuum sublimation and is collected in the first product storage tank below the crystallizer.

[0059] Illustratively, the reaction apparatus of the present invention is provided with a stirring device; the stirring device includes but is not limited to an anchor stirring device or a frame stirring device.

[0060] Preferably, the first fractionation device comprises a distillation column and a heavy phase storage tank; the heavy phase outlet of the distillation column is connected to the heavy phase storage tank; the light phase outlet of the sublimator is connected to the feed inlet of the distillation column; the first crystallization device comprises a first crystallizer and a first product storage tank;

[0061] The inert solvent is recovered in the heavy phase storage tank, and the dialkylamino metal complex M(NR 1 R 2 )3.

[0062] Preferably, the filtration unit comprises at least two filters connected in parallel; the discharge port of the reaction device and the feed port of the evaporator are connected to both ends of the filters respectively.

[0063] Exemplarily, the filter is a normal pressure filter or a pressure filter.

[0064] Preferably, the connecting pipeline between the filter and the reaction device and the connecting pipeline between the filter and the sublimator are respectively connected to the nitrogen supply pipeline of the nitrogen supply unit.

[0065] As a further preferred technical solution, the preparation method provided in the first aspect is carried out in the preparation device system provided in the second aspect.

[0066] In a third aspect, the present invention provides a method for preparing a triguanidine metal complex, the preparation method comprising the following steps:

[0067] (1) Under protective atmosphere, the halide MX3 is reacted with an excess of trimethylsilyldialkylamine Me3SiNR in an inert solvent. 1 R 2 The reaction obtains a dialkylamino metal complex solution, and the reaction formula is as follows:

[0068] MX3+3Me3SiNR 1 R 2 →M(NR 1 R 2 )3+3Me3SiX;

[0069] (2) Under protective atmosphere, dialkylcarbodiimide R3 -N=C=NR 3 and the dialkylamino metal complex M(NR 1 R 2 )3 solution for ligand reaction, and the product solution is purified to obtain the triguanidine metal complex, and the reaction formula is as follows:

[0070]

[0071] The M is a lanthanide element and / or yttrium;

[0072] Said X is a halogen;

[0073] The R 1 、R 2 With R 3 are independently alkyl, the N is amino nitrogen, and the Me is methyl.

[0074] In the preparation method of the triguanidine metal complex provided by the present invention, trimethylsilyldialkylamine Me3SiNR 1 R 2 As a reactant, it provides a dialkylamino ligand on the one hand, and can also serve as a dehalogenation agent for the halide MX3 on the other hand. The dehalogenation product Me3SiX escapes in the form of gas during the reaction, which is conducive to the forward progress of the reaction. Therefore, the boiling point of Me3SiX is particularly important to promote the forward progress of the entire reaction. According to the generation rate of Me3SiX, in order to make the reaction proceed in the forward direction, trimethylsilyldialkylamine Me3SiNR 1 R 2 It can be added in batches or by dropwise addition.

[0075] Preferably, M is lanthanum and / or yttrium.

[0076] For example, the melting and boiling points of trimethylsilyl halides are as follows: the melting point of Me3SiF is -74°C and the boiling point is 16°C; the melting point of Me3SiCl is -40°C and the boiling point is 57°C; the melting point of Me3SiBr is -43°C and the boiling point is 79°C; the melting point of Me3SiI is <0°C and the boiling point is 106°C. When the by-product Me3SiX escapes in the form of gas during the reaction, the reactant trimethylsilyldialkylamine as a dehalogenating agent is preferably retained in the system to continue the reaction. Therefore, trimethylsilyldialkylamine Me3SiNR is preferred. 1 R 2 The boiling point of the by-product trimethylsilyl halide is higher than that of the by-product trimethylsilyl halide.

[0077] For example, when trimethylsilyldialkylamine Me3SiNR 1 R 2When Me3SiNMe2 (boiling point 84 ° C), the boiling point of the released trimethylsilyl halide below 84 ° C is conducive to the forward reaction. At this time, the preferred halide is MF3 and / or MCl3; when trimethylsilyldialkylamine Me3SiNR 1 R 2 When the trimethylsilyl halide is Me3SiNEt2 (Et is ethyl, boiling point 125°C to 126°C), the boiling point of the released trimethylsilyl halide is below 125°C, which is conducive to the forward reaction. Considering the boiling point of the halide and the metal content in the halide, the halide is preferably MF3 and / or MCl3;

[0078] Therefore, the halide MX3 includes MF3 and / or MCl3.

[0079] Preferably, the R 1 With R 2 are each independently a methyl group and / or an ethyl group.

[0080] Correspondingly, the trimethylsilyldialkylamine Me3SiNR 1 R 2 Preferred is any one of trimethylsilyldimethylamine, trimethylsilyldiethylamine or trimethylsilylmethylethylamine, or a combination of at least two thereof.

[0081] Preferably, the R 3 is any one of isopropyl, tert-butyl, tert-pentyl, cyclohexyl, or cyclopentyl, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of isopropyl and tert-butyl, a combination of tert-pentyl and cyclohexyl, a combination of tert-butyl, cyclohexyl, and cyclopentyl, or a combination of isopropyl, tert-butyl, tert-pentyl, cyclohexyl, and cyclopentyl.

[0082] Correspondingly, the dialkylcarbodiimide R 3 -N=C=NR 3 Preferred is any one of diisopropylcarbodiimide, di-tert-butylcarbodiimide, di-tert-amylcarbodiimide, dicyclohexylcarbodiimide or dicyclopentylcarbodiimide, or a combination of at least two thereof.

[0083] The obtained triguanidine metal complex is Any one or a combination of at least two of .

[0084] In order to ensure that MX3 is completely converted into M(NR 1 R 2 ) 3, reduce the formation of other partially dehalogenated complexes, the trimethylsilyldialkylamine Me3SiNR in the preparation method of the triguanidine metal complex provided by the present invention 1 R 2 The feed ratio needs to be controlled.1 R 2 When the molar ratio of MX3 is lower than 3:1, a considerable proportion of M(NR 1 R 2 )2X or M(NR 1 R 2 )X2 is generated and then combined with R 3 -N=C=NR 3 When the reaction occurs, guanidine halides or even halogenated amidine metal complexes are obtained. 1 R 2 When the molar ratio of MX3 to the feed is higher than 9:1, the preparation efficiency of the triguanidine metal complex is affected.

[0085] To ensure the formation of favorable reaction, Me3SiNR needs to be removed in time. 1 R 2 Otherwise, the remaining Me3SiNR 1 R 2 It may be combined with the dialkylcarbodiimide R 3 -N=C=NR 3 The following reaction occurs:

[0086]

[0087] The generated trimethylsilyl-substituted guanidine ligand has a high boiling point and is difficult to remove, which makes it difficult to separate the triguanidine metal complex. In fact, the trimethylsilyl-substituted guanidine ligand can further react with the halide to form the triguanidine metal complex, as follows:

[0088]

[0089] However, to ensure complete dehalogenation of the halide to form the triguanidinium metal complex, an excess of trimethylsilyl-substituted guanidine ligand must be added, which also increases the difficulty of subsequent separation of the triguanidinium metal complex. Therefore, the route of completely dehalogenating the halide with trimethylsilyl-substituted guanidine ligand to prepare the triguanidinium metal complex is not preferred. The route of reacting the dialkylamino metal complex with a dialkylcarbodiimide to prepare the triguanidinium metal complex is preferred.

[0090] To ensure complete dehalogenation of the halide, trimethylsilyldialkylamine Me3SiNR 1 R 2 The molar ratio of the feed to the halide MX3 is 3:1 to 9:1, for example, 3:1, 4:1, 5:1, 6:1, 8:1 or 9:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0091] In addition to providing dialkylamino ligands and acting as a dehalogenating agent, trimethylsilyldialkylamine can also act as a chemical dehydrating agent. When trace water exists in the system, the following reaction occurs:

[0092] 2Me3SiNR 1 R 2 +H2O→Me3Si-O-SiMe3+2HNR 1 R 2 ;

[0093] From the reaction formula, we can see that one water molecule can be absorbed by two molecules of Me3SiNR 1 R 2 Consumption yields dialkylamine and hexamethyldisiloxane.

