A method for preparing tertiary amyltin stannous

Abstract

The present application relates to a kind of preparation method of tertiary amyl alcohol stannous, comprising the following steps: under the protection atmosphere, tin powder is reacted with tertiary amyl alcohol in the presence of composite initiator, after reaction, filtrate is collected, and the tertiary amyl alcohol stannous of the tertiary amyl alcohol stannous obtained by reduced pressure rectification treatment is obtained;The composite initiator includes cuprous bromide and triphenylphosphine.The present application uses tin powder and tertiary amyl alcohol as raw material, in the presence of specific composite initiator, the tertiary amyl alcohol stannous can be prepared by reaction, and the yield of target product can be as high as 85%.In addition, the target product obtained by the above preparation method is easy to purify, and the residual halogen element and lithium / sodium / potassium metal element can be effectively avoided, and the purity of metal is as high as 6N The tertiary amyl alcohol stannous meets the high-purity requirement of tertiary amyl alcohol stannous in the field of semiconductor.

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. BACKGROUND

[0002] Tertiary amyl stannous, 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 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 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:

[0004] (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 the raw materials such as lithium tert-pentoxide, sodium tert-pentoxide and potassium tert-pentoxide themselves have the characteristics of easy volatilization and sublimation (similar to compounds such as tert-butyllithium and hexamethyldisilazide), they are difficult to completely remove in the product, which seriously affects the nuclear magnetic purity and the metal impurity level detected by inductively coupled plasma mass spectrometry (ICP-MS).

[0005] (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 tert-pentanol) 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.

[0006] (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 preservation conditions are harsh, and the ligand replacement is often incomplete, with many side reactions, which is not conducive to large-scale production.

[0007] The above synthesis methods all have obvious defects: first, if a tin compound containing halogen is used as raw material, the residual halogen element and lithium / sodium / potassium metal element in the final product will exceed the standard, which cannot meet the strict restrictions of semiconductor process on halogen and metal impurities; second, the existing methods generally have low reaction selectivity, complicated post-treatment and large environmental pollution; in addition, the existing process does not design a corresponding purification system according to the liquid physical properties of tertiary amyl alcohol stannous, which makes it difficult to meet the requirements of high-end applications in terms of purity, impurity control and stability, and seriously limits the industrial production and popularization and application of the product.

[0008] Therefore, it is of great industrial significance and application value to develop a synthesis method of tertiary amyl alcohol stannous, which has no halogen in raw materials, is efficient in reaction, simple in post-treatment and can scaleably prepare high-purity tertiary amyl alcohol stannous. SUMMARY

[0009] To solve the problems of low yield, difficult purification and high halogen residue in the existing synthesis method of tertiary amyl alcohol stannous, the present application provides a preparation method of tertiary amyl alcohol stannous, which uses tin powder and tertiary amyl alcohol as reaction raw materials, and can efficiently prepare tertiary amyl alcohol stannous in the presence of a specific composite initiator (cuprous bromide and triphenylphosphine), greatly improving the yield of the target product, which can be as high as 85%. In addition, the target product prepared by the above preparation method is easy to purify, and can effectively avoid the residue of halogen element and metal element, obtaining tertiary amyl alcohol stannous with a purity of 6N, which meets the high-purity requirements of tertiary amyl alcohol stannous in the semiconductor field.

[0010] Specifically, the following technical solutions are provided:

[0011] The first aspect of the present application provides a preparation method of tertiary amyl alcohol stannous, comprising the following steps:

[0012] Under a protective atmosphere, the tin powder and the tertiary amyl alcohol are reacted in the presence of a composite initiator, the filtrate is collected after the reaction is completed, and the tertiary amyl alcohol stannous is obtained by vacuum rectification treatment; the composite initiator comprises cuprous bromide and triphenylphosphine.

[0013] Further, the protective atmosphere includes but is not limited to argon, nitrogen and the like.

[0014] Further, the purity of the tin powder is greater than 99%.

[0015] Further, the tin powder is preferably 100-200 mesh tin powder.

[0016] Further, the tin powder is a tin powder after drying treatment to remove surface moisture and impurities, and the drying treatment conditions are as follows: the vacuum degree is preferably 0.01-0.02 MPa, the temperature is preferably 80-100 ℃, and the time is preferably 4-6 h.

