Electronic-grade bromotrichloromethane, preparation method therefor, and use thereof

Abstract

Electronic-grade bromotrichloromethane, a preparation method therefor, and a use thereof. The preparation method for the electronic-grade bromotrichloromethane comprises the following steps: mixing a bromotrichloromethane raw material with a 13X molecular sieve for adsorption, and filtering the mixture to obtain a filtrate; and subjecting the filtrate to distillation treatment under atmospheric pressure, and sequentially collecting a first fraction and a second fraction, wherein the second fraction is the electronic-grade bromotrichloromethane; and the mass of the first fraction is 12-18% of the mass of the filtrate, and the mass of the second fraction is 65-75% of the mass of the filtrate. By means of the preparation method for electronic-grade bromotrichloromethane, bromotrichloromethane having higher purity can be prepared.

Description

Electronic grade bromochloromethane, preparation method and application thereof

[0001] The present invention claims priority to Chinese patent application No. 202311496052.8 filed with the Patent Office of China on November 10, 2023, entitled “Electronic-grade bromotrichloromethane, its preparation method and its application”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The present invention relates to the technical field of chemical purification, in particular to electronic-grade bromochloromethane, a preparation method thereof and application thereof. Background Art

[0003] Bromotrichloromethane is a new liquid carbon source that effectively overcomes the shortcomings of carbon tetrachloride and carbon tetrabromide. Bromotrichloromethane is a colorless, clear, heavy liquid with a melting point of -21°C, a boiling point of 104.7°C, a relative density (20 / 4°C) of 2.01, and a refractive index of 1.5051. It is miscible with most organic liquids and is light-sensitive. Currently, commercially available bromotrichloromethane is generally 98%-99% pure, which is considered relatively low purity.

[0004] The information disclosed in this background technology section is only intended to enhance understanding of the overall background of the invention and should not be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0005] Summary of the Invention

[0006] The object of the present invention is to provide a method for preparing electronic-grade bromochloromethane, which can produce bromochloromethane with higher purity.

[0007] To achieve the above object, an embodiment of the present invention provides a method for preparing electronic-grade bromotrichloromethane, comprising the following steps:

[0008] Mixing bromotrichloromethane and 13X molecular sieve for adsorption, and filtering to obtain a filtrate;

[0009] The filtrate is subjected to atmospheric distillation to collect a first fraction and a second fraction in sequence, wherein the second fraction is the electronic-grade bromochloromethane, and the mass of the first fraction is 12% to 18% of the mass of the filtrate; the mass of the second fraction is 65% to 75% of the mass of the filtrate.

[0010] In one or more embodiments of the present invention, the purity of bromochloromethane in the bromochloromethane raw material is greater than or equal to 98%, and the mass ratio of the 13X molecular sieve to the bromochloromethane raw material is greater than 8%.

[0011] In one or more embodiments of the present invention, the pore size of the 13X molecular sieve is 10 angstroms.

[0012] In one or more embodiments of the present invention, the time for mixed adsorption in the step of mixing bromochloroform with 13X molecular sieve is 22 to 26 hours.

[0013] In one or more embodiments of the present invention, the step of adsorbing the bromochloroform raw material mixed with the 13X molecular sieve comprises:

[0014] In anhydrous and oxygen-free conditions and an inert gas atmosphere, the trichlorobromomethane raw material is mixed with 13X molecular sieve for adsorption.

[0015] In one or more embodiments of the present invention, the distillation temperature in the step of subjecting the filtrate to atmospheric distillation is 105-108°C.

[0016] In one or more embodiments of the present invention, the preparation method further comprises the following steps:

[0017] The second fraction was subjected to nuclear magnetic resonance detection; and the inorganic purity of the second fraction was detected by ICP-OES.

[0018] An embodiment of the present invention further provides electronic-grade bromochloromethane, which is prepared by the above-mentioned method for preparing electronic-grade bromochloromethane.

[0019] In one or more embodiments of the present invention, the inorganic purity of the electronic grade bromochloromethane is greater than or equal to 99.9999%.