[0094] Preferably, the reaction temperature in step (1) is lower than trimethylsilyldialkylamine Me3SiNR 1 R 2 further preferably, the temperature of the reaction in step (1) is higher than the boiling point of trimethylhalosilane Me3SiX.

[0095] Preferably, the reaction temperature in step (1) is 0°C to 150°C, for example, 0°C, 10°C, 30°C, 50°C, 60°C, 80°C, 100°C, 120°C or 150°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0096] Me3SiNR 1 R 2 The dehalogenation reaction with MX3 can be carried out in the temperature range of 0°C to 150°C. When the reaction temperature of step (1) is lower than 0°C, the presence of Me3SiNR 1 R 2 The problem of precipitation in inert solvents will also reduce the volatilization of Me3SiX, affecting the smooth progress of the reaction; the higher the reaction temperature, the more conducive to the forward reaction, and it is conducive to reducing the formation of other partially dehalogenated complexes, and the more conducive to the formation of dialkylamino metal complexes, but the temperature should not be higher than Me3SiNR 1 R 2 boiling point, otherwise it will lead to Me3SiNR 1 R 2 The escape of halogenated metals may cause the dehalogenation reaction to fail to proceed smoothly, and there is also a risk of destroying the intermediate dialkylamino metal complex. Therefore, the reaction temperature in step (1) is preferably 20°C to 120°C.

[0097] Preferably, the reaction time of step (1) is 3 h to 30 h, for example, 3 h, 5 h, 8 h, 10 h, 15 h, 20 h, 25 h or 30 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0098] Preferably, the halide MX3 and the dialkylcarbodiimide R 3 -N=C=NR 3 The molar ratio of the feed is 1:3 to 1:6, for example, 1:3, 1:4 or 1:6, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0099] To generate triguanidine metal complexes, an excess of dialkylcarbodiimide is added to the reaction. 3 -N=C=NR 3 If the feed is too little, incomplete guanidine coordination products will be generated, such as biguanidine and monoguanidine metal complexes, and the amount of triguanidine metal complexes will be reduced. 3 -N=C=NR 3 If too much material is added, the production efficiency of the triguanidine metal complex will be reduced.

[0100] Step (2) the dialkylcarbodiimide and dialkylamino metal complex M (NR 1 R 2 )3. The solutions are mixed and can be added in batches by dropwise addition or all at once.

[0101] Preferably, the temperature of the ligand reaction in step (2) is lower than R 3 -N=C=NR 3 Further preferably, the temperature of the ligand reaction in step (2) is higher than that of the dialkylamine HNR 1 R 2 and the boiling point of (CH3)3SiX.

[0102] Preferably, the temperature of the ligand reaction in step (2) is 0°C to 150°C, for example, it can be 0°C, 10°C, 30°C, 50°C, 60°C, 80°C, 100°C, 120°C or 150°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0103] M(NR 1 R 2 )3 and R 3 -N=C=NR 3The ligand reaction can be carried out in the temperature range of 0℃ to 150℃. The lowest temperature of the ligand reaction depends on the melting point of the inert solvent. However, when the temperature is lower than 0℃, the rate of the ligand reaction slows down and the reaction efficiency decreases. For the ligand reaction, a higher reaction temperature is conducive to the formation of the product, especially when the reaction temperature of the ligand reaction is higher than that of the dialkylamine HNR. 1 R 2 and the boiling point of Me3SiX, which is beneficial for the residual HNR 1 R 2 and the volatilization of Me3SiX, which is beneficial to the purification of triguanidine metal products; but the temperature of the ligand reaction should not exceed R 3 -N=C=NR 3 boiling point, otherwise R 3 -N=C=NR 3 A large amount of volatiles escape, affecting the efficiency of the ligand reaction.

[0104] i Pr-N=C=N- i The boiling point of Pr is 145~148℃. t Bu-N=C=N- t The boiling point of Bu is 160°C, and that of Cy-N=C=N-Cy is 122-124°C / 6 mmHg. The boiling points of dimethylamine are 7°C, diethylamine is 55°C, and methylethylamine are 36-37°C. The boiling points of Me3SiF are 16°C, Me3SiCl is 57°C, and Me3SiBr is 79°C; the boiling point of Me3SiI is 106°C.

[0105] For example, when the dialkylcarbodiimide is i Pr-N=C=N- i When Pr is used, the temperature of the ligand reaction should not exceed 145°C, and is preferably 0°C to 145°C; if the raw materials of step (1) are MF3 and Me3SiNMe2, the temperature of the ligand reaction is preferably 16°C to 145°C; if the raw materials of step (1) are MF3 and Me3SiNEtMe, the temperature of the ligand reaction is preferably 57°C to 145°C.

[0106] For example, when the dialkylcarbodiimide is t Bu-N=C=N- tWhen Bu is used, the temperature of the ligand reaction should not exceed the limited maximum reaction temperature of 150°C, because the generated dialkylamino metal complex is easily destroyed, and is preferably 0°C to 150°C; if the raw materials of step (1) are MBr3 and Me3SiNMe2, the temperature of the ligand reaction is preferably 79°C to 150°C; if the raw materials of step (1) are MF3 and Me3SiNEtMe, the temperature of the ligand reaction is preferably 36°C to 150°C; if the raw materials of step (1) are MCl3 and Me3SiNEt2, the temperature of the ligand reaction is preferably 57°C to 150°C.

[0107] The temperature of the ligand reaction in step (2) of the present invention can be a constant temperature or can vary within a temperature range during the ligand reaction.

[0108] Preferably, the ligand reaction time in step (2) is 2 h to 20 h, for example, 2 h, 4 h, 5 h, 8 h, 10 h, 12 h, 15 h, 18 h or 20 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0109] Preferably, the inert solvent in step (1) comprises a hydrocarbon solvent that does not participate in the reaction; preferably a hydrocarbon solvent having a boiling point below 150°C; further preferably a hydrocarbon solvent having a boiling point higher than trimethylsilyldialkylamine Me3SiNR 1 R 2 Hydrocarbon solvents with a boiling point of 10°C or above.

[0110] The role of the inert solvent in step (1) of the present invention is to disperse the reactants; although MX3 and Me3SiNR 1 R 2 The reaction can also be carried out in the absence of solvent, but due to the dispersion and dissociation in the absence of solvent, it is easy to form a partially dehalogenated complex, and it is not easy to fully dehalogenate to form M(NR 1 R 2 )3; and in the process of R 3 -N=C=NR 3 When the ligand reacts, additional solvent is required for dispersion.

[0111] The boiling point of the inert solvent selected in the present invention is preferably higher than the boiling point of trimethylhalosilane Me3SiX, so as to avoid taking away too much inert solvent while removing Me3SiX, thereby avoiding the addition of additional inert solvent; further, in order to reduce the evaporation of the solvent during the purification process, the inert solvent is preferably higher than the boiling point of Me3SiNR 1 R 2 Moreover, in order to facilitate the removal of the solvent after the reaction, the boiling point of the inert solvent needs to be controlled not to exceed 150°C.

[0112] Preferably, the inert solvent in step (1) includes any one of n-hexane (boiling point 69°C), n-heptane (boiling point 98°C), n-octane (boiling point 125°C), toluene (boiling point 110°C), o-xylene (boiling point 144.4°C) or m-xylene (boiling point 138°C), or a combination of at least two thereof. Typical but non-limiting combinations include a combination of n-heptane and n-octane, a combination of n-octane and toluene, a combination of toluene and o-xylene, a combination of o-xylene and m-xylene, a combination of n-heptane, n-octane and toluene, a combination of toluene, o-xylene and m-xylene, or a combination of n-heptane, n-octane, toluene, o-xylene and m-xylene.

[0113] Preferably, the mass ratio of the halide MX3 to the inert solvent in step (1) is 1:4 to 1:40, for example, it can be 1:4, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35 or 1:40, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0114] In the present invention, in order to ensure uniform and stable dispersion of MX3 and reduce the formation of other partially dehalogenated complexes, the mass ratio of MX3 to inert solvent feed should not be less than 1:4. To ensure the efficiency of product formation, the mass ratio of MX3 to inert solvent feed should not exceed 1:40.