[0017] Further, the water content of the tertiary amyl alcohol is less than 50 ppm, and the tertiary amyl alcohol can be subjected to dehydration treatment by using 3A molecular sieves, and the dehydration effect is monitored by using a Karl Fischer moisture tester to ensure that the water content is less than 50 ppm.

[0018] Further, 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).

[0019] Further, the molar ratio of tin powder, cuprous bromide, and triphenylphosphine is preferably 1:(0.05-0.08):(0.1-0.15).

[0020] In the present application, the amount of the composite initiator added to the system and the molar ratio of cuprous bromide and triphenylphosphine in the composite initiator both affect the yield and purity of the target product. Too little amount of the composite initiator or too little relative content of a single component in the composite initiator (which makes it difficult to fully exert the synergistic effect) will both result in low reaction efficiency and low yield of the target product; however, too much amount of the composite initiator will not only fail to effectively improve the yield of the target product, but even reduce the yield (for example, too much triphenylphosphine will affect the rectification and purification of the target product from the reaction system, thereby reducing the yield of the product), in addition, too much cuprous bromide will also reduce the metal purity of the product. Preferably, the molar ratio of cuprous bromide and triphenylphosphine in the composite initiator is controlled within the range of 1:(1-2), and the molar ratio of tin powder, cuprous bromide, and triphenylphosphine is controlled within the range of 1:(0.05-0.08):(0.1-0.15), so as to obtain tertiary amyl tin with high yield and high purity at low cost.

[0021] Further, the molar ratio of tin powder and tertiary amyl alcohol is preferably 1:(10-15), wherein the tertiary amyl alcohol not only serves as a reaction ligand, but also acts as a solvent to dissolve reactants and products, and improves the activity of raw materials and promotes the reaction, so that much more tertiary amyl alcohol than required by the reaction needs to be added. Preferably, the molar ratio of tin powder and tertiary amyl alcohol is controlled within the range of 1:(10-15), so as to effectively improve the yield of the target product while avoiding resource waste.

[0022] Further, other organic solvents can also be added in the preparation method to dissolve reactants, including but not limited to tetrahydrofuran, toluene, diethyl ether, 2-methyltetrahydrofuran, n-hexane, dichloromethane, etc.

[0023] Further, the metal tin powder and the tertiary amyl alcohol are mixed first, and then a mixture of cuprous bromide and triphenylphosphine is added under stirring to form a mixed system at a stirring rate of 500-1000 rpm.

[0024] Further, the temperature of the reaction is preferably 40-80 ℃, and the time is not less than 6 h.

[0025] More preferably, the reaction is a staged temperature control reaction, specifically: first, the temperature is raised to 40-50 ℃, and the reaction is maintained for 2-3 h to promote the thorough mixing of the initiator and the raw material. In this process, the reaction system slowly produces hydrogen gas, which is harmless to air. The hydrogen gas can be collected and treated collectively. Subsequently, as the reaction proceeds, the tin powder is gradually consumed, the reaction rate gradually decreases, and the speed of gas production gradually slows down. Then, the temperature is raised to 70-80 ℃, and the reaction is maintained for 4-6 h. During this period, the inert gas is continuously introduced to maintain the inert atmosphere of the reaction system, ensuring the smooth progress of the reaction, until the final reaction system is completely degassed.

[0026] Further, after the reaction is completed, the reaction liquid is naturally cooled to room temperature, and then subjected to vacuum filtration to remove the unreacted tin powder and a small amount of solid impurities generated during the reaction, and the filtrate is collected.

[0027] Further, the vacuum rectification treatment specifically includes: 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.

[0028] Further, the glass rectification column has a column length of 80-100 cm and a glass packing height of 60-80 cm.

[0029] Further, the primary rectification treatment specifically includes: adjusting the vacuum degree to 50-100 torr, raising the temperature to 110-130 ℃ at a temperature rise rate of 2-3 ℃ / min, controlling the reflux ratio to be 1:1-2:1, and collecting the fraction at 90-100 ℃. The fraction mainly contains excess tertiary amyl alcohol and low-boiling-point impurities. The tertiary amyl alcohol can be recycled and purified for reuse to reduce production costs.