[0020] An embodiment of the present invention further provides an application of electronic-grade bromochloromethane in the semiconductor field. The electronic-grade bromochloromethane is prepared by the above-mentioned method for preparing electronic-grade bromochloromethane.

[0021] Compared with the prior art, the method for preparing electronic-grade bromochloromethane according to an embodiment of the present invention uses a specific 13X molecular sieve to adsorb impurities in the bromochloromethane raw material, and then combines it with a distillation process to collect a second fraction, thereby obtaining electronic-grade bromochloromethane with higher purity (for example, an inorganic purity of 99.9999%), thereby meeting the requirements of the semiconductor field. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG1 is a flow chart of a method for preparing electronic-grade bromotrichloromethane according to one embodiment of the present invention;

[0023] FIG2 is a method for preparing electronic-grade bromotrichloromethane according to another embodiment of the present invention;

[0024] FIG3 is a nuclear magnetic spectrum of bromotrichloromethane raw materials according to embodiments of the present invention and comparative examples;

[0025] FIG4 is a nuclear magnetic spectrum of the second fraction in Example 1 of the present invention;

[0026] FIG5 is a nuclear magnetic spectrum of the second fraction in Comparative Example 1 according to the present invention. DETAILED DESCRIPTION

[0027] The specific embodiments of the present invention are described in detail below with reference to the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0028] Unless expressly stated otherwise, throughout the specification and claims, the term "comprise" or variations such as "include" or "comprising", etc., will be understood to include the stated elements or components but not to exclude other elements or other components.

[0029] As shown in FIG1 , a method for preparing electronic-grade bromotrichloromethane according to a preferred embodiment of the present invention comprises the following steps:

[0030] S1. Mixing bromotrichloromethane and 13X molecular sieve for adsorption, and filtering to obtain a filtrate.

[0031] Specifically, the purity of bromochloromethane in the bromochloromethane raw material is greater than or equal to 98% (mass purity), and the mass ratio of 13X molecular sieve to bromochloromethane raw material is greater than 8%. If the mass ratio is too low, the amount of impurities may exceed the maximum adsorption capacity of the 13X molecular sieve, resulting in residual impurities. If the mass ratio is too high, material is wasted and costs increase.

[0032] Preferably, the 13X molecular sieve has a pore size of 10 angstroms, which allows it to adsorb any molecule larger than 3.64 angstroms and smaller than 10 angstroms. Therefore, it can effectively remove impurities such as water, hydrogen halide, chloroform, dibromochloromethane, dichloromethane, dichloroethane, and bromine from the trichlorobromomethane raw material. The 13X molecular sieve is composed of aluminosilicate.

[0033] Preferably, the 13X molecular sieve is a 13X molecular sieve that has been subjected to vacuum drying treatment, thereby ensuring the adsorption performance of the 13X molecular sieve.

[0034] The mixed adsorption time in the step of mixing the bromochloromethane raw material with the 13X molecular sieve is 22 to 26 hours. The adsorption time of 22 to 26 hours allows the 13X molecular sieve to fully contact the bromochloromethane raw material and provides sufficient adsorption time to adsorb various impurities in the bromochloromethane raw material as much as possible.

[0035] The step of mixing the bromochloroform raw material with the 13X molecular sieve for adsorption comprises: mixing the bromochloroform raw material with the 13X molecular sieve for adsorption in anhydrous and oxygen-free conditions and an inert gas atmosphere, thereby reducing the occurrence of side reactions. Specifically, the inert gas can be nitrogen, argon, etc.

[0036] S2. The filtrate is subjected to atmospheric distillation to collect a first fraction and a second fraction in sequence, wherein the second fraction is electronic grade bromochloroform. The mass of the first fraction is 12% to 18% of the mass of the filtrate; the mass of the second fraction is 65% to 75% of the mass of the filtrate.

[0037] Specifically, the distillation temperature in the step of subjecting the filtrate to atmospheric distillation is 105-108°C.

