A process for the preparation of triethylantimony

Abstract

The present application relates to triethyl antimony processing technical field, especially in kind of preparation triethyl antimony, including the following steps: under the protection of inert gas to the reaction bottle raw material antimony trichloride and ether solvent is added, and the atmospheric pressure reflux device is installed, and the stirring is started;Ethyl lithium ether solution is added dropwise to the reaction bottle, after dropwise addition is completed, 70~80 ℃ stirring reaction is kept for 3~6h;After the stirring reflux is finished, the solvent ether is distilled out first, and the triethyl antimony initial product is obtained;The vacuum distillation device is installed, and the triethyl antimony crude product is obtained by vacuum distillation;The obtained triethyl antimony crude product is subjected to twice vacuum rectification, and high-purity triethyl antimony is obtained, and the purity reaches 6N by nuclear magnetic resonance, ICP detection.Pure triethyl antimony is generated by the reaction of ethyl lithium and antimony trichloride under the protection of inert gas, the preparation method is safe and efficient, simple operation, raw material is easy to obtain, no by-product, high yield and high purity product.

Description

Technical Field

[0001] This invention relates to the field of triethylantimony processing technology, and more particularly to a method for preparing triethylantimony. Background Technology

[0002] High-purity electronic materials are support materials used in epitaxial growth processes employing metal-organic chemical vapor deposition (MOCVD) technology. They are used to produce ultra-high brightness LEDs, HEMT (high electron mobility transistor) devices, semiconductor lasers, infrared detectors, and solar cells, making them crucial materials for the development of the optoelectronic industry. Their purity has a vital impact on the final optoelectronic devices, especially playing a decisive role in the functionality of high-power, ultra-high brightness LED chips.

[0003] High-purity triethylantimony provides the antimony source for semiconductor materials such as AlSb, GaSb, and InSb. It is one of the most important sources for growing optoelectronic materials in metal-organic chemical vapor deposition (MOCVD) and chemical beam epitaxy (CBE) processes, playing an irreplaceable role in the semiconductor materials and LED industries. The performance of these semiconductor material deposits is highly dependent on the purity of triethylantimony; even trace amounts of impurities can affect its performance. Therefore, developing a simple and efficient method for preparing high-purity triethylantimony (6N, 99.9999%) is extremely important.

[0004] Currently, triethylantimony is mainly prepared in China using Grignard reagents and antimony trichloride. For example, Chinese invention patent application CN201610732503.7 discloses a method for preparing high-purity triethylantimony using the Grignard reagent method. However, this method has a low yield; the highest crude product yield in the examples is only 61%, and the purity can only be controlled above 5N. Chinese invention patent application CN202210679743.0 discloses a method for preparing high-purity triethylantimony, which effectively removes organic impurities introduced during the preparation of triethylantimony. Furthermore, ICP-OES elemental analysis shows that all inorganic impurities are <1 ppm. However, the yield is still not high enough; the highest crude product yield in the examples is 78%, which cannot meet the growing market demand for antimony sources. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a simple and efficient method for preparing triethylantimony, which is simple to operate, uses readily available raw materials, produces no by-products, has a high yield, and yields a product with high purity (6N).

[0006] To achieve the above objectives, the present invention provides a method for preparing triethylantimony, comprising the following steps:

[0007] S1. Under the protection of an inert gas, add antimony trichloride and diethyl ether solvent to the reaction flask, set up an atmospheric pressure reflux device, and start stirring;

[0008] S2. Add the ethyl lithium diethyl ether solution dropwise into the reaction flask. After the addition is complete, maintain the temperature at 70-80°C and stir for 3-6 hours.

[0009] S3. After stirring and reflux, the solvent diethyl ether is distilled off under normal pressure to obtain the initial product of triethylantimony.

[0010] S4. Modify the vacuum distillation apparatus to obtain crude triethylantimony by vacuum distillation;

[0011] S5. The obtained crude triethylantimony was subjected to two vacuum distillations to obtain high-purity triethylantimony, and the purity reached 6N as determined by NMR and ICP.

[0012] All steps are performed in an inert gas environment.

[0013] Optionally, the antimony trichloride needs to be dried, which is carried out by heating at 40~45℃ under absolute pressure vacuum drying, followed by cooling and weighing until constant weight is achieved.

