Preparation method of stannous tert-amyl alcohol

Abstract

The invention relates to a preparation method of stannous tert-amyl alcohol, which comprises the following steps: reacting tin powder with tert-amyl alcohol in the presence of a composite initiator in a protective atmosphere, collecting filtrate after the reaction is finished, and carrying out reduced pressure rectification treatment to obtain the stannous tert-amyl alcohol, the composite initiator comprises cuprous bromide and triphenylphosphine. Tin powder and tert-amyl alcohol serve as reaction raw materials, stannous tert-amyl alcohol can be prepared through reaction in the presence of the specific composite initiator, and the yield of the target product can reach 85%. Besides, the target product prepared by the preparation method is easy to purify, meanwhile, residues of halogen elements and metal elements such as lithium / sodium / potassium and the like can be effectively avoided, stannous tert-amyl alcohol with the metal purity as high as 6N is obtained, and the high-purity requirement of the semiconductor field on stannous tert-amyl alcohol is met.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic chemistry and microelectronic material technology, and in particular to a preparation method of tertiary amyl stannous alcoholate. BACKGROUND

[0002] Tertiary amyl stannous alcoholate, as an important organotin compound, is a colorless transparent liquid with unique chemical properties. It can be used as a highly efficient catalyst in organic synthesis reactions, especially in ester exchange reactions, polymerization reactions and other fields. At the same time, it also shows good application prospects in material surface modification, synthesis of pharmaceutical intermediates, etc. In recent years, with the popularization of atomic layer deposition (ALD) technology, tertiary amyl stannous alcoholate as a precursor is increasingly widely used in semiconductor manufacturing processes, and higher requirements are put forward for its purity, impurity control and cost. With the continuous improvement of product quality and cost control in related industries, the development of low-cost, high-purity tertiary amyl stannous alcoholate synthesis process has become the research focus in this field.

[0003] At present, the synthesis methods of divalent alkoxystannane compounds mainly include the following types: (1) Displacement method of halogenated tin and alkoxide: halogenated tin reacts with metal alkoxide such as lithium alkoxide, sodium alkoxide or potassium alkoxide to prepare. This method produces a large amount of by-products such as lithium halide, sodium halide or potassium halide during the reaction, which is difficult to separate and purify, resulting in high metal impurity content in the product, which is difficult to meet the 6N level ultra-high purity requirements of the semiconductor industry. In addition, since tertiary amyl lithium, tertiary amyl sodium, tertiary amyl potassium and other raw materials themselves have the characteristics of easy volatilization and sublimation (similar to tertiary butyl lithium, hexamethyl disilazane potassium and other compounds), they are difficult to completely remove in the product, which seriously affects the nuclear magnetic purity and the metal impurity level of inductively coupled plasma mass spectrometry (ICP-MS) detection.

[0004] (2) Alcohol exchange method: low-boiling-point divalent alkoxystannane such as methanol tin and ethanol tin is used as raw material, and high-boiling-point alcohol (such as tertiary amyl alcohol) is subjected to alcohol exchange by high-temperature cooking. This method has low reaction efficiency and is difficult to completely replace, which easily leads to the presence of various alkoxyl mixed ligands in the product, affecting the consistency of product composition.

[0005] (3) High-activity intermediate method: first prepare a high-activity divalent tin intermediate such as bis (bis (trimethylsilyl) amino) tin, and then replace the ligand with the target alcohol. This route is complex, the intermediate preparation and storage conditions are harsh, and the ligand replacement is often incomplete, with many side reactions, which is not conducive to large-scale production.

[0006] The above-mentioned synthesis methods all have obvious drawbacks: First, if halogen-containing tin compounds are used as raw materials, the final product will contain excessive residues of halogen elements and metal elements such as lithium, sodium, and potassium, which cannot meet the strict limits on halogen and metal impurities in semiconductor processes; second, existing methods generally suffer from low reaction selectivity, cumbersome post-processing, and significant environmental pollution; in addition, existing processes have not designed corresponding purification systems for the liquid properties of tert-amyl tin oxide, making it difficult for the product to meet the requirements of high-end applications in terms of purity, impurity control, and stability, which seriously limits its industrial production and widespread application.