[0030] The secondary rectification treatment specifically includes: 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 rise rate of 1-2 ℃ / min, controlling the reflux ratio to be 3:1-4:1, and collecting the fraction at 120-140 ℃. The fraction is the preliminarily purified tertiary amyl alcohol stannous.

[0031] The tertiary rectification treatment specifically includes: 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 rise 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 alcohol stannous.

[0032] Further, the tertiary amyl alcohol stannous has a nuclear magnetic purity of 99% or more, a metal purity of 6N, and a colority of 10 APHA or less.

[0033] Compared with the prior art, the present application has the following beneficial effects:

[0034] The present application provides a preparation method of tertiary amyl alcohol stannous. The tertiary amyl alcohol stannous can be efficiently prepared by using tin powder and tertiary amyl alcohol as raw materials in the presence of a specific composite initiator (cuprous bromide and triphenylphosphine). In combination with a multi-stage rectification purification process, the tertiary amyl alcohol stannous with a purity of 6N and a yield of 85% can be obtained. In addition, the reaction process of the above preparation method is more controllable and mild, and the by-products are less. Moreover, the raw materials are widely available and low in cost, and the method is suitable for batch production.

[0035] Compared with the prior art, the present application uses tin powder as the core metal raw material to replace stannic halide, avoiding the problem of difficult filtration caused by a large amount of lithium, sodium and potassium halide by-products generated in the reaction, and avoiding the residual of halogen elements and lithium / sodium / potassium metal elements in the product from the source. In addition, the present application uses tertiary amyl alcohol and a composite initiator to replace lithium tert-amyl alcohol, sodium tert-amyl alcohol and potassium tert-amyl alcohol, which can effectively avoid the residual of lithium tert-amyl alcohol, sodium tert-amyl alcohol and potassium tert-amyl alcohol, and greatly improve the purification efficiency. The tertiary amyl alcohol stannous prepared by the above reaction system in combination with a multi-stage rectification purification process meets the high-purity requirement of the semiconductor field for tertiary amyl alcohol stannous. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 Figure 1 is a structural schematic diagram of tertiary amyl alcohol stannous;

[0037] Figure 2 Figure 2 is a nuclear magnetic hydrogen spectrum of the tertiary amyl alcohol stannous prepared in Example 1;

[0038] Figure 3 Figure 3 is a nuclear magnetic hydrogen spectrum of the tertiary amyl alcohol stannous prepared in Comparative Example 1;

[0039] Figure 4 Figure 4 is a nuclear magnetic hydrogen spectrum of the tertiary amyl alcohol stannous prepared in Comparative Example 2;

[0040] Figure 5 Figure 5 is a structure of a substituted incomplete compound impurity contained in the tertiary amyl alcohol stannous product prepared in Comparative Example 2. DETAILED DESCRIPTION

[0041] The present application will be further described below in conjunction with the drawings and specific examples, so that those skilled in the art can better understand the present application and implement it. However, the examples are not intended to limit the present application.

[0042] 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 application belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting of the application. The use herein of "including", "comprising" or "having" also contemplates "consisting of" or "consisting essentially of".

[0043] Example 1: This example relates to a preparation method of tertiary amyltin stannane, the specific operation is as follows:

[0044] (1) 500 g of 100 mesh, 99.99% pure metal tin powder was placed in a vacuum drying oven and dried at a temperature of 80 °C and a vacuum degree of 0.01 MPa for 6 h; 5000 mL of tertiary amyl alcohol was dehydrated by 3A molecular sieve for 48 h, and the dehydration effect was monitored by Karl Fischer water tester to ensure that the water content was less than 50 ppm, and was ready for use.

[0045] (2) In a stainless steel reaction kettle, the air in the kettle was replaced with nitrogen for 30 min, the nitrogen flow rate was maintained at 0.5 L / min, the pretreated metal tin powder in step (1) was added, followed by tertiary amyl alcohol, and then cuprous bromide and triphenylphosphine were added, wherein the molar ratio of metal tin powder, tertiary amyl alcohol, cuprous bromide and triphenylphosphine was 1:10:0.05:0.1, the stirring device was started to stir uniformly at a speed of 500 r / min, then heated to 40 °C, the reaction system gradually produced gas, and the reaction was carried out for 3 h, then the temperature was raised to 70 °C, and the reaction was continued for 6 h until the reaction system stopped releasing gas, and nitrogen was continuously introduced during the reaction. After the reaction was completed, the reaction liquid was cooled to room temperature, filtered under reduced pressure through a filter device, and the filtrate was collected.