[0038] As shown in FIG2 , in another specific embodiment, the method for preparing electronic-grade bromotrichloromethane of the present invention further comprises the following steps:

[0039] S3. Perform nuclear magnetic resonance detection on the second fraction; and detect the inorganic purity of the second fraction using ICP-OES.

[0040] Organic NMR testing of the second fraction can be used to detect the presence of impurity peaks and determine its organic purity. ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry) can be used to determine its inorganic purity. This allows the purity of the second fraction to be determined, and its applicability in the semiconductor field to be determined.

[0041] An embodiment of the present invention further provides electronic-grade bromochloromethane, which is prepared by the above-mentioned method for preparing electronic-grade bromochloromethane.

[0042] Specifically, the inorganic purity of the electronic grade bromochloromethane is greater than or equal to 99.9999%.

[0043] An embodiment of the present invention further provides an application of electronic-grade bromochloromethane in the semiconductor field. The electronic-grade bromochloromethane is prepared by the above-mentioned method for preparing electronic-grade bromochloromethane.

[0044] The following is a detailed description of electronic-grade bromotrichloromethane, its preparation method, and its application with reference to specific examples.

[0045] Example 1

[0046] In an anhydrous and oxygen-free inert gas glove box, 1000 g of Anage's trichlorobromomethane raw material (purity of 98%) was added to a 1000 ml single-necked flask, and 13X molecular sieves (mass ratio of 8%, about 80 g) after vacuum drying were added for adsorption for 24 hours, and 912 g of filtrate was obtained by filtration.

[0047] An atmospheric distillation apparatus was built, and the kettle temperature was controlled at 105-108°C to collect 138 g of the first fraction, which was approximately 15% of the mass of the filtrate, and 635 g of the second fraction, which was approximately 70% of the mass of the filtrate.

[0048] Using nuclear magnetic resonance ( 1 The second fraction was detected by HNMR ( 1 The HNMR spectrum is shown in Figure 4, and the inorganic purity of the second fraction was determined by ICP-OES. The organic NMR spectrum of the second fraction showed no impurity peaks, and the inorganic purity reached 99.9999%, meeting the requirements for bromochloroform application in semiconductors.

[0049] Example 2

[0050] In an anhydrous and oxygen-free inert gas glove box, 500 g of Anage's trichlorobromomethane raw material (purity of 98%) was added to a 500 ml single-necked flask, and 13X molecular sieves (mass ratio of 8%, about 40 g, pore size 10 angstroms) after vacuum drying were added for adsorption for 24 hours, and 460 g of filtrate was obtained by filtration.

[0051] An atmospheric distillation apparatus was built, and the kettle temperature was controlled at 105-108°C to collect 67 g of the first fraction, which was approximately 15% of the mass of the filtrate, and 320 g of the second fraction, which was approximately 70% of the mass of the filtrate.

[0052] Using nuclear magnetic resonance ( 1 The second fraction was tested by HNMR and its inorganic purity was tested by ICP-OES. The organic NMR detection of the second fraction showed no impurity peaks and an inorganic purity of 99.9999%, which meets the requirements for the application of bromotrichloromethane in semiconductors.

[0053] Example 3

[0054] In an anhydrous and oxygen-free inert gas glove box, 500 g of Anage's trichlorobromomethane raw material (purity of 98%) was added to a 500 ml single-necked flask, and 13X molecular sieves (mass ratio of 10%, about 50 g, pore size of 10 angstroms) after vacuum drying were added for adsorption for 24 hours, and 446 g of filtrate was obtained by filtration.

[0055] An atmospheric distillation apparatus was built, and the kettle temperature was controlled at 105-108°C to collect 65 g of the first fraction, which was approximately 15% of the mass of the filtrate, and 315 g of the second fraction, which was approximately 70% of the mass of the filtrate.

