Method for separating isomeride, high-purity ether compound and application of high-purity ether compound

Abstract

The invention relates to the field of substance purification, in particular to a method for separating an isomeride, a high-purity ether compound and application of the high-purity ether compound. The method comprises the following steps: carrying out contact reaction on a mixture containing compounds shown in a formula (2) and a formula (3) and a compound shown in a formula (1), and then purifying, # imgabs0, wherein the formula (2) and the formula (3) are isomers; in the formula, R1 and R2 are respectively selected from one of H, halogen, a benzene ring and C1-C3 alkyl; each of L1 and L2 is an alkylene chain with 1 to 10 carbon atoms; r3 is alkyl with the carbon number of 1-10; and at least one of R4 and R5 is alkyl with 1-4 carbon atoms. According to the technical scheme, the content of the primary alcohol ether impurities in the alcohol ether product is reduced to 1 ppm or below, and the requirements of the electronic industry are met.

Description

Technical Field

[0001] The present invention relates to the field of material purification, and particularly to a method for separating isomers, a high-purity ether compound and its application. Background Art

[0002] Alcohol ethers are known as universal solvents due to their good solubility. In the field of the electronics industry, alcohol ethers are the most commonly used cleaning solvents and are widely used for cleaning and etching the surfaces of chips, silicon wafers and liquid crystal displays. For the field of electronic chemicals, the purity of products has a crucial impact on the yield, electrical properties and reliability, etc.

[0003] Alcohol ethers produced industrially are often mixtures composed of multiple isomers, and usually the primary alcohol isomer has higher toxicity. The most significant applicability of this rule is propylene glycol methyl ether, and its isomer 2-methoxy-1-propanol has higher toxicity. To reduce the content of 2-methoxy-1-propanol, the original acid catalyst was abandoned and sodium alkoxide was used as the reaction process catalyst during the industrial production of propylene glycol methyl ether. However, about 5% of 2-methoxy-1-propanol will still be inevitably produced in this process. Although after rectification separation, the content of 2-methoxy-1-propanol in the system can be reduced to less than 0.5%, the content of 2-methoxy-1-propanol cannot be reduced to less than 1 ppm, which cannot meet the requirements of the electronics industry. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problems that the purification efficiency of alcohol ethers in the prior art is not high and the purification effect is insufficient, resulting in products that cannot meet the requirements of the electronics industry, and to provide a method for separating isomers, a high-purity ether compound and its application. This method has the characteristics of high separation efficiency and good separation effect.

[0005] To achieve the aforementioned purpose of the present invention, in the first aspect, the present invention provides a method for separating isomers, which is characterized in that the method includes: contacting and reacting a mixture containing the compounds shown in formula (2) and formula (3) with the compound shown in formula (1), and then performing purification;

[0006]

[0007] Among them, formula (2) and formula (3) are isomers;

[0008] In the formula, R 1 and R 2 each independently selected from one of H, halogen, benzene ring and C1-C3 alkyl; L 1 , L 2 are each an alkylene chain with 1-10 carbon atoms; R 3 is an alkyl with 1-10 carbon atoms; R 4 and R 5At least one is an alkyl group having 1 to 4 carbon atoms.

[0009] The second aspect of the present invention provides a high-purity ether compound prepared by the method described in the first aspect, and the ether compound is a compound represented by formula (3).

[0010] The third aspect of the present invention provides an application of the high-purity ether compound described in the second aspect in the field of preparation of electronic chemicals.

[0011] Through the above technical solutions, the beneficial effects of the present invention are as follows:

[0012] Through the technical solution of the present invention, the content of primary alcohol ether impurities in the alcohol ether product is reduced to less than 1 ppm, meeting the requirements of the electronic industry. Detailed implementation manners

[0013] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0014] The present invention provides a method for separating isomers, characterized in that the method includes: contacting and reacting a mixture containing the compounds represented by formula (2) and formula (3) with the compound represented by formula (1), and then performing purification;

[0015]

[0016] Among them, formula (2) and formula (3) are isomers;

[0017] In the formula, R 1 and R 2 each independently selected from one of H, halogen, benzene ring and C1-C3 alkyl; L 1 , L 2 are each an alkylene chain having 1 to 10 carbon atoms; R 3 is an alkyl group having 1 to 10 carbon atoms; R 4 and R 5 At least one is an alkyl group having 1 to 4 carbon atoms.