[0046] (3) The filtrate collected in step (2) was transferred to a distillation device equipped with a glass rectifying column, the vacuum degree was adjusted to 100 torr, the heating rate was 2 °C / min, the reflux ratio was controlled at 2:1, the temperature range of 90-100 °C was collected (mainly excess tertiary amyl alcohol and low boiling point impurities), and the highest heating temperature was 120 °C; The kettle liquid remaining after the above distillation was further distilled, the vacuum degree was adjusted to 2 torr, the heating rate was reduced to 1 °C / min, the reflux ratio was controlled at 4:1, the temperature range of 120-140 °C was collected, and the tertiary amyl tin stannane was obtained, and the highest heating temperature was 200 °C; The above preliminary purified tertiary amyl tin stannane was distilled again, the vacuum degree was adjusted to 1 torr, the heating rate was controlled at 0.5 °C / min, the reflux ratio was increased to 5:1, the temperature range of 120-125 °C was collected, and the required tertiary amyl tin stannane product (colorless and transparent, yield 85%) was obtained, and the highest heating temperature was 190 °C.

[0047] The tertiary amyl alcohol stannous product prepared in the embodiment was subjected to nuclear magnetic resonance hydrogen spectrum, colorimeter and ICP-MS test, and the test results were as follows: the nuclear magnetic spectrum was as shown in Figure 2 , the nuclear magnetic purity of the product was ≥ 99%, the colority was ≤ 10 APHA, and the metal purity was 6N.

[0048] Embodiment 2: The embodiment relates to a preparation method of tertiary amyl alcohol stannous, and the specific operation is as follows:

[0049] (1) 500 g of 200-mesh metal tin powder with a purity of 99.99% was placed in a vacuum drying box and dried at a temperature of 80 ℃ and a vacuum degree of 0.01 MPa for 6 h; 5000 mL of tertiary amyl alcohol was subjected to dehydration treatment with 3A molecular sieves for 48 h, and the dehydration effect was monitored by using a Karl Fischer water tester to ensure that the water content was lower than 50 ppm, and the tertiary amyl alcohol was prepared.

[0050] (2) In a stainless steel reaction kettle, nitrogen was introduced to replace the air in the kettle for 30 min, the nitrogen introduction rate was maintained at 0.5 L / min, the pretreated metal tin powder in step (1) was added, then tertiary amyl alcohol was added, and then cuprous bromide and triphenylphosphine were added, wherein the molar ratio of the metal tin powder, the tertiary amyl alcohol, the cuprous bromide and the triphenylphosphine was 1:15:0.08:0.15, a stirring device was started to uniformly stir at a speed of 800 r / min, then heating was started to 40 ℃, the reaction system gradually produced gas, and the reaction was kept for 3 h, then the temperature was increased to 70 ℃, and the reaction was continued for 6 h until the reaction system stopped producing gas, and nitrogen was continuously introduced during the reaction. After the reaction was completed, the reaction liquid was cooled to room temperature, and the filtrate was collected by filtration under reduced pressure through a filter device.

[0051] (3) The filtrate collected in step (2) was transferred to a rectification device equipped with a glass rectification column, the vacuum degree was first adjusted to 80 torr, heating was started at a temperature increasing rate of 3 ℃ / min, the reflux ratio was controlled to be 1:1, the fraction in the temperature range of 90-100 ℃ (mainly excess tertiary amyl alcohol and low-boiling-point impurities) was collected, and the highest heating temperature was 120 ℃; the kettle liquid remaining after the above rectification was continuously rectified, the vacuum degree was adjusted to 2 torr, the temperature increasing rate was reduced to 2 ℃ / min, the reflux ratio was controlled to be 3:1, the fraction in the temperature range of 120-140 ℃ was collected, the initially purified tertiary amyl alcohol stannous was obtained, and the highest heating temperature was 200 ℃; the initially purified tertiary amyl alcohol stannous was rectified again, the vacuum degree was adjusted to 1.5 torr, the temperature increasing rate was controlled to be 0.5 ℃ / min, the reflux ratio was increased to 5:1, the fraction in the temperature range of 120-125 ℃ was collected, the required tertiary amyl alcohol stannous product (colorless and transparent, the yield was 83%) was obtained, and the highest heating temperature was 190 ℃.