[0014] Optionally, the atmospheric pressure reflux device includes a condenser tube, which is refrigerated by cooling oil, and the cooling oil temperature is set to -5±1℃.

[0015] Optionally, the molar ratio of antimony trichloride to ethyl lithium is 1:3.15 to 4.5, preferably 1:3.6.

[0016] Optionally, the dropping speed needs to be adjusted according to the intensity of the reaction in the reaction flask.

[0017] Optionally, the stirring reaction for 3-6 hours is started when the temperature rises to 70-80°C and the stirring reaction is carried out for 3-6 hours, preferably 5 hours.

[0018] Optionally, the reduced pressure distillation is controlled at 100 Torr, and the fraction obtained is at 94~95℃.

[0019] Optionally, in both vacuum distillations, the initial and final fractions are removed at a ratio of 5-10% of the triethylantimony content, and the resulting middle fraction is high-purity triethylantimony.

[0020] This invention provides a method for preparing triethylantimony, the core of which lies in the reaction of ethyllithium and antimony trichloride under inert gas protection to generate triethylantimony. The specific reaction equation is as follows:

[0021]

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] 1. This invention provides a method for preparing triethylantimony, which utilizes the reaction of ethyllithium and antimony trichloride under inert gas protection to generate triethylantimony. The operation is simple and the raw materials are readily available.

[0024] 2. This invention provides a method for preparing triethylantimony, which significantly improves the yield and yields a product with higher purity (6N) compared to the conventional Grignard reagent method. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this invention. For those skilled in the art, other drawings obtained from these drawings without creative effort are also within the protection scope of this invention.

[0026] Figure 1 The present invention provides a method for preparing triethylantimony, comprising the following process steps:

[0027] Figure 2 This is the 1H NMR spectrum of high-purity triethylantimony in an embodiment of the present invention. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the specific embodiments.

[0029] It should be noted that, unless otherwise defined, the technical or scientific terms used in this invention should have the ordinary meaning understood by one of ordinary skill in the art to which this invention pertains. The terms "first," "second," and similar terms used in this invention do not indicate any order, quantity, or importance, but are merely used to distinguish different components. Terms such as "comprising" or "including" mean that the element or object preceding the word encompasses the elements or objects listed following the word and their equivalents, without excluding other elements or objects. Terms such as "connected" or "linked" are not limited to physical or mechanical connections, but can include electrical connections, whether direct or indirect. Terms such as "upper," "lower," "left," and "right" are used only to indicate relative positional relationships; when the absolute position of the described object changes, the relative positional relationship may also change accordingly.

[0030] like Figure 1 As shown in the figure, a specific embodiment of the present invention provides a method for preparing triethylantimony, comprising:

[0031] S1. Under the protection of an inert gas, add antimony trichloride and diethyl ether solvent to the reaction flask, set up an atmospheric pressure reflux device, and start stirring;

[0032] S2. Add the ethyl lithium diethyl ether solution dropwise into the reaction flask. After the addition is complete, maintain the temperature at 70-80°C and stir for 3-6 hours.

[0033] S3. After stirring and reflux, the solvent diethyl ether is distilled off under normal pressure to obtain the initial product of triethylantimony.

[0034] S4. Modify the vacuum distillation apparatus to obtain crude triethylantimony by vacuum distillation;

[0035] S5. The obtained crude triethylantimony was subjected to two vacuum distillations to obtain high-purity triethylantimony, and the purity reached 6N as determined by NMR and ICP.

[0036] All steps are performed in an inert gas environment.

[0037] In some optional specific embodiments, the antimony trichloride needs to be dried, which is carried out by heating to 40~45°C under absolute pressure vacuum drying, followed by cooling and weighing until constant weight.

[0038] In some optional embodiments, the atmospheric pressure reflux device includes a condenser tube, which is refrigerated by cooling oil, with the oil temperature set to -5±1℃.

[0039] In some optional embodiments, the molar ratio of antimony trichloride to ethyl lithium is 1:3.15 to 4.5, preferably 1:3.6.

[0040] In some optional embodiments, the dropping rate needs to be adjusted according to the intensity of the reaction in the reaction flask.