[0007] Therefore, developing a synthetic method for preparing high-purity tert-amyl stannous oxide from halogen-free raw materials, with high reaction efficiency, simple post-processing, and scalable production is of significant industrial importance and application value. Summary of the Invention

[0008] To address the problems of low yield, difficult purification, and high halogen residue in existing methods for synthesizing tert-amyl tin oxide, this invention provides a method for preparing tert-amyl tin oxide. Using tin powder and tert-amyl alcohol as reactants, and in the presence of a specific composite initiator (cuprous bromide and triphenylphosphine), tert-amyl tin oxide can be efficiently prepared, significantly improving the yield of the target product to as high as 85%. Furthermore, the target product prepared by this method is easy to purify, effectively avoiding the residue of halogen and metal elements, and obtaining tert-amyl tin oxide with a purity as high as 6N, meeting the high purity requirements of the semiconductor industry.

[0009] Specifically, the following technical solutions are provided: The first aspect of this invention provides a method for preparing tert-amyl stannous oxide, comprising the following steps: Under a protective atmosphere, tin powder and tert-amyl alcohol are reacted in the presence of a composite initiator. After the reaction is completed, the filtrate is collected and subjected to vacuum distillation to obtain the tert-amyl tin(II) alcohol. The composite initiator comprises cuprous bromide and triphenylphosphine.

[0010] Furthermore, the protective atmosphere includes, but is not limited to, argon, nitrogen, etc.

[0011] Furthermore, the purity of the tin powder is greater than 99%.

[0012] Furthermore, the tin powder is preferably 100-200 mesh tin powder.

[0013] Furthermore, the tin powder is dried tin powder to remove surface moisture and impurities. The drying conditions are: preferably a vacuum degree of 0.01-0.02 MPa, preferably a temperature of 80-100 ℃, and preferably a time of 4-6 h.

[0014] Furthermore, the moisture content of the tert-amyl alcohol is less than 50 ppm. The tert-amyl alcohol can be dehydrated using a 3A molecular sieve, and the dehydration effect can be monitored using a Karl Fischer moisture analyzer to ensure that the moisture content is less than 50 ppm.

[0015] Furthermore, the composite initiator is composed of cuprous bromide and triphenylphosphine; preferably, the molar ratio of cuprous bromide and triphenylphosphine in the composite initiator is 1:(1-2).

[0016] Furthermore, the preferred molar ratio of the tin powder to cuprous bromide and triphenylphosphine is 1:(0.05-0.08):(0.1-0.15).

[0017] In this invention, the amount of composite initiator added to the system and the molar ratio of cuprous bromide to triphenylphosphine in the composite initiator both affect the yield and purity of the target product. Insufficient addition of the composite initiator or a relatively low content of any single component in the composite initiator (making it difficult to fully utilize the synergistic effect) will lead to low reaction efficiency and a low yield of the target product. However, excessive addition of the composite initiator will not only fail to effectively improve the yield of the target product but may even reduce it (for example, excessive addition of triphenylphosphine will affect the distillation and purification of the target product from the reaction system, thus reducing the product yield). Furthermore, excessive addition of cuprous bromide will also reduce the metal purity of the product. Preferably, by controlling the molar ratio of cuprous bromide to triphenylphosphine in the composite initiator within the range of 1:(1-2), and controlling the molar ratio of tin powder to cuprous bromide and triphenylphosphine within the range of 1:(0.05-0.08):(0.1-0.15), high-yield and high-purity tert-amyl tin oxide can be obtained at low cost.

[0018] Furthermore, the preferred molar ratio of tin powder to tert-amyl alcohol is 1:(10-15). Tert-amyl alcohol acts as a reaction ligand and a solvent to dissolve the reactants and products, and also enhances the activity of the raw materials and promotes the reaction. Therefore, a much larger amount of tert-amyl alcohol is required for the reaction. Preferably, controlling the molar ratio of tin powder to tert-amyl alcohol within the range of 1:(10-15) can effectively improve the yield of the target product while avoiding resource waste.

[0019] Furthermore, other organic solvents may be added to the preparation method to dissolve the reactants, including but not limited to tetrahydrofuran, toluene, diethyl ether, 2-methyltetrahydrofuran, n-hexane, dichloromethane, etc.

[0020] Further, tin powder and tert-amyl alcohol are first mixed, and then a mixture of cuprous bromide and triphenylphosphine is added under stirring conditions to form a mixed system at a stirring rate of 500-1000 rpm.

[0021] Furthermore, the reaction temperature is preferably 40-80 °C, and the reaction time is not less than 6 h.