[0115] Preferably, the protective atmosphere comprises nitrogen and / or an inert gas.

[0116] Preferably, the reaction in step (1) and / or the ligand reaction in step (2) are carried out under stirring conditions;

[0117] Preferably, the stirring speed of the stirring condition is 30 rpm to 150 rpm, for example, it can be 30 rpm, 40 rpm, 50 rpm, 60 rpm, 80 rpm, 100 rpm, 120 rpm or 150 rpm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0118] In a fourth aspect, the present invention provides a triguanidine metal complex device system, the device system comprising a reaction unit, a pre-treatment unit, a filtration unit, a purification unit and a nitrogen supply unit;

[0119] The reaction unit includes a reaction device, a trimethylsilyldialkylamine supply device, a halide supply device, and a dialkylcarbodiimide supply device; the trimethylsilyldialkylamine supply device, the halide supply device, and the dialkylcarbodiimide supply device are independently connected to the reaction device through feed pipelines;

[0120] The nitrogen supply pipeline of the nitrogen supply unit is connected to the feed pipeline of the trimethylsilyldialkylamine supply device and the feed pipeline of the halide supply device respectively;

[0121] The pre-treatment unit includes a condensing device and a first vacuum generating device connected in sequence; the condensing device includes at least one condenser connected in series, and the bottom discharge port of the last condenser is connected to the light phase storage tank; the first vacuum generating device is used to control the vacuum degree of the condensing device;

[0122] The purification unit includes a sublimator, a fractionating device, a second vacuum generating device, a first crystallizer, a second crystallizer and a third vacuum generating device; the light phase outlet of the sublimator is connected to the fractionating device; the second vacuum generating device is used to control the vacuum degree of the fractionating device; the sublimator is also connected to the first crystallizer and the second crystallizer; the third vacuum generating device is used to control the vacuum degree of the first crystallizer and the second crystallizer;

[0123] The discharge port of the reaction device and the feed port of the evaporator are independently connected to the filtering unit respectively.

[0124] Illustratively, the reaction apparatus of the present invention is provided with a stirring device; the stirring device includes but is not limited to an anchor stirring device or a frame stirring device.

[0125] Preferably, the fractionation device comprises a rectification column and a heavy phase storage tank; the first crystallization device comprises a first crystallizer and a first product storage tank, and the second crystallization device comprises a second crystallizer and a second product storage tank;

[0126] The heavy phase outlet of the distillation column is connected to a heavy phase storage tank; the light phase outlet of the sublimator is connected to the feed inlet of the distillation column. The first crystallizer is connected to the first product storage tank below and to a third vacuum generator above; the second crystallizer is connected to the second product storage tank below and to a third vacuum generator above.

[0127] The inert solvent is recovered in the heavy phase storage tank, and the dialkylamino metal complex M(NR 1 R 2 )3, triguanidine lanthanum is obtained in the second product storage tank.

[0128] Preferably, the filtration unit comprises at least two filters connected in parallel; the discharge port of the reaction device and the feed port of the sublimator are connected to both ends of the filters respectively.

[0129] Preferably, the connecting pipeline between the filter and the reaction device and the connecting pipeline between the filter and the sublimator are respectively connected to the nitrogen supply pipeline of the nitrogen supply unit.

[0130] As a further preferred technical solution, the preparation method provided in the third aspect is carried out in the preparation device system provided in the fourth aspect.

[0131] Compared with the prior art, the present invention has the following beneficial effects:

[0132] (1) The preparation method of the dialkylamino metal complex provided by the present invention utilizes trimethylsilyldialkylamine to completely dehalogenate the halide, the reaction is easy to control, the operation is simple, no solid waste such as lithium halide that is inconvenient to separate is generated, the obtained product is high in purity, and it is easy to achieve industrial production;

[0133] (2) The preparation method of the triguanidine metal complex provided by the present invention is a method of using trimethylsilyldialkylamine to completely dehalogenate the halide to prepare the intermediate product dialkylamino metal complex, and then reacting it with dialkylcarbodiimide to prepare the product; this method is a solid-liquid reaction of the halide and the dehalogenating agent, which is different from the solid-solid reaction of alkylamide lithium and the halide, and is easier to disperse evenly. Within the range allowed by the boiling point of the dehalogenating agent, the dehalogenation reaction can be carried out at a higher temperature and the reaction rate is faster; this method can avoid the introduction of metal impurities due to the impure n-butyl lithium used in the technical route of dialkylamide lithium, and can also avoid the generation of solid waste such as lithium salts that are not convenient for subsequent separation, thereby facilitating product purification, and the obtained product can easily meet the purity requirements of the precursor material in the manufacture of integrated circuits;

[0134] Trimethylsilyldialkylamine, as a reactant, acts as a dehalogenating agent to dehalogenate the halide, a donor of dialkylamino ligands, and a chemical dehydrating agent. Adding an excess of trimethylsilyldialkylamine to the reaction ensures complete dehalogenation of the halide and removes trace moisture remaining in the reaction apparatus and materials, thereby facilitating product formation. Using dialkylcarbodiimide as a guanidine precursor allows the reaction to proceed at a higher temperature within the boiling point range, resulting in a faster reaction rate.

[0135] (3) The reaction device provided by the present invention adopts the technical route of trimethylsilyldialkylamine, and the reaction conditions are easy to control; the reaction unit and the purification unit in the device are combined, and in addition to purifying the product, the by-products and unreacted trimethylsilyldialkylamine and solvent can be recovered, and the low-boiling point dialkylamine and trimethylhalosilane are collected at the same time for regenerating trimethylsilyldialkylamine. BRIEF DESCRIPTION OF THE DRAWINGS

[0136] Figure 1 A schematic structural diagram of the device system for preparing triguanidine metal complexes provided by the present invention;

[0137] Wherein: 11, reaction device; 12, trimethylsilyldialkylamine supply device; 13, halide mixing tank; 14, solvent tank; 15, dialkylcarbodiimide supply device;

[0138] 21, front condenser; 22, rear condenser; 23, light phase storage tank; 24, first cold trap; 25, first vacuum generator;

[0139] 31, first filter; 32, second filter;

[0140] 41, sublimator; 42, waste tank; 43, fractionation device; 44, heavy phase storage tank; 45, second cold trap; 46, second vacuum generating device; 47, first crystallizer; 48, first product storage tank; 49, second crystallizer; 410, second product storage tank; 411, third cold trap; 412, third vacuum generating device. DETAILED DESCRIPTION

[0141] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0142] In the specific embodiment of the present invention, the preparation method of the dialkylamino metal complex and the preparation method of the triguanidinyl metal complex can be carried out as follows: Figure 1 The triguanidinium metal complex preparation system is shown. That is, the dialkylamino metal complex preparation system and the triguanidinium metal complex preparation system have the same parts. When the dialkylamino metal complex is prepared using the triguanidinium metal complex preparation system, only the corresponding device units are used.

[0143] like Figure 1 The triguanidine metal complex preparation device system shown includes a reaction unit, a pre-treatment unit, a filtration unit, a purification unit and a nitrogen supply unit;

[0144] The reaction unit includes a reaction device 11, a trimethylsilyldialkylamine supply device 12, a halide supply device and a dialkylcarbodiimide supply device; the trimethylsilyldialkylamine supply device 12, the halide supply device and the dialkylcarbodiimide supply device are independently connected to the reaction device 11 through feed pipelines;

[0145] The halide supply device includes a solvent tank 14 and a halide mixing tank 13 . The solvent outlet of the solvent tank 14 is connected to the halide mixing tank 13 . The discharge port of the halide mixing tank 13 is connected to the reaction device 11 through a feed pipe.