[0018] Through the technical solution of the present invention, the content of primary alcohol ether impurities in the alcohol ether product is reduced to less than 1 ppm, meeting the requirements of the electronic industry.

[0019] According to the present invention, in formula (2) and formula (3), L 1 , L 2It can be a straight-chain alkylene chain or a branched alkylene chain.

[0020] According to a preferred embodiment of the present invention, in the formula, L 1 and L 2 are each an alkylene chain having 1 to 5 carbon atoms, and R 3 is an alkyl group having 1 to 4 carbon atoms.

[0021] According to a preferred embodiment of the present invention, in the formula, R 1 and R 2 are each independently selected from one of H, F, Cl, Br, benzene ring, methyl and ethyl.

[0022] According to a preferred embodiment of the present invention, the compound represented by the formula (3) is selected from one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, and preferably propylene glycol monomethyl ether or propylene glycol monoethyl ether.

[0023] According to a preferred embodiment of the present invention, the content of the compound represented by the formula (2) in the mixture is not higher than 1 wt%, preferably not higher than 0.5 wt%.

[0024] According to a preferred embodiment of the present invention, the conditions of the contact reaction include: temperature -20 - 50 °C, preferably -20 - 30 °C. The reaction time is adjusted according to the reaction temperature, for example, it can be: 0.01 - 3 h, preferably 0.01 - 1 h.

[0025] According to a preferred embodiment of the present invention, the conditions of the contact reaction include: pressure 0 - 5 MPa, preferably 0 - 3 MPa.

[0026] According to a preferred embodiment of the present invention, the conditions of the contact reaction include: the molar ratio of the amount of the compound of formula (1) added to the molar amount of the compound of formula (2) in the mixture is 1 - 5, preferably 1 - 3.

[0027] The prior art usually needs to be carried out in the presence of a catalyst, generally in the presence of an acidic catalyst, and the acidic catalyst is selected from at least one of concentrated sulfuric acid, p-toluenesulfonic acid, heteropolyacid, acidic ionic liquid and solid acid. However, in the present invention, the contact reaction is directly carried out without adding a catalyst. Compared with the prior art using a catalyst, the present invention has the advantage of not introducing other impurities into the system without using a catalyst.

[0028] According to a preferred embodiment of the present invention, the purification method includes rectification.

[0029] In the present invention, there are no special requirements for the rectification conditions, which are demonstrated below, but do not limit the scope of the present invention thereby.

[0030] For example, according to a preferred embodiment of the present invention, the rectification (reboiler) temperature is 120 - 150 °C.

[0031] For example, according to a preferred embodiment of the present invention, the rectification pressure is 50 - 150 kPa.

[0032] For example, according to a preferred embodiment of the present invention, the rectification reflux ratio is 0.2 - 10, preferably 0.2 - 5.

[0033] For example, according to a preferred embodiment of the present invention, during the rectification process, the fraction with a top - tower temperature of 110 - 125 °C is collected as the product fraction.

[0034] The present invention provides a high - purity ether compound prepared by the method described above, and the ether compound is the compound shown in formula (3).

[0035] According to a preferred embodiment of the present invention, the purity of the compound shown in formula (3) in the high - purity ether compound is ≥99.9%, preferably ≥99.98%; the content of the compound shown in formula (2) is not higher than 1 ppm, preferably not higher than 0.5 ppm.

[0036] The present invention provides an application of the high - purity ether compound in the field of preparation of electronic chemicals. The present invention will be described in detail below through examples.