[0022] More preferably, the reaction is a staged temperature-controlled reaction, specifically: first, the temperature is raised to 40-50 °C and held for 2-3 hours to promote the thorough mixing of the initiator and raw materials. During this process, the reaction system will slowly generate gas, which is hydrogen gas that is harmless to the air and can be collected and centrally treated. Subsequently, as the reaction proceeds, the tin powder is gradually consumed, the reaction rate gradually decreases, and the rate of gas generation gradually slows down. Then, the temperature is raised to 70-80 °C and held for 4-6 hours, during which inert gas is continuously introduced to maintain the inert atmosphere of the reaction system and ensure that the reaction proceeds smoothly until the final reaction system is completely degassed.

[0023] Furthermore, after the reaction is complete, the reaction solution is allowed to cool naturally to room temperature, then filtered under reduced pressure to remove unreacted tin powder and a small amount of solid impurities generated during the reaction, and the filtrate is collected.

[0024] Furthermore, the vacuum distillation process specifically involves transferring the filtrate to a distillation apparatus equipped with a glass distillation column, and sequentially performing primary distillation, secondary distillation, and tertiary distillation.

[0025] Furthermore, the glass distillation column has a length of 80-100 cm and a glass packing height of 60-80 cm.

[0026] Further, the first-stage distillation process specifically involves: adjusting the vacuum to 50-100 torr, heating to 110-130 ℃ at a heating rate of 2-3 ℃ / min, controlling the reflux ratio to 1:1-2:1, and collecting the fraction at 90-100 ℃. This fraction mainly consists of excess tert-amyl alcohol and low-boiling-point impurities. The tert-amyl alcohol can be recovered, purified, and reused to reduce production costs. The secondary distillation process specifically involves: further distilling the remaining portion after the primary distillation process, adjusting the vacuum to 1-2 torr, heating to 190-210 ℃ at a heating rate of 1-2 ℃ / min, controlling the reflux ratio to 3:1-4:1, and collecting the fraction at 120-140 ℃, which is a preliminarily purified tert-amyl tin oxide. The tertiary distillation process specifically involves: re-distilling the fraction collected from the secondary distillation process, adjusting the vacuum to 1-2 torr, heating to 180-200 ℃ at a heating rate of 0.5-1 ℃ / min, controlling the reflux ratio to 5:1-8:1, and collecting the fraction in the temperature range of 120-125 ℃ to obtain the tert-amyl tin oxide.

[0027] Furthermore, the tert-amyl tin oxide has an NMR purity of ≥99%, a metal purity of 6 N, and a color of ≤10 APHA.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides a method for preparing tert-amyl stannous oxide. Using tin powder and tert-amyl alcohol as reactants, and in the presence of a specific composite initiator (cuprous bromide and triphenylphosphine), tert-amyl stannous oxide can be efficiently prepared. Furthermore, combined with a multi-stage distillation purification process, tert-amyl stannous oxide with a purity up to 6N and a yield up to 85% can be obtained. In addition, the reaction process of the above preparation method is milder and more controllable, with fewer byproducts, and the raw materials are widely available and low in cost, making it suitable for mass production.

[0029] Compared to existing synthesis methods, this invention uses tin powder as the core metal raw material to replace tin halides, avoiding the problem of difficult filtration caused by the generation of large amounts of lithium, sodium, and potassium halides as byproducts. It also avoids the residue of halogen elements and other metal elements such as lithium, sodium, and potassium in the product from the source. Furthermore, this invention uses tert-amyl alcohol and a composite initiator to replace lithium, sodium, and potassium tert-amyl alcohol, effectively avoiding the subsequent residue of these substances and greatly improving purification efficiency. The tert-amyl tin oxide prepared by the above reaction system combined with a multi-stage distillation purification process meets the high purity requirements of the semiconductor industry for tert-amyl tin oxide. Attached Figure Description

[0030] Figure 1 This is a schematic diagram of the structure of tert-amyl tin(II) alcohol; Figure 2 The 1H NMR spectrum of tert-amyl stannous oxide prepared in Example 1; Figure 3 The 1H NMR spectrum of tert-amyl stannous alcohol prepared in Comparative Example 1; Figure 4 The 1H NMR spectrum of tert-amyl stannous alcohol prepared in Comparative Example 2; Figure 5 The structure of the incompletely substituted compound impurities contained in the tert-amyl tin oxide product prepared for Comparative Example 2. Detailed Implementation

[0031] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The terms “comprising” or “including” used in this invention may also be replaced with the closed form “is” or “consisting of”.

[0033] Example 1: This example relates to a method for preparing tert-amyl stannous alcohol, the specific operation of which is as follows: (1) Take 500 g of 100 mesh tin powder with a purity of 99.99% and place it in a vacuum drying oven. Dry it for 6 h at a temperature of 80 ℃ and a vacuum of 0.01 MPa. Take 5000 mL of tert-amyl alcohol and dehydrate it using 3A molecular sieve for 48 h. Use a Karl Fischer moisture analyzer to monitor the dehydration effect and ensure that the moisture content is less than 50 ppm. Keep it for later use.