[0146] The nitrogen supply pipeline of the nitrogen supply unit is connected to the feed pipeline of the trimethylsilyldialkylamine supply device 12 and the feed pipeline of the halide supply device respectively;

[0147] The pre-treatment unit includes a condensing device and a first vacuum generating device 25 connected in sequence; the condensing device includes a front condenser 21 and a rear condenser 22 connected in series, and the bottom discharge port of the rear condenser 22 is connected to the light phase storage tank 23; the first vacuum generating device 25 is used to control the vacuum degree of the condensing device; a first cold trap 24 is provided between the first vacuum generating device 25 and the condenser to protect the first vacuum generating device 25;

[0148] The purification unit includes a sublimator 41, a waste tank 42, a fractionation device 43, a second vacuum generating device 46, a first crystallization device 47, a second crystallization device 49 and a third vacuum generating device 412; the light phase outlet of the sublimator 41 is connected to the fractionation device 43, and the bottom discharge port of the sublimator 41 is connected to the waste tank 42; the second vacuum generating device 46 is used to control the vacuum degree of the fractionation device 42; the connecting pipeline between the second vacuum generating device 46 and the fractionation device 43 is provided with a second cold trap 45 to protect the second vacuum generating device 46; the bottom of the diverter 43 is provided with a second cold trap 45 to protect the second vacuum generating device 46; The discharge port is connected to the heavy phase storage tank 44; the sublimator 41 is connected to the first crystallization device 47 and the second crystallization device 49 respectively, and the third vacuum generating device 412 is used to control the vacuum degree of the first crystallization device 47 and the second crystallization device 49; the lower discharge port of the first crystallization device 47 is connected to the first product storage tank 48, and the lower discharge port of the second crystallization device 49 is connected to the second product storage tank 410; the connecting pipelines of the third vacuum generating device 412 and the first crystallization device 47 and the second crystallization device 49 are provided with a third cold trap 411 to protect the third vacuum generating device 412;

[0149] The discharge port of the reaction device 11 and the feed port of the sublimator 41 are independently connected to a filtration unit; the filtration unit includes a first filter 31 and a second filter 32 connected in parallel; the discharge port of the reaction device 11 and the feed port of the sublimator 41 are connected to both ends of the filter respectively;

[0150] The inert solvent is recovered in the heavy phase storage tank 44, and the dialkylamino metal complex M (NR 1 R 2 )3. A triguanidine metal complex is obtained in the second product storage tank 410.

[0151] The connecting pipeline between the filter and the reaction device 11 and the connecting pipeline between the filter and the sublimator 41 are respectively connected to the nitrogen supply pipeline of the nitrogen supply unit.

[0152] When the triguanidine metal complex device system is used to prepare the triguanidine metal complex, the method includes the following steps:

[0153] (a) nitrogen replacement is performed on each unit and connecting pipeline involved in the device system, and an inert solvent, a halide, trimethylsilyldialkylamine, and a dialkylcarbodiimide are prepared according to the feed amount;

[0154] (b) dispersing a portion of the inert solvent in the solvent tank with the halide in a halide mixing tank, and transferring the mixture to a reaction apparatus; then rinsing the halide mixing tank with the remaining solvent, and transferring the mixture to the reaction apparatus; adding trimethylsilyldialkylamine to the reaction apparatus, and controlling the temperature in the reaction apparatus to allow the reaction to proceed; after the reaction is completed, removing the generated trimethylhalosilane by distillation, adjusting the temperature in the reaction apparatus to below the boiling point of the dialkylcarbodiimide, adding the dialkylcarbodiimide, and conducting a ligand reaction;

[0155] (c) After the low-boiling point components are removed by distillation in the reaction unit, the product solution is filtered through a filtration unit and then enters a sublimator;

[0156] (d) controlling the temperature and pressure of the sublimator to perform vacuum distillation, wherein the inert solvent enters a fractionation device through a light phase outlet above the sublimator, and the inert solvent is recovered by the fractionation device; the dialkylamino metal complex in the solid in the sublimator is treated by a first crystallization device and collected in a first product storage tank, and the triguanidine metal complex in the remaining solid is treated by a second crystallization device and collected in a second product storage tank.

[0157] Example 1-1

[0158] This embodiment provides a method for preparing tris(dimethylamino)lanthanum, which comprises the following steps:

[0159] Under nitrogen atmosphere, in a 1L reaction apparatus, 34.3g (0.14mol) of LaCl3 was reacted with 73.9g (0.63mol) of Me3SiNMe2 in 343g (501mL) of the inert solvent n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0160] The obtained tris(dimethylamino)lanthanum La(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)lanthanum in a first crystallization device.

[0161] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C., and the reaction time was 6 h.

[0162] In this embodiment, the molar ratio of Me3SiNMe2 to LaCl3 is 4.5:1; the mass ratio of LaCl3 to n-heptane is 1:10.

[0163] Example 1-2

[0164] This embodiment provides a method for preparing tris(dimethylamino)lanthanum, which comprises the following steps:

[0165] Under nitrogen atmosphere, in a 1L reaction apparatus, 68.7g (0.28mol) of LaCl3 was reacted with 98.5g (0.84mol) of Me3SiNMe2 in 275g (402mL) of the inert solvent n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0166] The obtained tris(dimethylamino)lanthanum La(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)lanthanum in a first crystallization device.

[0167] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C., and the reaction time was 6 h.

[0168] In this embodiment, the molar ratio of Me3SiNMe2 to LaCl3 is 3:1; the mass ratio of LaCl3 to n-heptane is 1:4.

[0169] Examples 1-3

[0170] This embodiment provides a method for preparing tris(dimethylamino)lanthanum, which comprises the following steps:

[0171] Under nitrogen atmosphere, in a 1L reaction apparatus, 12.3g (0.05mol) of LaCl3 was reacted with 52.8g (0.45mol) of Me3SiNMe2 in 492g (718mL) of the inert solvent n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0172] The obtained tris(dimethylamino)lanthanum La(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)lanthanum in a first crystallization device.

[0173] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C., and the reaction time was 6 h.

[0174] In this embodiment, the molar ratio of Me3SiNMe2 to LaCl3 is 9:1; the mass ratio of LaCl3 to n-heptane is 1:40.

[0175] Examples 1-4

[0176] This example provides a method for preparing tris(methylethylamino)lanthanum, which is the same as Example 1-1 except that the molar amount of Me3SiNMe2 is replaced by Me3SiNEtMe and the mass of n-heptane is replaced by n-octane.

[0177] Examples 1-5

[0178] This example provides a method for preparing tris(diethylamino)lanthanum, which is the same as Example 1-1 except that the molar amount of Me3SiNMe2 is replaced by Me3SiNEt2 and the mass of n-heptane is replaced by n-nonane.

[0179] Examples 1-6

[0180] This embodiment provides a method for preparing tris(dimethylamino)lanthanum, which comprises the following steps:

[0181] Under nitrogen atmosphere, in a 1L reaction apparatus, 34.3g (0.175mol) of LaF3 was reacted with 92.4g (0.788mol) of Me3SiNMe2 in 343g (520mL) of the inert solvent n-hexane. After the by-product Me3SiF ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0182] The obtained tris(dimethylamino)lanthanum La(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)lanthanum in a first crystallization device.

[0183] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C., and the reaction time was 6 h.

[0184] In this embodiment, the molar ratio of Me3SiNMe2 to LaF3 is 4.5:1; the mass ratio of LaF3 to n-hexane is 1:10.

[0185] Examples 1-7

[0186] This embodiment provides a method for preparing tris(dimethylamino)lanthanum, which comprises the following steps:

[0187] Under nitrogen atmosphere, in a 1L reaction apparatus, 34.3g (90.6mmol) of LaBr3 reacted with 47.8g (0.408mol) of Me3SiNMe2 in 343g (394mL) of the inert solvent toluene. The unreacted Me3SiNMe2 and the generated by-product Me3SiBr were distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0188] The obtained tris(dimethylamino)lanthanum La(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)lanthanum in a first crystallization device.

[0189] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 80° C., and the reaction time was 6 h.

[0190] In this embodiment, the molar ratio of Me3SiNMe2 to LaBr3 is 4.5:1; the mass ratio of LaBr3 to toluene is 1:10.