[0056] Using nuclear magnetic resonance ( 1 The second fraction was tested by HNMR and its inorganic purity was tested by ICP-OES. The organic NMR detection of the second fraction showed no impurity peaks and an inorganic purity of 99.9999%, which meets the requirements for the application of bromotrichloromethane in semiconductors.

[0057] Example 4

[0058] In an anhydrous and oxygen-free inert gas glove box, 500 g of Anage's trichlorobromomethane raw material (purity of 98%) was added to a 500 ml single-necked flask, and 13X molecular sieves (mass ratio of 10%, about 50 g, pore size of 10 angstroms) after vacuum drying were added for adsorption for 24 hours, and 446 g of filtrate was obtained by filtration.

[0059] An atmospheric distillation apparatus was built, and the kettle temperature was controlled at 105-108°C to collect 54 g of the first fraction, which was approximately 12% of the mass of the filtrate, and 345 g of the second fraction, which was approximately 75% of the mass of the filtrate.

[0060] Using nuclear magnetic resonance ( 1 The second fraction was tested by HNMR and its inorganic purity was tested by ICP-OES. The organic NMR detection of the second fraction showed no impurity peaks and an inorganic purity of 99.9999%, which meets the requirements for the application of bromotrichloromethane in semiconductors.

[0061] Example 5

[0062] In an anhydrous and oxygen-free inert gas glove box, 500 g of Anage's trichlorobromomethane raw material (purity of 98%) was added to a 500 ml single-necked flask, and 13X molecular sieves (mass ratio of 10%, about 50 g, pore size of 10 angstroms) after vacuum drying were added for adsorption for 24 hours, and 446 g of filtrate was obtained by filtration.

[0063] An atmospheric distillation apparatus was built, and the kettle temperature was controlled at 105-108°C to collect 80 g of the first fraction, which was approximately 18% of the mass of the filtrate, and 290 g of the second fraction, which was approximately 65% ​​of the mass of the filtrate.

[0064] Using nuclear magnetic resonance ( 1 The second fraction was tested by HNMR and its inorganic purity was tested by ICP-OES. The organic NMR detection of the second fraction showed no impurity peaks and an inorganic purity of 99.9999%, which meets the requirements for the application of bromotrichloromethane in semiconductors.

[0065] Comparative Example 1

[0066] In an anhydrous and oxygen-free inert gas glove box, 500 g of Anage trichlorobromomethane raw material was added to a 500 ml single-necked flask, and 13X molecular sieves (5% by mass, about 25 g, pore size 10 angstroms) after drying were added for adsorption for 24 hours, and 472 g of filtrate was obtained by filtration.

[0067] An atmospheric distillation apparatus was built, and the kettle temperature was controlled at 105-108°C to collect 72 g of the first fraction, which was about 15% of the mass of the filtrate, and 332 g of the second fraction, which was about 70% of the mass of the filtrate.

[0068] Using nuclear magnetic resonance ( 1 The second fraction was detected by HNMR ( 1 The HNMR spectrum is shown in Figure 5, and the inorganic purity of the second fraction was determined by ICP-OES. The organic NMR spectrum of the second fraction showed a small amount of impurity peaks, and the inorganic purity reached 99.9999%, which does not meet the requirements for the application of bromochloroform in semiconductors.

[0069] Comparative Example 2

[0070] In an anhydrous and oxygen-free inert gas glove box, 500 g of Anage's trichlorobromomethane raw material (purity of 98%) was added to a 500 ml single-necked flask, and 13X molecular sieves (mass ratio of 8%, about 40 g, pore size 10 angstroms) after vacuum drying were added for adsorption for 24 hours, and 460 g of filtrate was obtained by filtration.

[0071] Using nuclear magnetic resonance ( 1 The second fraction was tested by HNMR and its inorganic purity was tested by ICP-OES. The organic NMR detection of the second fraction showed a small amount of impurity peaks, and the inorganic purity reached 99.9999%, which did not meet the requirements for the application of bromochloroform in semiconductors.