[0034] (2) In a stainless steel reactor, nitrogen gas was introduced to replace the air in the reactor for 30 min, maintaining a nitrogen gas introduction rate of 0.5 L / min. The pretreated tin powder and tert-amyl alcohol from step (1) were added sequentially, followed by cuprous bromide and triphenylphosphine. The molar ratio of tin powder, tert-amyl alcohol, cuprous bromide, and triphenylphosphine was 1:10:0.05:0.1. The stirring device was turned on and stirred evenly at a rate of 500 r / min. The mixture was then heated to 40 °C, and gas was gradually generated in the reaction system. The reaction was maintained at this temperature for 3 h, and then the temperature was raised to 70 °C and the reaction continued for 6 h until the gas release from the reaction system stopped. Nitrogen gas was continuously introduced during this period. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure using a filtration device, and the filtrate was collected.

[0035] (3) Transfer the filtrate collected in step (2) to a distillation apparatus equipped with a glass distillation column. First, adjust the vacuum to 100 torr, heat at a heating rate of 2 ℃ / min, control the reflux ratio to 2:1, and collect the fraction in the temperature range of 90-100 ℃ (mainly excess tert-amyl alcohol and low-boiling-point impurities), heating to a maximum of 120 ℃; continue distilling the remaining liquid in the distillation vessel, adjusting the vacuum to 2 torr, reducing the heating rate to 1 ℃ / min, controlling the reflux ratio to 4:1, and collecting the fraction in the temperature range of 120-140 ℃ to obtain preliminarily purified tert-amyl tin oxide, heating to a maximum of 200 ℃; distill the preliminarily purified tert-amyl tin oxide again, adjusting the vacuum to 1 torr, controlling the heating rate to 0.5 ℃ / min, increasing the reflux ratio to 5:1, and collecting the fraction in the temperature range of 120-125 ℃. The fraction in the ℃ temperature range is the desired tert-amyl stannous product (colorless and transparent, yield 85%), which can be heated up to 190℃.

[0036] The tert-amyl tin oxide product prepared in this embodiment was subjected to 1H NMR spectroscopy, colorimetry, and ICP-MS analysis. The test results are as follows: NMR spectrum as shown. Figure 2 As shown, the product has an NMR purity of ≥99%, a chromaticity of ≤10 APHA, and a metal purity of 6N.

[0037] Example 2: This example relates to a method for preparing tert-amyl stannous alcohol, the specific operation of which is as follows: (1) Take 500 g of tin powder with a purity of 99.99% and 200 mesh and place it in a vacuum drying oven. Dry it for 6 h at a temperature of 80 ℃ and a vacuum of 0.01 MPa. Take 5000 mL of tert-amyl alcohol and dehydrate it using 3A molecular sieve for 48 h. Use a Karl Fischer moisture analyzer to monitor the dehydration effect and ensure that the moisture content is less than 50 ppm. Keep it for later use.

[0038] (2) In a stainless steel reactor, nitrogen gas was introduced to replace the air in the reactor for 30 min, maintaining a nitrogen gas introduction rate of 0.5 L / min. The pretreated tin powder and tert-amyl alcohol from step (1) were added sequentially, followed by cuprous bromide and triphenylphosphine. The molar ratio of tin powder, tert-amyl alcohol, cuprous bromide, and triphenylphosphine was 1:15:0.08:0.15. The stirring device was turned on and stirred evenly at a rate of 800 r / min. The mixture was then heated to 40 °C, and gas was gradually generated in the reaction system. The reaction was maintained at this temperature for 3 h, and then the temperature was raised to 70 °C and the reaction continued for 6 h until the gas release from the reaction system stopped. Nitrogen gas was continuously introduced during this period. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure using a filtration device, and the filtrate was collected.

[0039] (3) Transfer the filtrate collected in step (2) to a distillation apparatus equipped with a glass distillation column. First, adjust the vacuum to 80 torr, heat at a heating rate of 3 ℃ / min, control the reflux ratio to 1:1, and collect the fraction in the temperature range of 90-100 ℃ (mainly excess tert-amyl alcohol and low-boiling-point impurities). The maximum temperature is 120 ℃. Continue to distill the remaining liquid in the distillation vessel, adjust the vacuum to 2 torr, reduce the heating rate to 2 ℃ / min, control the reflux ratio to 3:1, and collect the fraction in the temperature range of 120-140 ℃ to obtain preliminarily purified tert-amyl tin oxide. The maximum temperature is 200 ℃. Distill the preliminarily purified tert-amyl tin oxide again, adjust the vacuum to 1.5 torr, control the heating rate to 0.5 ℃ / min, increase the reflux ratio to 5:1, and collect the fraction in the temperature range of 120-125 ℃. The fraction in the ℃ temperature range is the desired tert-amyl stannous product (colorless and transparent, yield 83%), which can be heated up to 190 ℃.