[0191] Examples 1-8

[0192] This embodiment provides a method for preparing tris(dimethylamino)lanthanum, which comprises the following steps:

[0193] Under nitrogen atmosphere, in a 1L reaction apparatus, 34.3g (0.066mol) of LaI3 and 34.8g (0.297mol) of Me3SiNMe2 were reacted in 343g (396mL) of the inert solvent national standard mixed xylene (GB / T3407-2019). The unreacted Me3SiNMe2 and the generated by-product Me3SiI were distilled at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0194] The obtained tris(dimethylamino)lanthanum La(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)lanthanum in a first crystallization device.

[0195] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 80° C., and the reaction time was 6 h.

[0196] In this embodiment, the molar ratio of Me3SiNMe2 to LaI3 is 4.5:1; the mass ratio of LaI3 to national standard mixed xylene is 1:10.

[0197] Examples 1-9

[0198] This embodiment provides a method for preparing tris(dimethylamino)lanthanum, which is the same as Example 1-1 except that the feeding amount of Me3SiNMe2 is changed so that the feeding molar ratio of Me3SiNMe2 to LaCl3 is 2:1.

[0199] In this embodiment, since LaCl3 is not completely dechlorinated, no product is generated.

[0200] Examples 1-10

[0201] This embodiment provides a method for preparing tris(dimethylamino)lanthanum, which is the same as Examples 1-3 except that the feeding amount of Me3SiNMe2 is changed so that the feeding molar ratio of Me3SiNMe2 to LaCl3 is 10:1.

[0202] The amount of Me3SiNMe2 added in this embodiment is too much, which affects the preparation efficiency of the product.

[0203] Examples 1-11

[0204] This example provides a method for preparing tris(dimethylamino)lanthanum, which is the same as Example 1-2 except that the feeding amount of n-heptane is changed so that the feeding mass ratio of LaCl3 to n-heptane is 1:3.

[0205] Examples 1-12

[0206] This example provides a method for preparing tris(dimethylamino)lanthanum, which is the same as that of Examples 1-3 except that the amount of n-heptane added is changed so that the mass ratio of LaCl3 to n-heptane is 1:42.

[0207] The amount of n-heptane added in this embodiment is too much, which affects the preparation efficiency of the product.

[0208] The mass of the tri(dialkylamino)lanthanum prepared in the above example, the yield calculated based on the lanthanum halide feed, and the HPLC purity were measured. The results are shown in Table 1.

[0209] Table 1

[0210]

[0211]

[0212] The “——” in Table 1 indicates that no product was generated in Examples 1-9, and therefore no relevant measurement results were obtained.

[0213] Example 2-1

[0214] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0215] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 34.3 g (0.14 mol) of LaCl3 reacted with 73.9 g (0.63 mol) of Me3SiNMe2 in 343 g (501 mL) of an inert solvent, n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0216] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0217] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C to carry out the reaction of 79.5 g (0.63 mol) of diisopropylcarbodiimide. i Pr-N=C=N- i Pr was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h of addition to obtain a product solution;

[0218] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0219] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and a tris(dimethyldiisopropylguanidino)lanthanum complex is obtained in a second crystallization device.

[0220] In this embodiment, the molar ratio of Me3SiNMe2 to LaCl3 is 4.5:1; the mass ratio of LaCl3 to n-heptane is 1:10; the mass ratio of LaCl3 to i Pr-N=C=N- i The feeding molar ratio of Pr is 1:4.5.

[0221] Example 2-2

[0222] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0223] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 68.7 g (0.28 mol) of LaCl3 reacted with 98.5 g (0.84 mol) of Me3SiNMe2 in 275 g (402 mL) of an inert solvent, n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0224] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C., and the reaction time was 6 h.

[0225] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C to carry out the reaction of 106.0 g (0.84 mol) of diisopropylcarbodiimide. i Pr-N=C=N- i Pr was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h of addition to obtain a product solution;

[0226] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0227] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and a tris(dimethyldiisopropylguanidino)lanthanum complex is obtained in a second crystallization device.

[0228] In this embodiment, the molar ratio of Me3SiNMe2 to LaCl3 is 3:1; the mass ratio of LaCl3 to n-heptane is 1:4, and the mass ratio of LaCl3 to i Pr-N=C=N- i The feeding molar ratio of Pr is 1:3.

[0229] Example 2-3

[0230] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0231] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 12.3 g (0.05 mol) of LaCl3 reacted with 52.8 g (0.45 mol) of Me3SiNMe2 in 492 g (718 mL) of an inert solvent, n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0232] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C., and the reaction time was 6 h.

[0233] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C to carry out the reaction of 37.9 g (0.30 mol) of diisopropylcarbodiimide. i Pr-N=C=N- i Pr was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h of addition to obtain a product solution;

[0234] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0235] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(dimethyldiisopropylguanidino)lanthanum is obtained in a second crystallization device.

[0236] In this embodiment, the molar ratio of Me3SiNMe2 to LaCl3 is 9:1; the mass ratio of LaCl3 to n-heptane is 1:40, and the mass ratio of LaCl3 to i Pr-N=C=N- i The feeding molar ratio of Pr is 1:6.

[0237] Examples 2-4

[0238] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0239] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 34.3 g (0.14 mol) of LaCl3 reacted with 73.9 g (0.63 mol) of Me3SiNMe2 in 343 g (501 mL) of an inert solvent, n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum La(NMe2)3 solution.

[0240] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0241] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C to carry out the reaction of 97.2 g (0.63 mol) of di-tert-butylcarbodiimide. t Bu-N=C=N- t Bu was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h of addition to obtain a product solution;

[0242] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0243] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(dimethyldi-tert-butylguanidino)lanthanum is obtained in a second crystallization device.

[0244] In this embodiment, the molar ratio of Me3SiNMe2 to LaCl3 is 4.5:1; the mass ratio of LaCl3 to n-heptane is 1:10; the mass ratio of LaCl3 to t Bu-N=C=N-t The feeding molar ratio of Bu is 1:4.5.

[0245] Examples 2-5

[0246] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0247] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 34.3 g (0.14 mol) of LaCl3 reacted with 82.7 g (0.63 mol) of Me3SiNEtMe in 343 g (488 mL) of an inert solvent, n-octane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNEtMe was distilled off at elevated temperature to obtain a tris(methylethylamino)lanthanum La(NEtMe)3 solution.

[0248] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0249] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C to prepare 114.9 g (0.63 mol) of di-tert-amylcarbodiimide. t Am-N=C=N- t Am was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h to obtain a product solution;

[0250] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0251] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(methylethyldi-tert-amylguanidino)lanthanum is obtained in a second crystallization device.

[0252] In this embodiment, the molar ratio of Me3SiNEtMe to LaCl3 is 4.5:1; the mass ratio of LaCl3 to n-octane is 1:10; the mass ratio of LaCl3 to t Am-N=C=N- t The feeding molar ratio of Am is 1:4.5.

[0253] Examples 2-6

[0254] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0255] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 34.3 g (0.14 mol) of LaCl3 reacted with 82.7 g (0.63 mol) of Me3SiNEtMe in 343 g (488 mL) of an inert solvent, n-octane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNEtMe was distilled off at elevated temperature to obtain a tris(methylethylamino)lanthanum La(NEtMe)3 solution.

[0256] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0257] (2) Under nitrogen atmosphere, 112.3 g (0.63 mol) of dicyclopentylcarbodiimide Cp-N=C=N-Cp was added dropwise while maintaining the temperature at 60° C., stirring was continued during the addition, and the ligand reaction was carried out after 2 h of the addition to obtain a product solution;

[0258] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0259] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(methylethyldicyclopentylguanidino)lanthanum is obtained in a second crystallization device.

[0260] In this embodiment, the molar ratio of Me3SiNEtMe to LaCl3 is 4.5:1; the mass ratio of LaCl3 to n-octane is 1:10; and the molar ratio of LaCl3 to Cp-N=C=N-Cp is 1:4.5.

[0261] Examples 2-7

[0262] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0263] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 34.3 g (0.14 mol) of LaCl3 reacted with 91.6 g (0.63 mol) of Me3SiNEt2 in 343 g (476 mL) of the inert solvent n-nonane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNEt2 was distilled off at elevated temperature to obtain a tris(diethylamino)lanthanum solution.