[0037] In the following examples, the product purity and impurity content were measured by gas chromatography analysis; unless otherwise specified, the raw materials were commercially available products, and the relevant raw materials satisfied the structures shown in formula (1), formula (2), and formula (3):

[0038]

[0039] Example 1

[0040] In a propylene glycol methyl ether (structure of formula 3) solution with a 2 - methoxy - 1 - propanol (structure of formula 2) content of 0.13 wt%, a substance A with the structure shown in formula (1) containing R 1 being F and R 2 being methyl was added. The molar ratio of substance A to 2 - methoxy - 1 - propanol was 2. The contact reaction conditions included: temperature of - 20 °C, pressure of 0.5 MPa, reaction duration of 0.01 h. After the reaction, the resulting reaction solution was rectified. The rectification reboiler temperature was 130 °C, the tower pressure was 100 kPa, the reflux ratio was 1, and the top - tower temperature was 120 °C.

[0041] The fraction taken from the top of the tower was collected and analyzed by gas chromatography. The content of 2 - methoxy - 1 - propanol in the product was 0.15 ppm, and the product purity was 99.99%.

[0042] Example 2

[0043] In a propylene glycol methyl ether (structure of Formula 3) solution with a 2-methoxy-1-propanol (structure of Formula 2) content of 0.13 wt%, a substance A with the structure shown in Formula (1) containing R 1 and R 2 both being benzene rings is added. The molar ratio of substance A to 2-methoxy-1-propanol is 1. The contact reaction conditions include: temperature of 20°C, pressure of 0.5 MPa, reaction duration of 0.5 h. The resulting reaction solution after the reaction is subjected to distillation. The temperature at the bottom of the distillation column is 130°C, the temperature at the top of the column is 120°C, the column pressure is 100 kPa, and the reflux ratio is 1.

[0044] The fraction taken out at the top of the column at the top column temperature is collected and analyzed by gas chromatography. The content of 2-methoxy-1-propanol in the product is 0.031 ppm, and the product purity is 99.98%.

[0045] Example 3

[0046] In a propylene glycol methyl ether (structure of Formula 3) solution with a 2-methoxy-1-propanol (structure of Formula 2) content of 0.32 wt%, a substance A with the structure shown in Formula (1) containing R 1 being Cl and R 2 being ethyl is added. The molar ratio of substance A to 2-methoxy-1-propanol is 3. The contact reaction conditions include: temperature of 30°C, pressure of 0.5 MPa, reaction duration of 1 h. The resulting reaction solution after the reaction is subjected to distillation. The temperature at the bottom of the distillation column is 130°C, the temperature at the top of the column is 120°C, the column pressure is 100 kPa, and the reflux ratio is 3.

[0047] The fraction taken out at the top of the column at the top column temperature is collected and analyzed by gas chromatography. The content of 2-methoxy-1-propanol in the product is 0.25 ppm, and the product purity is 99.99%.

[0048] Example 4

[0049] Same as Example 2, except that: a substance A with the structure shown in Formula (1) containing R 1 being a benzene ring and R 2 being a methyl group is added;

[0050] The fraction taken out at the top of the column at the top column temperature is collected and analyzed by gas chromatography. The content of 2-methoxy-1-propanol in the product is 0.31 ppm, and the product purity is 99.98%.

[0051] Example 5

[0052] Same as Example 2, except that: the molar ratio of substance A to 2-methoxy-1-propanol is 5.

[0053] Collect the distillate at the top temperature of the tower and analyze it by gas chromatography. The content of 2-methoxy-1-propanol in the product is 0.027 ppm, and the product purity is 99.99%.

[0054] Example 6

[0055] Same as Example 2, except that: the ether substance is butylene glycol methyl ether (structure of Formula 3); the alcohol isomers of the ether substance are 3-methoxy-1-butanol (structure of Formula 2) and 2-methoxy-1-butanol (structure of Formula 2);

[0056] Collect the distillate at the top temperature of the tower and analyze it by gas chromatography. The contents of 3-methoxy-1-butanol and 2-methoxy-1-butanol in the product are 0.15 ppm and 0.24 ppm respectively, and the product purity is 99.98%.

[0057] Example 7

[0058] Same as Example 2, except that: the content of 2-methoxy-1-propanol is a propylene glycol methyl ether solution of 0.78 wt%;

[0059] Collect the distillate at the top temperature of the tower and analyze it by gas chromatography. The content of 2-methoxy-1-propanol in the product is 0.73 ppm, and the product purity is 99.97%.