[0040] The tert-amyl tin oxide product prepared in this embodiment was tested by 1H NMR, colorimetry and ICP-MS. The test results are as follows: the NMR purity of the product is ≥99%, the colorimetry is ≤10 APHA and the metal purity is 6 N.

[0041] Example 3: This example relates to a method for preparing tert-amyl tin oxide. The only difference from Example 1 is that in step (2), the molar ratio of tin powder, tert-amyl alcohol, cuprous bromide, and triphenylphosphine is 1:10:0.05:0.05. All other operations are the same, and the corresponding tert-amyl tin oxide product is prepared with a yield of 68%.

[0042] The tert-amyl tin oxide product prepared in this embodiment was tested by 1H NMR, colorimetry and ICP-MS. The test results are as follows: the NMR purity of the product is ≥99%, the colorimetry is ≤10 APHA and the metal purity is 6 N.

[0043] Example 4: This example relates to a method for preparing tert-amyl tin oxide. The only difference from Example 1 is that in step (2), the molar ratio of tin powder, tert-amyl alcohol, cuprous bromide, and triphenylphosphine is 1:10:0.05:0.15. All other operations are the same, and the corresponding tert-amyl tin oxide product is prepared with a yield of 84%.

[0044] The tert-amyl tin oxide product prepared in this embodiment was tested by 1H NMR, colorimetry and ICP-MS. The test results are as follows: the NMR purity of the product is ≥99%, the colorimetry is ≤10 APHA and the metal purity is 6 N.

[0045] Example 5: This example relates to a method for preparing tert-amyl tin oxide. The only difference from Example 1 is that in step (2), the molar ratio of tin powder, tert-amyl alcohol, cuprous bromide, and triphenylphosphine is 1:10:0.1:0.3. All other operations are the same, and the corresponding tert-amyl tin oxide product is prepared with a yield of 81%.

[0046] The tert-amyl tin oxide product prepared in this embodiment was tested by 1H NMR, colorimetry and ICP-MS. The test results are as follows: the NMR purity of the product is ≥99%, the colorimetry is ≤10 APHA and the metal purity is 5 N.

[0047] Comparative Example 1: This comparative example relates to a method for preparing tert-amyl stannous chloride, using anhydrous stannous chloride and potassium tert-amyl oxide as reactants. The specific operation is as follows: (1) Take 500 g of anhydrous stannous chloride purchased from the market, place it in a vacuum drying oven, and dry it for 6 h at a temperature of 80 ℃ and a vacuum of 0.01 MPa; prepare potassium tert-amyloxide for later use; take 5000 mL of tetrahydrofuran, dehydrate it using 3A molecular sieve for 48 h, and use a Karl Fischer moisture analyzer to monitor the dehydration effect to ensure that the moisture content is less than 50 ppm, and set it aside for later use.

[0048] (2) In a stainless steel reactor, nitrogen gas was introduced to replace the air in the reactor for 30 min, maintaining a nitrogen gas introduction rate of 0.5 L / min. Pretreated anhydrous stannous chloride and tetrahydrofuran were added sequentially, followed by potassium tert-amyloxide. The molar ratio of stannous chloride, potassium tert-amyloxide, and tetrahydrofuran was 1:2.2:15. The stirring device was turned on, and the mixture was stirred evenly at a rate of 800 r / min. Then, the mixture was heated to 50 °C and kept at that temperature for 3 h. Subsequently, the temperature was increased to 80 °C, and the reaction was continued for 6 h, during which nitrogen gas was continuously introduced. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure, and the filtrate was collected. (3) Transfer the filtrate collected in step (2) to a distillation apparatus equipped with a glass distillation column. First, adjust the vacuum to 80 torr, heat at a heating rate of 3 ℃ / min, control the reflux ratio to 1:1, and collect the fraction in the temperature range of 60-70 ℃ (mainly tetrahydrofuran and low-boiling impurities), heating to a maximum of 120 ℃; continue distilling the remaining liquid in the distillation vessel, adjusting the vacuum to 2 torr, reducing the heating rate to 2 ℃ / min, controlling the reflux ratio to 3:1, and collecting the fraction in the temperature range of 120-140 ℃ to obtain preliminarily purified tert-amyl tin oxide, heating to a maximum of 200 ℃; distill the preliminarily purified tert-amyl tin oxide again, adjusting the vacuum to 1.5 torr, controlling the heating rate to 0.5 ℃ / min, increasing the reflux ratio to 5:1, and collecting the fraction in the temperature range of 120-125 ℃. The fraction in the ℃ temperature range is the desired tert-amyl stannous product (colorless and transparent, yield 23%), which can be heated up to 190℃.