[0264] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0265] (2) Under nitrogen atmosphere, 130.0 g (0.63 mol) of dicyclohexylcarbodiimide Cy-N=C=N-Cy was added dropwise while maintaining the temperature at 60° C., stirring was continued during the addition, and the ligand reaction was carried out after 2 h of the addition to obtain a product solution;

[0266] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0267] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(diethyldicyclohexylguanidino)lanthanum is obtained in a second crystallization device.

[0268] In this embodiment, the molar ratio of Me3SiNEt2 to LaCl3 is 4.5:1; the mass ratio of LaCl3 to n-nonane is 1:10; and the molar ratio of LaCl3 to Cy-N=C=N-Cy is 1:4.5.

[0269] Examples 2-8

[0270] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0271] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 34.3 g (0.175 mol) of LaF3 and 92.4 g (0.788 mol) of Me3SiNMe2 were reacted in 343 g (520 mL) of an inert solvent, n-hexane. After the by-product Me3SiF ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum solution.

[0272] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 30° C. and the reaction time was 6 h;

[0273] (2) Under nitrogen atmosphere, the temperature was maintained at 30°C to carry out the reaction of 99.4 g (0.788 mol) of diisopropylcarbodiimide. i Pr-N=C=N- i Pr was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h of addition to obtain a product solution;

[0274] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0275] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(dimethyldiisopropylguanidino)lanthanum is obtained in a second crystallization device.

[0276] In this embodiment, the molar ratio of Me3SiNMe2 to LaF3 is 4.5:1; the mass ratio of LaF3 to n-hexane is 1:10; i Pr-N=C=N- i The feeding molar ratio of Pr is 1:4.5.

[0277] Examples 2-9

[0278] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0279] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 34.3 g (90.6 mmol) of LaBr3 reacted with 47.8 g (0.408 mol) of Me3SiNMe2 in 343 g (394 mL) of an inert solvent, toluene. The unreacted Me3SiNMe2 and the generated by-product Me3SiBr were distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum solution.

[0280] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 80° C. and the reaction time was 6 h;

[0281] (2) Under nitrogen atmosphere, the temperature was maintained at 80°C to carry out the reaction of 51.5 g (0.408 mol) of diisopropylcarbodiimide. i Pr-N=C=N- i Pr was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h of addition to obtain a product solution;

[0282] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 80° C. for 2 h, and then 100° C. for 2 h;

[0283] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(dimethyldiisopropylguanidino)lanthanum is obtained in a second crystallization device.

[0284] In this embodiment, the molar ratio of Me3SiNMe2 to LaBr3 is 4.5:1; the mass ratio of LaBr3 to toluene is 1:10; the mass ratio of LaBr3 to i Pr-N=C=N- i The feeding molar ratio of Pr is 1:4.5.

[0285] Example 2-10

[0286] This embodiment provides a method for preparing a triguanidinyl lanthanum complex, which comprises the following steps:

[0287] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 34.3 g (0.066 mol) of LaI3 reacted with 34.8 g (0.297 mol) of Me3SiNMe2 in 343 g (396 mL) of an inert solvent, the national standard mixed xylene (GB / T3407-2019), and the unreacted Me3SiNMe2 and the generated by-product Me3SiI were distilled off at elevated temperature to obtain a tris(dimethylamino)lanthanum solution;

[0288] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 80° C. and the reaction time was 6 h;

[0289] (2) Under nitrogen atmosphere, the temperature was maintained at 80°C to carry out the reaction of 37.5 g (0.297 mol) of diisopropylcarbodiimide. i Pr-N=C=N- i Pr was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h of addition to obtain a product solution;

[0290] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 80° C. for 2 h, and then 100° C. for 2 h;

[0291] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(dimethyldiisopropylguanidino)lanthanum is obtained in a second crystallization device.

[0292] In this embodiment, the molar ratio of Me3SiNMe2 to LaI3 is 4.5:1; the mass ratio of LaI3 to national standard mixed xylene is 1:10; i Pr-N=C=N- i The feeding molar ratio of Pr is 1:4.5.

[0293] Example 2-11

[0294] This embodiment provides a method for preparing triguanidinyl lanthanum, except that the diisopropylcarbodiimide is changed i Pr-N=C=N- i The amount of Pr added makes the lanthanum chloride and i Pr-N=C=N- i Except that the molar ratio of Pr was 1:2, the rest were the same as in Example 2-1.

[0295] The amount of diisopropylcarbodiimide added in the reaction is insufficient, resulting in the generation of a partially guanidine-substituted lanthanum-containing complex and no product.

[0296] Example 2-12

[0297] This embodiment provides a method for preparing triguanidinyl lanthanum, except that the diisopropylcarbodiimide is changed i Pr-N=C=N- i The amount of Pr added is such that the tungsten chloride and i Pr-N=C=N- i Except that the molar ratio of Pr was 1:7, the rest were the same as in Example 2-1.

[0298] The mass of the triguanidinyl lanthanum complex prepared in the above example, the yield calculated based on the lanthanum halide feed, and the HPLC purity were measured. The results are shown in Table 2.

[0299] Table 2

[0300] Product mass (g) Yield (%) Purity (wt%) Example 2-1 83.7 92 99.99 Example 2-2 154.6 85 99.4 Example 2-3 29.6 91 99.99 Examples 2-4 92.5 90 99.99 Examples 2-5 107.2 89 99.97 Examples 2-6 108.0 91 99.95 Examples 2-7 117.3 86 99.94 Examples 2-8 106.9 94 99.99 Examples 2-9 47.7 81 99.5 Example 2-10 27.4 64 98.1 Example 2-11 —— —— —— Example 2-12 82.8 91 99.98

[0301] The “——” in Table 2 indicates that no product was generated in Example 2-11, and therefore no relevant measurement results were obtained.

[0302] Example 3-1

[0303] This embodiment provides a method for preparing tris(dimethylamino)yttrium, which comprises the following steps:

[0304] Under nitrogen atmosphere, in a 1L reaction apparatus, 35.1g (0.18mol) of YCl3 was reacted with 95.0g (0.81mol) of Me3SiNMe2 in 351g (513mL) of the inert solvent n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)yttrium Y(NMe2)3 solution.

[0305] The obtained tris(dimethylamino)yttrium Y(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)yttrium in a first crystallization device.

[0306] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C., and the reaction time was 6 h.

[0307] In this embodiment, the molar ratio of Me3SiNMe2 to YCl3 is 4.5:1; the mass ratio of YCl3 to n-heptane is 1:10.

[0308] Example 3-2

[0309] This example provides a method for preparing tris(methylethylamino)yttrium, which is the same as Example 3-1 except that the molar amount of Me3SiNMe2 is replaced by Me3SiNEtMe and the mass of n-heptane is replaced by n-octane.

[0310] Example 3-3

[0311] This example provides a method for preparing tris(diethylamino)yttrium, which is the same as Example 3-1 except that the molar amount of Me3SiNMe2 is replaced by Me3SiNEt2 and the mass of n-heptane is replaced by n-nonane.

[0312] Examples 3-4

[0313] This embodiment provides a method for preparing tris(dimethylamino)yttrium, which comprises the following steps:

[0314] Under nitrogen atmosphere, in a 1L reaction apparatus, 35.1g (0.241mol) of YF3 was reacted with 127.0g (1.083mol) of Me3SiNMe2 in 351g (532mL) of the inert solvent n-hexane. After the by-product Me3SiF ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)yttrium Y(NMe2)3 solution.

[0315] The obtained tris(dimethylamino)yttrium Y(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)yttrium in a first crystallization device.

[0316] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C., and the reaction time was 6 h.

[0317] In this embodiment, the molar ratio of Me3SiNMe2 to YF3 is 4.5:1; the mass ratio of YF3 to n-hexane is 1:10.