[0052] The product of the tertiary amyl alcohol stannous prepared in the example was tested by nuclear magnetic resonance hydrogen spectrum, colorimeter and ICP-MS, and the test results were as follows: the nuclear magnetic purity of the product was ≥ 99%, the colority was ≤ 10 APHA, and the metal purity was 6 N.

[0053] Example 3: The example relates to a preparation method of tertiary amyl alcohol stannous, and the difference from example 1 is only that the molar ratio of the tin powder, tertiary amyl alcohol, cuprous bromide and triphenylphosphine in step (2) is 1:10:0.05:0.05, and the rest of the operations are consistent, and the corresponding tertiary amyl alcohol stannous product is prepared, and the yield is 68%.

[0054] The product of the tertiary amyl alcohol stannous prepared in the example was tested by nuclear magnetic resonance hydrogen spectrum, colorimeter and ICP-MS, and the test results were as follows: the nuclear magnetic purity of the product was ≥ 99%, the colority was ≤ 10 APHA, and the metal purity was 6 N.

[0055] Example 4: The example relates to a preparation method of tertiary amyl alcohol stannous, and the difference from example 1 is only that the molar ratio of the tin powder, tertiary amyl alcohol, cuprous bromide and triphenylphosphine in step (2) is 1:10:0.05:0.15, and the rest of the operations are consistent, and the corresponding tertiary amyl alcohol stannous product is prepared, and the yield is 84%.

[0056] The product of the tertiary amyl alcohol stannous prepared in the example was tested by nuclear magnetic resonance hydrogen spectrum, colorimeter and ICP-MS, and the test results were as follows: the nuclear magnetic purity of the product was ≥ 99%, the colority was ≤ 10 APHA, and the metal purity was 6 N.

[0057] Example 5: The example relates to a preparation method of tertiary amyl alcohol stannous, and the difference from example 1 is only that the molar ratio of the tin powder, tertiary amyl alcohol, cuprous bromide and triphenylphosphine in step (2) is 1:10:0.1:0.3, and the rest of the operations are consistent, and the corresponding tertiary amyl alcohol stannous product is prepared, and the yield is 81%.

[0058] The product of the tertiary amyl alcohol stannous prepared in the example was tested by nuclear magnetic resonance hydrogen spectrum, colorimeter and ICP-MS, and the test results were as follows: the nuclear magnetic purity of the product was ≥ 99%, the colority was ≤ 10 APHA, and the metal purity was 5 N.

[0059] Comparative Example 1: The comparative example relates to a preparation method of tertiary amyl alcohol stannous, and the tertiary amyl alcohol stannous is prepared by using anhydrous stannous chloride and potassium tertiary amyl alcohol as the reaction raw materials, and the specific operation is as follows:

[0060] (1) Take 500 g of anhydrous stannous chloride purchased on the market and place it in a vacuum drying oven. Dry it at a temperature of 80 °C and a vacuum degree of 0.01 MPa for 6 h. Prepare potassium tert-pentoxide by yourself. Take 5000 mL of tetrahydrofuran and dehydrate it with 3A molecular sieves for 48 h. Monitor the dehydration effect with a Karl Fischer water tester to ensure that the water content is less than 50 ppm. Prepare it for use.

[0061] (2) In a stainless steel reaction kettle, replace the air in the kettle with nitrogen for 30 min. Maintain the nitrogen flow rate at 0.5 L / min. Add the pretreated anhydrous stannous chloride, tetrahydrofuran, and potassium tert-pentoxide in sequence. The molar ratio of stannous chloride, potassium tert-pentoxide, and tetrahydrofuran is 1:2.2:15. Turn on the stirring device and stir uniformly at a rate of 800 r / min. Then heat to 50 °C and maintain the temperature for 3 h. Then increase the temperature to 80 °C and continue to react for 6 h. During the reaction, continuously introduce nitrogen. After the reaction is completed, cool the reaction liquid to room temperature. Filter it under reduced pressure with a filter device and collect the filtrate.