[0041] In some optional specific embodiments, the stirring reaction for 3-6 hours is started when the temperature rises to 70-80°C and the stirring reaction is carried out for 3-6 hours, with 5 hours being preferred.

[0042] In some optional embodiments, the vacuum distillation is carried out at a controlled pressure of 100 Torr, and a fraction at 94-95°C is received.

[0043] In some optional specific embodiments, the two vacuum distillations remove the front and rear fractions at a ratio of 5-10% of the triethylantimony content, and the final middle fraction is high-purity triethylantimony.

[0044] The following are three specific examples:

[0045] Example 1

[0046] In an inert gas environment, add 114.1 g (0.5 mol) of antimony trichloride and 100 mL of diethyl ether solvent to a 2 L four-necked flask, set up an atmospheric pressure reflux apparatus, and start stirring;

[0047] The condenser is cooled by circulating cold oil, and the temperature of the cold oil is set to -4℃. When the temperature of the cold oil drops to the set temperature, 1L of ethyl lithium ether solution (1.6M) is slowly added dropwise. The reaction is relatively vigorous, and the dropwise addition is gradually increased. After the ethyl lithium is completely added, the temperature is adjusted to 70℃ and the reaction is stirred for 3 hours.

[0048] After stirring and reflux, the solvent diethyl ether is first distilled off under normal pressure to obtain the initial product of triethylantimony.

[0049] The pressure was controlled at 100 Torr by modifying the vacuum distillation apparatus and collecting the fraction at 94-95℃ to obtain crude triethylantimony.

[0050] The obtained crude triethylantimony was subjected to two vacuum distillations: the initial and final fractions were removed at a ratio of 5% to 10% of the triethylantimony content, and the resulting middle fraction was high-purity triethylantimony. Samples of the middle fraction were taken for NMR and ICP analysis to confirm its purity.

[0051] All the above steps were carried out in an inert gas environment. In this case, the yield of triethylantimony synthesis was 80%. The product was confirmed to be triethylantimony by JNM-ECZ400S nuclear magnetic resonance spectrometer. Inductively coupled plasma atomic emission spectrometry (Optima8000) detected that all inorganic elements were <1ppm, and the purity reached 6N.

[0052] Example 2

[0053] Add 171.1g (0.75mol) of antimony trichloride and 150mL of diethyl ether to a 3L four-necked flask under an inert gas atmosphere, set up a normal pressure reflux apparatus, and start stirring;

[0054] The condenser was cooled by circulating cold oil, with the oil temperature set to -5℃. When the oil temperature dropped to the set temperature, 2.1L of ethyl lithium ether solution (1.6M) was slowly added dropwise. The reaction was quite vigorous, so the addition was gradually increased. After the ethyl lithium was added, the temperature was adjusted to 80℃ and the reaction was stirred for 4 hours.

[0055] After stirring and reflux, the solvent diethyl ether is first distilled off under normal pressure to obtain the initial product of triethylantimony.

[0056] The pressure was controlled at 100 Torr by modifying the vacuum distillation apparatus and collecting the fraction at 94-95℃ to obtain crude triethylantimony.

[0057] The obtained crude triethylantimony was subjected to two vacuum distillations: the initial and final fractions were removed at a ratio of 5% to 10% of the triethylantimony content, and the resulting middle fraction was high-purity triethylantimony. Samples of the middle fraction were taken for NMR and ICP analysis to confirm its purity.

[0058] All the above steps were carried out in an inert gas environment. In this case, the yield of triethylantimony synthesis was 84%. The product was confirmed to be triethylantimony by JNM-ECZ400S nuclear magnetic resonance spectrometer. Inductively coupled plasma atomic emission spectrometry (Optima8000) detected that all inorganic elements were <1ppm, and the purity reached 6N.

[0059] Example 3

[0060] In an inert gas environment, add 114.1 g (0.5 mol) of antimony trichloride and 100 mL of diethyl ether solvent to a 2 L four-necked flask, set up an atmospheric pressure reflux apparatus, and start stirring;

[0061] The condenser is cooled by circulating cold oil, with the oil temperature set to -5℃. When the oil temperature drops to the set temperature, 1.13L of ethyl lithium ether solution (1.6M) is slowly added dropwise. The reaction is relatively vigorous, so the dropwise addition is gradually increased. After the ethyl lithium is completely added, the temperature is adjusted to 80℃ and the reaction is stirred for 5 hours.