[0318] Examples 3-5

[0319] This embodiment provides a method for preparing tris(dimethylamino)yttrium, which comprises the following steps:

[0320] Under nitrogen atmosphere, in a 1L reaction apparatus, 35.1g (0.107mol) of YBr3 reacted with 56.4g (0.481mol) of Me3SiNMe2 in 351g (403mL) of the inert solvent toluene. The unreacted Me3SiNMe2 and the generated by-product Me3SiBr were distilled off at elevated temperature to obtain a tris(dimethylamino)yttrium Y(NMe2)3 solution.

[0321] The obtained tris(dimethylamino)yttrium Y(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)yttrium in a first crystallization device.

[0322] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 80° C., and the reaction time was 6 h.

[0323] In this embodiment, the molar ratio of Me3SiNMe2 to YBr3 is 4.5:1; the mass ratio of YBr3 to toluene is 1:10.

[0324] Examples 3-6

[0325] This embodiment provides a method for preparing tris(dimethylamino)yttrium, which comprises the following steps:

[0326] Under nitrogen atmosphere, in a 1L reaction apparatus, 35.1g (74.7mmol) of YI3 reacted with 39.4g (0.336mol) of Me3SiNMe2 in 351g (405mL) of the inert solvent national standard mixed xylene (GB / T3407-2019). The unreacted Me3SiNMe2 and the generated by-product Me3SiI were distilled at elevated temperature to obtain tris(dimethylamino)yttrium Y(NMe2)3 solution.

[0327] The obtained tris(dimethylamino)yttrium Y(NMe2)3 solution is subjected to reduced pressure distillation and sublimation in a sublimator to obtain tris(dimethylamino)yttrium in a first crystallization device.

[0328] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 80° C., and the reaction time was 6 h.

[0329] In this embodiment, the molar ratio of Me3SiNMe2 to YI3 is 4.5:1; the mass ratio of YI3 to mixed xylene is 1:10.

[0330] The mass of tris(dialkylamino)yttrium prepared in the above example, the yield calculated based on the yttrium halide feed, and the HPLC purity were measured. The results are shown in Table 3.

[0331] Table 3

[0332] Product mass (g) Yield (%) HPLC purity (wt%) Example 3-1 34.6 87 99.99 Example 3-2 39.2 83 99.99 Example 3-3 44.0 80 99.99 Examples 3-4 48.0 90 99.99 Examples 3-5 16.8 71 99.76 Examples 3-6 7.8 47 98.1

[0333] Example 4-1

[0334] This embodiment provides a method for preparing a triguanidinium yttrium complex, which comprises the following steps:

[0335] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 35.1 g (0.18 mol) of YCl3 reacted with 95.0 g (0.81 mol) of Me3SiNMe2 in 351 g (513 mL) of the inert solvent n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)yttrium Y(NMe2)3 solution.

[0336] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0337] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C to carry out the reaction of 102.2 g (0.81 mol) of diisopropylcarbodiimide. i Pr-N=C=N- i Pr was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h of addition to obtain a product solution;

[0338] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0339] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and a tris(dimethyldiisopropylguanidino)yttrium complex is obtained in a second crystallization device.

[0340] In this embodiment, the molar ratio of Me3SiNMe2 to YCl3 is 4.5:1; the mass ratio of YCl3 to n-heptane is 1:10; i Pr-N=C=N- i The feeding molar ratio of Pr is 1:4.5.

[0341] Example 4-2

[0342] This embodiment provides a method for preparing a triguanidinium yttrium complex, the preparation method comprising the following steps:

[0343] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 35.1 g (0.18 mol) of YCl3 reacted with 95.0 g (0.81 mol) of Me3SiNMe2 in 351 g (513 mL) of the inert solvent n-heptane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNMe2 was distilled off at elevated temperature to obtain a tris(dimethylamino)yttrium Y(NMe2)3 solution.

[0344] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0345] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C to carry out the reaction of 125.0 g (0.81 mol) of di-tert-butylcarbodiimide. t Bu-N=C=N- t Bu was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h to obtain a product solution;

[0346] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0347] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(dimethyldi-tert-butylguanidino)yttrium is obtained in a second crystallization device.

[0348] In this embodiment, the molar ratio of Me3SiNMe2 to YCl3 is 4.5:1; the mass ratio of YCl3 to n-heptane is 1:10; t Bu-N=C=N- t The feeding molar ratio of Bu is 1:4.5.

[0349] Example 4-3

[0350] This embodiment provides a method for preparing a triguanidinium yttrium complex, which comprises the following steps:

[0351] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 35.1 g (0.18 mol) of YCl3 reacted with 106.3 g (0.81 mol) of Me3SiNEtMe in 351 g (499 mL) of an inert solvent, n-octane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNEtMe was distilled off at elevated temperature to obtain a tris(methylethylamino)yttrium Y(NEtMe)3 solution.

[0352] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0353] (2) Under nitrogen atmosphere, the temperature was maintained at 60°C to prepare 147.7 g (0.81 mol) of di-tert-amylcarbodiimide. t Am-N=C=N- t Am was added dropwise with continuous stirring during the addition process, and the ligand reaction was carried out after 2 h to obtain a product solution;

[0354] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0355] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(methylethyldi-tert-amylguanidino)yttrium is obtained in a second crystallization device.

[0356] In this embodiment, the molar ratio of Me3SiNEtMe to YCl3 is 4.5:1; the mass ratio of YCl3 to n-octane is 1:10; t Am-N=C=N- t The feeding molar ratio of Am is 1:4.5.

[0357] Example 4-4

[0358] This embodiment provides a method for preparing a triguanidinium yttrium complex, the preparation method comprising the following steps:

[0359] (1) Under nitrogen atmosphere, in a 1 L reaction apparatus, 35.1 g (0.18 mol) of YCl3 reacted with 106.3 g (0.81 mol) of Me3SiNEtMe in 351 g (499 mL) of an inert solvent, n-octane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNEtMe was distilled off at elevated temperature to obtain a tris(methylethylamino)yttrium Y(NEtMe)3 solution.

[0360] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0361] (2) Under nitrogen atmosphere, 144.4 g (0.81 mol) of dicyclopentylcarbodiimide Cp-N=C=N-Cp was added dropwise while maintaining the temperature at 60° C., stirring was continued during the addition, and the ligand reaction was carried out after 2 h of the addition to obtain a product solution;

[0362] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0363] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(methylethyldicyclopentylguanidino)yttrium is obtained in a second crystallization device.

[0364] In this embodiment, the molar ratio of Me3SiNEtMe to YCl3 is 4.5:1; the mass ratio of YCl3 to n-octane is 1:10; and the molar ratio of YCl3 to Cp-N=C=N-Cp is 1:4.5.

[0365] Examples 4-5

[0366] This embodiment provides a method for preparing a triguanidinium yttrium complex, the preparation method comprising the following steps:

[0367] (1) In a 1 L reaction apparatus, 35.1 g (0.18 mol) of YCl3 reacted with 117.7 g (0.81 mol) of Me3SiNEt2 in 351 g (488 mL) of the inert solvent n-nonane. After the by-product Me3SiCl ceased to evaporate, the unreacted Me3SiNEt2 was distilled off at elevated temperature to obtain a tris(diethylamino)yttrium solution.

[0368] The reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the reaction temperature was 60° C. and the reaction time was 6 h;

[0369] (2) Under nitrogen atmosphere, 167.1 g (0.81 mol) of dicyclohexylcarbodiimide Cy-N=C=N-Cy was added dropwise while maintaining the temperature at 60° C., stirring was continued during the addition, and the ligand reaction was carried out after 2 h of the addition to obtain a product solution;

[0370] The ligand reaction was carried out under stirring conditions at a stirring speed of 100 rpm; the temperature of the ligand reaction was 60° C. for 2 h, and then 80° C. for 2 h;

[0371] The obtained product solution is subjected to reduced pressure distillation and sublimation in a sublimator, and tris(diethyldicyclohexylguanidino)yttrium is obtained in a second crystallization device.

[0372] In this embodiment, the molar ratio of Me3SiNEt2 to YCl3 is 4.5:1; the mass ratio of YCl3 to n-nonane is 1:10; and the molar ratio of YCl3 to Cy-N=C=N-Cy is 1:4.5.