[0062] (3) Transfer the filtrate collected in step (2) to a distillation device equipped with a glass rectifying column. First, adjust the vacuum degree to 80 torr. Heat at a rate of 3 °C / min. Control the reflux ratio to be 1:1. Collect the fraction in the temperature range of 60-70 °C (mainly tetrahydrofuran and low-boiling-point impurities). The maximum heating temperature is 120 °C. Continue to distill the remaining kettle liquid from the above step. Adjust the vacuum degree to 2 torr. Reduce the heating rate to 2 °C / min. Control the reflux ratio to be 3:1. Collect the fraction in the temperature range of 120-140 °C. Obtain the preliminarily purified tert-pentoxide stannous. The maximum heating temperature is 200 °C. Distill the preliminarily purified tert-pentoxide stannous again. Adjust the vacuum degree to 1.5 torr. Control the heating rate to be 0.5 °C / min. Increase the reflux ratio to 5:1. Collect the fraction in the temperature range of 120-125 °C. This is the desired tert-pentoxide stannous product (colorless and transparent, yield 23%). The maximum heating temperature is 190 °C.

[0063] Test the tert-pentoxide stannous product prepared in this comparative example by nuclear magnetic resonance hydrogen spectrum and ICP-MS. The test results are as follows: the nuclear magnetic spectrum is as shown in Figure 3 The nuclear magnetic purity of the product is ≤80%, and the metal purity is 4 N.

[0064] Comparative Example 2: This comparative example relates to a method for preparing tert-pentoxide stannous. Anhydrous stannous chloride, tert-pentoxide, and potassium bis(trimethylsilyl)amide are used as reaction raw materials to prepare tert-pentoxide stannous. The specific operation is as follows:

[0065] (1) Take 500 g of anhydrous stannous chloride purchased on the market and place it in a vacuum drying oven. Dry it at a temperature of 80 °C and a vacuum degree of 0.01 MPa for 6 h. Prepare potassium tert-pentoxide by yourself. Take 5000 mL of tetrahydrofuran and dehydrate it with 3A molecular sieves for 48 h. Monitor the dehydration effect with a Karl Fischer water tester to ensure that the water content is less than 50 ppm. Prepare it for use.

[0066] (2) In a stainless steel reaction kettle, replace the air in the kettle with nitrogen for 30 min. Maintain the nitrogen flow rate at 0.5 L / min. Add the pretreated anhydrous stannous chloride, tetrahydrofuran, and potassium bis(trimethylsilyl)amide tetrahydrofuran solution (1.0 M) in sequence. Turn on the stirring device and stir uniformly at a rate of 800 r / min. Then, heat it to 50 °C and keep it at this temperature for 3 h. Then, increase the temperature to 80 °C and continue to react for 6 h. After the reaction is completed, restore it to room temperature. Add potassium tert-pentoxide and stir it uniformly. Heat it to 50 °C and keep it at this temperature for 3 h. Then, increase the temperature to 80 °C and continue to react for 6 h. During the reaction, continuously introduce nitrogen. After the reaction is completed, cool the reaction liquid to room temperature. Filter it under reduced pressure with a filter device and collect the filtrate. The molar ratio of stannous chloride, potassium bis(trimethylsilyl)amide tetrahydrofuran solution, potassium tert-pentoxide, and tetrahydrofuran is 1:2.1:2.5:15.

[0067] (3) Transfer the filtrate collected in step (2) to a rectification device equipped with a glass rectifying column. First, adjust the vacuum degree to 80 torr. Heat it at a rate of 3 °C / min. Control the reflux ratio to be 1:1. Collect the fraction in the temperature range of 60-70 °C (mainly tetrahydrofuran and low-boiling-point impurities). The maximum heating temperature is 120 °C. Continue to rectify the remaining kettle liquid after the above rectification. Adjust the vacuum degree to 2 torr. Reduce the heating rate to 2 °C / min. Control the reflux ratio to be 3:1. Collect the fraction in the temperature range of 120-140 °C. Obtain the preliminarily purified potassium tert-pentoxide stannous. The maximum heating temperature is 200 °C. Further rectify the preliminarily purified potassium tert-pentoxide stannous. Adjust the vacuum degree to 1.5 torr. Control the heating rate to be 0.5 °C / min. Increase the reflux ratio to 5:1. Collect the fraction in the temperature range of 120-125 °C. It is the desired potassium tert-pentoxide stannous product (colorless and transparent, with a yield of 45%). The maximum heating temperature is 190 °C.