[0062] After stirring and reflux, the solvent diethyl ether is first distilled off under normal pressure to obtain the initial product of triethylantimony.

[0063] The pressure was controlled at 100 Torr by modifying the vacuum distillation apparatus and collecting the fraction at 94-95℃ to obtain crude triethylantimony.

[0064] The obtained crude triethylantimony was subjected to two vacuum distillations: the initial and final fractions were removed at a ratio of 5% to 10% of the triethylantimony content, and the resulting middle fraction was high-purity triethylantimony. Samples of the middle fraction were taken for NMR and ICP analysis to confirm its purity.

[0065] All the above steps were carried out in an inert gas environment. In this case, the yield of triethylantimony synthesis was 86%. The product was confirmed as triethylantimony by JNM-ECZ400S nuclear magnetic resonance spectrometer. Inductively coupled plasma atomic emission spectrometry (Optima8000) detected that all inorganic elements were <1ppm (the content was lower than the detection limit of the corresponding inorganic elements, see Table 1), and the purity reached 6N.

[0066] Table 1. Impurity content of triethylantimony after purification (unit: ppm)

[0067]

[0068] Note: ND indicates not detected; purity ≥ 99.9999%, i.e. total impurities ≤ 1 ppm.

[0069] Figure 2 The image shows the 1H NMR spectrum of high-purity triethylantimony prepared in a specific embodiment of the present invention. As can be seen from the image, there are only peaks of triethylantimony and the solvent deuterium benzene.

[0070] Therefore, the present invention provides a method for preparing triethylantimony, which generates triethylantimony by reacting ethyllithium and antimony trichloride under inert gas protection. The method is simple to operate, the raw materials are readily available, and the yield is significantly improved compared with the conventional Grignard reagent method, and the obtained product has a high purity (6N).

[0071] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention (including the claims) is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in the details for the sake of brevity.

[0072] This invention is intended to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. A method for preparing triethylantimony, characterized in that, Includes the following steps: S1. Under the protection of an inert gas, add antimony trichloride and diethyl ether solvent to the reaction flask, set up an atmospheric pressure reflux device, and start stirring; S2. Add the ethyl lithium diethyl ether solution dropwise into the reaction flask. After the addition is complete, maintain the temperature at 70-80°C and stir for 3-6 hours. S3. After stirring and reflux, the solvent diethyl ether is distilled off under normal pressure to obtain the initial product of triethylantimony. S4. Modify the vacuum distillation apparatus to obtain crude triethylantimony by vacuum distillation; S5. The obtained crude triethylantimony was subjected to two vacuum distillations to obtain triethylantimony, and the purity reached 6N as determined by NMR and ICP. All steps are performed in an inert gas environment; The atmospheric pressure reflux device includes a condenser tube, which is refrigerated by cooling oil, and the temperature of the cooling oil is set to -5±1℃. The stirring reaction time of 3 to 6 hours is defined as starting the timer when the temperature reaches 70 to 80°C and stirring for 3 to 6 hours.

2. The method for preparing triethylantimony according to claim 1, characterized in that, The antimony trichloride needs to be dried, which is carried out by heating at 40-45°C under absolute pressure and vacuum drying, followed by cooling and weighing until constant weight is achieved.

3. The method for preparing triethylantimony according to claim 1, characterized in that, The molar ratio of antimony trichloride to ethyl lithium is 1:3.15 ~ 4.

5.

4. The method for preparing triethylantimony according to claim 1, characterized in that, The dropping rate needs to be adjusted according to the intensity of the reaction in the reaction flask.

5. The method for preparing triethylantimony according to claim 1, characterized in that, The vacuum distillation is carried out at a controlled pressure of 100 Torr, and the fraction collected is 94-95°C.

6. The method for preparing triethylantimony according to claim 1, characterized in that, Both vacuum distillations removed the front and rear fractions at a ratio of 5-10% of the triethylantimony content, and the final middle fraction was triethylantimony.

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