[0373] The mass of the triguanidine yttrium complex prepared in the above example, the yield calculated based on the yttrium halide feed, and the HPLC purity were measured. The results are shown in Table 4.

[0374] Table 4

[0375]

[0376]

[0377] In summary:

[0378] (1) The preparation method of the dialkylamino metal complex provided by the present invention utilizes trimethylsilyldialkylamine to completely dehalogenate the halide, the reaction is easy to control, the operation is simple, no solid waste such as lithium halide that is inconvenient to separate is generated, the obtained product is high in purity, and it is easy to achieve industrial production;

[0379] (2) The preparation method of the triguanidine metal complex provided by the present invention is a method of using trimethylsilyldialkylamine to completely dehalogenate the halide to prepare the intermediate product dialkylamino metal complex, and then reacting it with dialkylcarbodiimide to prepare the product; this method is a solid-liquid reaction of the halide and the dehalogenating agent, which is different from the solid-solid reaction of alkylamide lithium and the halide, and is easier to disperse evenly. Within the range allowed by the boiling point of the dehalogenating agent, the dehalogenation reaction can be carried out at a higher temperature and the reaction rate is faster; this method can avoid the introduction of metal impurities due to the impure n-butyl lithium used in the technical route of dialkylamide lithium, and can also avoid the generation of solid waste such as lithium salts that are not convenient for subsequent separation, thereby facilitating product purification, and the obtained product can easily meet the purity requirements of the precursor material in the manufacture of integrated circuits;

[0380] Trimethylsilyldialkylamine, as a reactant, acts as a dehalogenating agent to dehalogenate the halide, a donor of dialkylamino ligands, and a chemical dehydrating agent. Adding an excess of trimethylsilyldialkylamine to the reaction ensures complete dehalogenation of the halide and removes trace moisture remaining in the reaction apparatus and materials, thereby facilitating product formation. Using dialkylcarbodiimide as a guanidine precursor allows the reaction to proceed at a higher temperature within the boiling point range, resulting in a faster reaction rate.

[0381] (3) The reaction device provided by the present invention adopts the technical route of trimethylsilyldialkylamine, and the reaction conditions are easy to control; the reaction unit and the purification unit in the device are combined, and in addition to purifying the product, the by-products and unreacted trimethylsilyldialkylamine and solvent can be recovered, and the low-boiling point dialkylamine and trimethylhalosilane are collected at the same time for regenerating trimethylsilyldialkylamine.

[0382] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a dialkylamino metal complex, characterized in that: The preparation method comprises the following steps: Under protective atmosphere, the halide MX3 reacts with excess trimethylsilyldialkylamine Me3SiNR in an inert solvent. 1 R 2 The reaction yields dialkylamino metal complex M(NR 1 R 2 ) 3 solution, the reaction formula is as follows: MX3+Me3SiNR 1 R 2 →M(NR 1 R 2 )3+Me3SiX; The trimethylsilyldialkylamine Me3SiNR 1 R 2 The molar ratio of the halide MX3 to the inert solvent is 3:1 to 9:1; the mass ratio of the halide MX3 to the inert solvent is 1:4 to 1:40; the inert solvent includes a hydrocarbon solvent that does not participate in the reaction; the inert solvent is a hydrocarbon solvent with a boiling point of 60°C to 150°C; the reaction temperature is 0°C to 150°C; The M is a lanthanide element and / or yttrium; Said X is a halogen; The R 1 With R 2 are independently methyl and / or ethyl, the N is amino nitrogen, and the Me is methyl.

2. The preparation method according to claim 1, characterized in that The halide MX3 includes MF3 and / or MCl3.

3. The preparation method according to claim 1, characterized in that The inert solvent includes any one of n-hexane, n-heptane, n-octane, n-nonane, n-decane, toluene, xylene or trimethylbenzene, or a combination of at least two thereof.

4. The preparation method according to claim 1, characterized in that The protective atmosphere includes nitrogen and / or inert gas.

5. The preparation method according to claim 1, characterized in that The reaction temperature is 20°C to 120°C.

6. The preparation method according to claim 1, characterized in that The reaction time is 3 h to 30 h.

7. The preparation method according to claim 1, characterized in that The reaction is carried out under stirring conditions.

8. The preparation method according to claim 7, characterized in that The stirring speed of the stirring condition is 30 rpm to 150 rpm.

9. A method for preparing a triguanidine metal complex, characterized in that: The preparation method comprises the following steps: (1) Under protective atmosphere, the halide MX3 is reacted with an excess of trimethylsilyldialkylamine Me3SiNR in an inert solvent. 1 R 2 The reaction yields dialkylamino metal complex M(NR 1 R 2 ) 3 solution, the reaction formula is as follows: MX3+Me3SiNR 1 R 2 →M(NR 1 R 2 )3+Me3SiX; (2) Under protective atmosphere, excess dialkylcarbodiimide R 3 -N=C=NR 3 and the dialkylamino metal complex M(NR 1 R 2 )3 solution for ligand reaction, and the product solution is purified to obtain the triguanidine metal complex, and the reaction formula is as follows: The trimethylsilyldialkylamine Me3SiNR 1 R 2 The molar ratio of the halide MX3 to the dialkylcarbodiimide R is 3:1 to 9:1; 3 -N=C=NR 3 The molar ratio of the feed materials is 1:3 to 1:6; the feed mass ratio of the halide MX3 to the inert solvent is 1:4 to 1:40; the temperature of the reaction in step (1) is 0°C to 150°C; the inert solvent in step (1) includes a hydrocarbon solvent that does not participate in the reaction; the inert solvent is a hydrocarbon solvent with a boiling point lower than 150°C; the temperature of the ligand reaction in step (2) is 0°C to 150°C; The M is a lanthanide element and / or yttrium; Said X is a halogen; The R 1 With R 2 are independently methyl and / or ethyl, and the R 3 It is any one of isopropyl, tert-butyl, tert-pentyl, cyclohexyl or cyclopentyl, or a combination of at least two thereof; N is amino nitrogen; and Me is methyl.

10. The preparation method according to claim 9, characterized in that The halide MX3 includes MF3 and / or MCl3.

11. The preparation method according to claim 9, characterized in that The reaction temperature in step (1) is lower than trimethylsilyldialkylamine Me3SiNR 1 R 2 boiling point.

12. The preparation method according to claim 11, characterized in that The reaction temperature in step (1) is higher than the boiling point of trimethylhalosilane Me3SiX.

13. The preparation method according to claim 9, characterized in that The reaction temperature in step (1) is 20°C to 120°C.

14. The preparation method according to claim 9, characterized in that The reaction time of step (1) is 3h to 30h.

15. The preparation method according to claim 9, characterized in that The temperature of the ligand reaction in step (2) is lower than that of the dialkylcarbodiimide R 3 -N=C=NR 3 boiling point.

16. The preparation method according to claim 15, characterized in that The temperature of the ligand reaction in step (2) is higher than that of trimethylhalosilane Me3SiX and dialkylamine HNR 1 R 2 boiling point.

17. The preparation method according to claim 9, characterized in that The temperature of the ligand reaction in step (2) is 20°C to 120°C.

18. The preparation method according to claim 9, characterized in that The ligand reaction time in step (2) is 2 h to 20 h.

19. The preparation method according to claim 9, characterized in that The inert solvent in step (1) is an inert solvent having a boiling point higher than trimethylsilyldialkylamine Me3SiNR 1 R 2 Hydrocarbon solvents with a boiling point of 10°C or above.

20. The preparation method according to claim 9, characterized in that The inert solvent in step (1) includes any one of n-hexane, n-heptane, n-octane, toluene, o-xylene or m-xylene, or a combination of at least two thereof.

21. The preparation method according to claim 9, characterized in that The protective atmosphere includes nitrogen and / or inert gas.

22. The preparation method according to claim 9, characterized in that The reaction in step (1) and / or the ligand reaction in step (2) are carried out under stirring conditions.

23. The preparation method according to claim 22, characterized in that The stirring speed of the stirring condition is 30 rpm to 150 rpm.

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