[0068] Test the potassium tert-pentoxide stannous product prepared in this comparative example by nuclear magnetic resonance hydrogen spectrum. The test results are as follows: The nuclear magnetic spectrum is shown in Figure 4 . The nuclear magnetic purity of the product is ≤70%. It contains incompletely substituted compounds (structures are shown in Figure 5 ).

[0069] Comparative Example 3: This comparative example relates to a preparation method of tertiary amyltin stannous, which is different from Example 1 only in that the initiator type is different, and aluminum chloride is used instead of the composite initiator of cuprous bromide and triphenylphosphine, and the rest of the operations are consistent, as follows:

[0070] (1) 500 g of 100 mesh, 99.99% pure metal tin powder was placed in a vacuum drying oven and dried at a temperature of 80 °C and a vacuum degree of 0.01 MPa for 6 h; 5000 mL of tertiary amyl alcohol was treated with 3A molecular sieves for 48 h, and the water removal effect was monitored using a Karl Fischer water tester to ensure that the water content was less than 50 ppm, ready for use.

[0071] (2) In a stainless steel reaction kettle, nitrogen was introduced to replace the air in the kettle for 30 min, and the nitrogen flow rate was maintained at 0.5 L / min. The pretreated metal tin powder, tertiary amyl alcohol, and aluminum chloride in step (1) were added in sequence, and the molar ratio of metal tin powder, tertiary amyl alcohol, and aluminum chloride was 1:10:0.15. The stirring device was turned on at a speed of 800 r / min to stir uniformly, and then heated to 40 °C and kept at this temperature for 3 h. Then the temperature was raised to 70 °C and the reaction was continued for 6 h, during which nitrogen was continuously introduced. After the reaction was completed, the reaction liquid was cooled to room temperature, filtered under reduced pressure through a filter device, and the filtrate was collected.

[0072] (3) The filtrate collected in step (2) was transferred to a distillation device equipped with a glass rectifying column. The vacuum degree was adjusted to 100 torr, and the temperature was raised at a rate of 2 °C / min. The reflux ratio was controlled at 2:1, and the fraction collected at a temperature range of 90-100 °C (mainly excess tertiary amyl alcohol and low boiling point impurities) was collected. The maximum heating temperature was 120 °C. The remaining kettle liquid after the above distillation was further distilled. The vacuum degree was adjusted to 2 torr, the temperature was raised at a rate of 1 °C / min, and the reflux ratio was controlled at 4:1. The maximum heating temperature was 200 °C, and no product was collected.

[0073] Comparative Example 4: This comparative example relates to a preparation method of tertiary amyltin stannous, which is different from Example 1 only in that only cuprous bromide is added as an initiator, and the rest of the operations are consistent, as follows:

[0074] (1) 500 g of 100 mesh, 99.99% pure metal tin powder was placed in a vacuum drying oven and dried at a temperature of 80 °C and a vacuum degree of 0.01 MPa for 6 h; 5000 mL of tertiary amyl alcohol was treated with 3A molecular sieves for 48 h, and the water removal effect was monitored using a Karl Fischer water tester to ensure that the water content was less than 50 ppm, ready for use.

[0075] (2) In a stainless steel reaction kettle, nitrogen was introduced to replace the air in the kettle for 30 min, the nitrogen flow rate was maintained at 0.5 L / min, the pretreated tin powder in step (1) was added, followed by the addition of tert-pentanol, and then cuprous bromide was added, wherein the molar ratio of tin powder, tert-pentanol and cuprous bromide was 1:10:0.15, the stirring device was turned on, and the mixture was stirred uniformly at a speed of 800 r / min, then heated to 40 ℃, and kept at this temperature for 3 h, then heated to 70 ℃, and continued to react for 6 h, during which nitrogen was continuously introduced. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure through a filter device, and the filtrate was collected.