[0072] Comparative Example 3

[0073] In an anhydrous and oxygen-free inert gas glove box, 500 g of Anage's trichlorobromomethane raw material (purity of 98%) was added to a 500 ml single-necked flask, and Japanese BAC-70R octa-spherical activated carbon (mass ratio of 10%, about 50 g) after vacuum drying was added for adsorption for 24 hours, and 452 g of filtrate was obtained by filtration.

[0074] An atmospheric distillation apparatus was built, and the kettle temperature was controlled at 105-108°C to collect 68g of the first fraction, which was about 15% of the mass of the filtrate, and 314g of the second fraction, which was about 70% of the mass of the filtrate.

[0075] Using nuclear magnetic resonance ( 1 The second fraction was tested by HNMR and its inorganic purity was tested by ICP-OES. The organic NMR detection of the second fraction showed impurity peaks and the inorganic purity was 99.999%, which did not meet the requirements for the application of bromochloroform in semiconductors.

[0076] Figure 3 is the NMR of bromochloromethane raw material of Anaiji ( 1 HNMR) spectrum, it can be seen that there are many miscellaneous peaks and impurities.

[0077] The foregoing descriptions of specific exemplary embodiments of the present invention are for purposes of illustration and description. These descriptions are not intended to limit the invention to the precise forms disclosed, and it is apparent that many variations and modifications are possible in light of the foregoing teachings. The exemplary embodiments have been selected and described for the purpose of explaining the specific principles of the invention and their practical application, thereby enabling those skilled in the art to realize and utilize a variety of exemplary embodiments of the invention and various options and modifications. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A method for preparing electronic grade bromochloromethane, characterized in that: The following steps are involved: Mixing bromotrichloromethane raw material with 13X molecular sieve for adsorption, filtering to obtain a filtrate; The filtrate is subjected to atmospheric distillation to collect a first fraction and a second fraction in sequence, wherein the second fraction is the electronic grade bromochloromethane, and the mass of the first fraction is 12% to 18% of the mass of the filtrate; the mass of the second fraction is 65% to 75% of the mass of the filtrate.

2. The method for preparing electronic grade bromochloroform as claimed in claim 1, characterized in that: The purity of bromochloromethane in the bromochloromethane raw material is greater than or equal to 98%, and the mass ratio of the 13X molecular sieve to the bromochloromethane raw material is greater than 8%.

3. The method for preparing electronic grade bromochloroform as claimed in claim 1, characterized in that: The pore size of the 13X molecular sieve is 10 angstroms.

4. The method for preparing electronic grade bromochloroform as claimed in claim 1, characterized in that: The time of mixed adsorption of the bromotrichloromethane raw material and the 13X molecular sieve in the mixed adsorption step is 22 to 26 hours.

5. The method for preparing electronic grade bromochloromethane as claimed in claim 1, characterized in that: The steps of mixing bromotrichloromethane raw material with 13X molecular sieve for adsorption include: In anhydrous and oxygen-free conditions and an inert gas atmosphere, bromotrichloromethane raw material is mixed with 13X molecular sieve for adsorption.

6. The method for preparing electronic grade bromochloromethane as claimed in claim 1, characterized in that: The distillation temperature in the step of subjecting the filtrate to atmospheric distillation treatment is 105-108°C.

7. The method for preparing electronic grade bromochloromethane as claimed in claim 1, characterized in that: The second fraction is subjected to nuclear magnetic resonance detection; and the inorganic purity of the second fraction is detected by ICP-OES.

8. An electronic grade bromochloromethane, characterized in that: The electronic grade bromotrichloromethane is prepared by the preparation method of electronic grade bromotrichloromethane according to any one of claims 1 to 7.

9. The electronic grade bromochloromethane as claimed in claim 8, characterized in that The inorganic purity of the electronic grade bromochloromethane is greater than or equal to 99.9999%.

10. An application of electronic grade bromochloromethane in the semiconductor field, characterized in that: The electronic grade bromotrichloromethane is prepared by the preparation method of electronic grade bromotrichloromethane according to any one of claims 1 to 7.

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