[0049] The tert-amyl stannous oxide product prepared in this comparative example was subjected to 1H NMR and ICP-MS analysis. The results are as follows: NMR spectrum as shown. Figure 3 As shown, the NMR purity of the product is ≤80%, and the metal purity is 4 N.

[0050] Comparative Example 2: This comparative example relates to a method for preparing tert-amyl stannous chloride, using anhydrous stannous chloride, tert-amyl alcohol, and bis(trimethylsilyl)aminopotassium as reactants. The specific operation is as follows: (1) Take 500 g of anhydrous stannous chloride purchased from the market, place it in a vacuum drying oven, and dry it for 6 h at a temperature of 80 ℃ and a vacuum of 0.01 MPa; prepare potassium tert-amyloxide for later use; take 5000 mL of tetrahydrofuran, dehydrate it using 3A molecular sieve for 48 h, and use a Karl Fischer moisture analyzer to monitor the dehydration effect to ensure that the moisture content is less than 50 ppm, and set it aside for later use.

[0051] (2) In a stainless steel reactor, nitrogen gas was introduced to replace the air in the reactor for 30 min, maintaining a nitrogen gas introduction rate of 0.5 L / min. Pretreated anhydrous stannous chloride and tetrahydrofuran were added sequentially, followed by bis(trimethylsilyl)aminopotassium tetrahydrofuran solution (1.0 M). The stirring device was turned on, and the mixture was stirred evenly at a rate of 800 r / min. Then, the mixture was heated to 50 ℃ and kept at that temperature for 3 h. Subsequently, the temperature was raised to 80 ℃ and the reaction was continued for 6 h. After the reaction was completed, the mixture was restored to room temperature, and tert-amyl alcohol was added and stirred evenly. The mixture was then heated to 50 ℃ and kept at that temperature for 3 h. Subsequently, the temperature was raised to 80 ℃ and the reaction was continued for 6 h. During this period, nitrogen gas was continuously introduced. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure, and the filtrate was collected. The molar ratio of stannous chloride, bis(trimethylsilyl)aminopotassium tetrahydrofuran solution, tert-amyl alcohol, and tetrahydrofuran was 1:2.1:2.5:15.

[0052] (3) Transfer the filtrate collected in step (2) to a distillation apparatus equipped with a glass distillation column. First, adjust the vacuum to 80 torr, heat at a heating rate of 3 ℃ / min, control the reflux ratio to 1:1, and collect the fraction in the temperature range of 60-70 ℃ (mainly tetrahydrofuran and low-boiling impurities), heating to a maximum of 120 ℃; continue distilling the remaining liquid in the distillation vessel, adjusting the vacuum to 2 torr, reducing the heating rate to 2 ℃ / min, controlling the reflux ratio to 3:1, and collecting the fraction in the temperature range of 120-140 ℃ to obtain preliminarily purified tert-amyl tin oxide, heating to a maximum of 200 ℃; distill the preliminarily purified tert-amyl tin oxide again, adjusting the vacuum to 1.5 torr, controlling the heating rate to 0.5 ℃ / min, increasing the reflux ratio to 5:1, and collecting the fraction in the temperature range of 120-125 ℃. The fraction in the ℃ temperature range is the desired tert-amyl stannous product (colorless and transparent, yield 45%), which can be heated up to 190℃.

[0053] The 1H NMR spectrum of the tert-amyl tin oxide product prepared in this comparative example was analyzed, and the results are as follows: NMR spectrum as shown. Figure 4 As shown, the NMR purity of the product is ≤70%, and it contains compounds with incomplete substitution (structure as shown). Figure 5 (As shown).