[0060] Example 8

[0061] Same as Example 2, except that: the conditions of the contact reaction include: temperature is 50 °C, pressure is 5 MPa, and the reaction duration is 2 h;

[0062] Collect the distillate at the top temperature of the tower and analyze it by gas chromatography. The content of 2-methoxy-1-propanol in the product is 0.33 ppm, and the product purity is 99.91%.

[0063] Comparative Example 1

[0064] Same as Example 2, directly distill the propylene glycol methyl ether solution with a 2-methoxy-1-propanol content of 0.13 wt%. The temperature at the bottom of the distillation column is 130 °C, the temperature at the top of the column is 120 °C, the column pressure is 100 kPa, and the reflux ratio is 1.

[0065] Collect the distillate. Analyze it by gas chromatography. The content of 2-methoxy-1-propanol in the product is 96.54 ppm, and the product purity is 99.58%.

[0066] Comparative Example 2

[0067] Same as Example 2, select R 1 is n-butyl and R 2Substance A with a structure shown in formula (1) where the group is n-hexyl;

[0068] Collect the fraction drawn at the top temperature of the tower and analyze it by gas chromatography. The content of 2-methoxy-1-propanol in the product is 72.58 ppm, and the product purity is 99.69%.

[0069] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for separating isomers, characterized in that, the method comprises: contacting and reacting a mixture containing the compounds shown in formula (2) and formula (3) with the compound shown in formula (1), and then performing purification; wherein, formula (2) and formula (3) are isomers; Wherein, R 1 and R 2 each independently selected from one of H, halogen, a benzene ring, and an alkyl group having 1 to 3 carbon atoms; L 1 , L 2 each is an alkylene chain having 1 to 10 carbon atoms; R 3 is an alkyl group having 1 to 10 carbon atoms; at least one of R 4 and R 5 is an alkyl group having 1 to 4 carbon atoms.

2. The method according to claim 1, wherein, L 1 and L 2 are each an alkylene chain having 1 to 5 carbon atoms, and R 3 is an alkyl group having 1 to 4 carbon atoms.

3. The method according to claim 1 or 2, wherein, wherein, R 1 and R 2 each independently selected from one of H, F, Cl, Br, benzene ring, methyl and ethyl.

4. The method according to any one of claims 1-3, wherein, the compound shown in formula (3) is selected from one of methyl glycol ether, ethyl glycol ether, methyl pentanediol ether, ethyl pentanediol ether, ethyl propylene glycol ether and methyl propylene glycol ether, preferably methyl propylene glycol ether or ethyl propylene glycol ether.

5. The method according to any one of claims 1-4, wherein, the content of the compound shown in formula (2) in the mixture is not higher than 1 wt%, preferably not higher than 0.5 wt%.

6. The method according to any one of claims 1-5, wherein, the conditions of the contacting reaction include: temperature -20 - 50 °C, preferably -20 - 30 °C; and / or pressure 0 - 5 MPa, preferably 0 - 3 MPa; and / or the molar ratio of the amount of the compound of formula (1) added to the molar amount of the compound of formula (2) in the mixture is 1 - 5.

7. The method according to any one of claims 1-6, wherein, the purification method includes rectification; preferably, the rectification conditions include: temperature 120 - 150 °C; and / or pressure 50 - 150 kPa; and / or reflux ratio 0.2 - 10, preferably 0.2 - 5; collecting the fraction with a top temperature of 110 - 125 °C as the product fraction.

8. A high-purity ether compound prepared by the method according to any one of claims 1-7, characterized in that, the ether compound is the compound shown in formula (3).

9. The high-purity ether compound according to claim 8, wherein, the purity of the compound shown in formula (3) ≥ 99.9%, preferably ≥ 99.98%; the content of the compound shown in formula (2) is not higher than 1 ppm, preferably not higher than 0.5 ppm.

10. Use of the high-purity ether compound according to claim 8 or 9 in the field of preparation of electronic chemicals.

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