[0076] (3) The filtrate collected in step (2) was transferred to a distillation device equipped with a glass rectifying column, the vacuum degree was first adjusted to 100 torr, heated at a temperature rise rate of 2 ℃ / min, the reflux ratio was controlled at 2:1, the temperature range of 90-100 ℃ was collected (mainly excess tert-pentanol and low boiling point impurities), and the highest heating temperature was 120 ℃; the kettle liquid remaining after the above distillation was further distilled, the vacuum degree was adjusted to 2 torr, the temperature rise rate was reduced to 1 ℃ / min, the reflux ratio was controlled at 4:1, the highest heating temperature was 200 ℃, and no product was collected.

[0077] Comparative Example 5: This comparative example relates to a method for preparing tert-pentanol stannous, which is different from Example 1 only in that triphenylphosphine is added as an initiator, and the rest of the operations are consistent, as follows:

[0078] (1) 500 g of 100 mesh, 99.99% pure tin powder was placed in a vacuum drying oven and dried at a temperature of 80 ℃ and a vacuum degree of 0.01 MPa for 6 h; 5000 mL of tert-pentanol was treated with 3A molecular sieves for 48 h, and a Karl Fischer water tester was used to monitor the water removal effect to ensure that the water content was less than 50 ppm.

[0079] (2) In a stainless steel reaction kettle, nitrogen was introduced to replace the air in the kettle for 30 min, the nitrogen flow rate was maintained at 0.5 L / min, the pretreated tin powder in step (1) was added, followed by the addition of tert-pentanol, and then cuprous bromide was added, wherein the molar ratio of tin powder, tert-pentanol and cuprous bromide was 1:10:0.15, the stirring device was turned on, and the mixture was stirred uniformly at a speed of 800 r / min, then heated to 40 ℃, and kept at this temperature for 3 h, then heated to 70 ℃, and continued to react for 6 h, during which nitrogen was continuously introduced. After the reaction was completed, the reaction solution was cooled to room temperature, filtered under reduced pressure through a filter device, and the filtrate was collected.

[0080] (3) The filtrate collected in step (2) is transferred to a distillation device equipped with a glass rectifying column, the vacuum degree is first adjusted to 100 torr, heating is performed at a temperature increasing rate of 2 ℃ / min, the reflux ratio is controlled to be 2:1, the fraction in the temperature range of 90-100 ℃ (mainly excess tertiary amyl alcohol and low-boiling impurities) is collected, and the highest heating temperature is 120 ℃; the remaining kettle liquid after the above distillation is continuously distilled, the vacuum degree is adjusted to 2 torr, the temperature increasing rate is reduced to 1 ℃ / min, the reflux ratio is controlled to be 4:1, the highest heating temperature is 200 ℃, and no product is collected.

[0081] The above-described embodiments are only preferred embodiments for fully illustrating the present application, and the protection scope of the present application is not limited thereto. Any equivalent replacement or transformation made by those skilled in the art on the basis of the present application is within the protection scope of the present application. The protection scope of the present application is subject to the claims.

Claims

1. A method for preparing tert-amyl stannous oxide, characterized in that, Includes 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.

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

3. The preparation method according to claim 1, characterized in that, The tin powder is dried tin powder, and the drying conditions are: vacuum degree of 0.01-0.02 MPa, temperature of 80-100 ℃, and time of 4-6 h.

4. The preparation method according to claim 1, characterized in that, The water content of the tert-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 preparation method according to claim 1, characterized in that, The molar ratio of tin powder to tert-amyl alcohol is 1:(10-15). The molar ratio of tin powder to cuprous bromide and triphenylphosphine is 1:(0.05-0.08):(0.1-0.15).

7. The preparation method according to claim 1, characterized in that, The reaction is carried out at a temperature of 40-80 °C for a time of not less than 6 h.

8. The preparation method according to claim 1, characterized in that, The reaction is a staged temperature-controlled reaction, specifically: first, the temperature is raised to 40-50 ℃ and held for 2-3 h, then the temperature is raised to 70-80 ℃ and held for 4-6 h.

9. The preparation method according to claim 1, characterized in that, 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. 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 ℃. 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 ℃. 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.

10. The preparation method according to claim 9, characterized in that, The tert-amyl tin oxide has an NMR purity of ≥99%, a metallic purity of 6 N, and a chromaticity of ≤10 APHA.

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