[0054] Comparative Example 3: This comparative example relates to a method for preparing tert-amyl stannous alcohol. The only difference from Example 1 is the type of initiator. Aluminum trichloride is used instead of the composite initiator of cuprous bromide and triphenylphosphine. All other operations are the same, as follows: (1) Take 500 g of 100 mesh tin powder with a purity of 99.99% and place it in a vacuum drying oven. Dry it for 6 h at a temperature of 80 ℃ and a vacuum of 0.01 MPa. Take 5000 mL of tert-amyl alcohol and dehydrate it using 3A molecular sieve for 48 h. Use a Karl Fischer moisture analyzer to monitor the dehydration effect and ensure that the moisture content is less than 50 ppm. Keep it for later use.

[0055] (2) In a stainless steel reactor, nitrogen gas was introduced to replace the air in the reactor for 30 min, maintaining a nitrogen gas introduction rate of 0.5 L / min. The pretreated tin powder and tert-amyl alcohol from step (1) were added sequentially, followed by aluminum trichloride. The molar ratio of tin powder, tert-amyl alcohol, and aluminum trichloride was 1:10:0.15. The stirring device was turned on and stirred evenly at a rate of 800 r / min. The mixture was then heated to 40 ℃ and kept at that temperature for 3 h. Subsequently, the temperature was increased to 70 ℃ and the reaction was continued for 6 h, during which nitrogen gas was continuously introduced. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure using a filtration device, and the filtrate was collected.

[0056] (3) Transfer the filtrate collected in step (2) to a distillation apparatus equipped with a glass distillation column. First, adjust the vacuum to 100 torr and heat at a heating rate of 2 ℃ / min. Control the reflux ratio to 2:1 and collect the fraction in the temperature range of 90-100 ℃ (mainly excess tert-amyl alcohol and low-boiling impurities). The maximum temperature is 120 ℃. Continue to distill the remaining liquid in the pot of the above distillation. Adjust the vacuum to 2 torr, reduce the heating rate to 1 ℃ / min, control the reflux ratio to 4:1, and heat to 200 ℃. No product is collected.

[0057] Comparative Example 4: This comparative example relates to a method for preparing tert-amyl stannous alcohol. The only difference from Example 1 is that only cuprous bromide is added as an initiator; all other operations are the same, as follows: (1) Take 500 g of 100 mesh tin powder with a purity of 99.99% and place it in a vacuum drying oven. Dry it for 6 h at a temperature of 80 ℃ and a vacuum of 0.01 MPa. Take 5000 mL of tert-amyl alcohol and dehydrate it using 3A molecular sieve for 48 h. Use a Karl Fischer moisture analyzer to monitor the dehydration effect and ensure that the moisture content is less than 50 ppm. Keep it for later use.

[0058] (2) In a stainless steel reactor, nitrogen gas was introduced to replace the air in the reactor for 30 min, maintaining a nitrogen gas introduction rate of 0.5 L / min. The pretreated tin powder and tert-amyl alcohol from step (1) were added sequentially, followed by cuprous bromide. The molar ratio of tin powder, tert-amyl alcohol, and cuprous bromide was 1:10:0.15. The stirring device was turned on and stirred evenly at a rate of 800 r / min. The mixture was then heated to 40 °C and kept at that temperature for 3 h. Subsequently, the temperature was increased to 70 °C and the reaction was continued for 6 h, with nitrogen gas continuously introduced during the reaction. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure using a filtration device, and the filtrate was collected.

[0059] (3) Transfer the filtrate collected in step (2) to a distillation apparatus equipped with a glass distillation column. First, adjust the vacuum to 100 torr and heat at a heating rate of 2 ℃ / min. Control the reflux ratio to 2:1 and collect the fraction in the temperature range of 90-100 ℃ (mainly excess tert-amyl alcohol and low-boiling impurities). The maximum temperature is 120 ℃. Continue to distill the remaining liquid in the pot of the above distillation. Adjust the vacuum to 2 torr, reduce the heating rate to 1 ℃ / min, control the reflux ratio to 4:1, and heat to 200 ℃. No product is collected.

[0060] Comparative Example 5: This comparative example relates to a method for preparing tert-amyl stannous oxide. The only difference from Example 1 is that only triphenylphosphine is added as an initiator; all other operations are the same, as follows: (1) Take 500 g of 100 mesh tin powder with a purity of 99.99% and place it in a vacuum drying oven. Dry it for 6 h at a temperature of 80 ℃ and a vacuum of 0.01 MPa. Take 5000 mL of tert-amyl alcohol and dehydrate it using 3A molecular sieve for 48 h. Use a Karl Fischer moisture analyzer to monitor the dehydration effect and ensure that the moisture content is less than 50 ppm. Keep it for later use.

[0061] (2) In a stainless steel reactor, nitrogen gas was introduced to replace the air in the reactor for 30 min, maintaining a nitrogen gas introduction rate of 0.5 L / min. The pretreated tin powder and tert-amyl alcohol from step (1) were added sequentially, followed by triphenylphosphine. The molar ratio of tin powder, tert-amyl alcohol, and triphenylphosphine was 1:10:0.15. The stirring device was turned on and stirred evenly at a rate of 800 r / min. The mixture was then heated to 40 °C and kept at that temperature for 3 h. Subsequently, the temperature was increased to 70 °C and the reaction was continued for 6 h, with nitrogen gas continuously introduced during the reaction. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure using a filtration device, and the filtrate was collected.

[0062] (3) Transfer the filtrate collected in step (2) to a distillation apparatus equipped with a glass distillation column. First, adjust the vacuum to 100 torr and heat at a heating rate of 2 ℃ / min. Control the reflux ratio to 2:1 and collect the fraction in the temperature range of 90-100 ℃ (mainly excess tert-amyl alcohol and low-boiling impurities). The maximum temperature is 120 ℃. Continue to distill the remaining liquid in the pot of the above distillation. Adjust the vacuum to 2 torr, reduce the heating rate to 1 ℃ / min, control the reflux ratio to 4:1, and heat to 200 ℃. No product is collected.

[0063] The above-described embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention. The scope of protection of the present invention is defined by the claims.

Claims

1. A process for the preparation of tertiary amyltin hydride, characterized in that, The method comprises the following steps: The tin powder is reacted with tertiary amyl alcohol in the presence of a composite initiator under a protective atmosphere, and after the reaction is completed, the filtrate is collected and treated by vacuum rectification to obtain the tertiary amyl stannane; the composite initiator comprises cuprous bromide and triphenylphosphine.

2. The production method according to claim 1, characterized by, The purity of the tin powder is greater than 99%.

3. The production method according to claim 1, characterized by, The tin powder is a tin powder after drying treatment, and the drying treatment is performed under the conditions of a vacuum degree of 0.01-0.02 MPa, a temperature of 80-100 ℃ and a time of 4-6 h.

4. The preparation method according to claim 1, characterized in that, The moisture content of the tertiary amyl alcohol is less than 50 ppm.

5. The preparation method according to claim 1, characterized in that, The composite initiator is composed of cuprous bromide and triphenylphosphine. The molar ratio of cuprous bromide to triphenylphosphine in the composite initiator is 1:(1-2).

6. The method of claim 1, wherein, The molar ratio of the tin powder to tertiary amyl alcohol is 1:(10-15). The molar ratio of the tin powder to cuprous bromide, triphenylphosphine is 1:(0.05-0.08):(0.1-0.15).

7. The preparation method according to claim 1, characterized in that, The temperature of the reaction is 40-80 ℃, and the time is not less than 6 h.

8. The method of claim 1, wherein, The reaction is a staged temperature control reaction, specifically, first, the temperature is raised to 40-50 ℃, and the reaction is kept for 2-3 h, and then the temperature is raised to 70-80 ℃, and the reaction is kept for 4-6 h.

9. The method of claim 1, wherein, The vacuum rectification treatment specifically comprises: transferring the filtrate to a rectification device equipped with a glass rectification column, and sequentially performing primary rectification treatment, secondary rectification treatment and tertiary rectification treatment; The primary rectification treatment specifically comprises: adjusting the vacuum degree to 50-100 torr, raising the temperature to 110-130 ℃ at a temperature rising rate of 2-3 ℃ / min, controlling the reflux ratio to be 1:1-2:1, and collecting the fraction at 90-100 ℃; The secondary rectification treatment specifically comprises: continuing to rectify the remaining part after the primary rectification treatment, adjusting the vacuum degree to 1-2 torr, raising the temperature to 190-210 ℃ at a temperature rising rate of 1-2 ℃ / min, controlling the reflux ratio to be 3:1-4:1, and collecting the fraction at 120-140 ℃; The tertiary rectification treatment specifically comprises: rectifying the fraction collected in the secondary rectification treatment again, adjusting the vacuum degree to 1-2 torr, raising the temperature to 180-200 ℃ at a temperature rising rate of 0.5-1 ℃ / min, controlling the reflux ratio to be 5:1-8:1, and collecting the fraction in the temperature range of 120-125 ℃ to obtain the tertiary amyl stannane.

10. The method of claim 9, wherein, The nuclear magnetic purity of the tertiary amyl stannane is ≥99%, the metal purity is 6 N, and the colority is ≤10 APHA.

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