Method for producing high-purity cyclobutane derivatives

Abstract

To provide a method for producing high-purity cyclobutane derivatives.SOLUTION: This method includes the steps for: adding a starting mixture comprising cyclobutane derivatives having structures as shown in the following formula (1) and formula (2), where R1 is an alkyl group having 1 to 20 carbon atoms, to a tetrahydrofuran derivative to form a cyclobutane derivative mixed solution; and filtering the cyclobutane derivative mixed solution to obtain a solid comprising a cyclobutane derivative having the structure as shown in the formula (1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to the technical field of a method for producing a cyclobutane derivative, and more particularly to a method for producing a high-purity cyclobutane derivative. [Background technology]

[0002] Cyclobutanetetracarboxylic dianhydride is one of the important raw materials for producing polyimide polymer materials, as well as its derivatives. Currently, materials such as polyimides synthesized from cyclobutanetetracarboxylic dianhydride derivatives and other diamine monomers are widely used in various technical fields.

[0003] In conventional technology, cyclobutane tetracarboxylic dianhydride derivatives can be synthesized by photocycloaddition of maleic anhydride derivatives. This photopolymerization reaction can produce a mixture of both 1,3-substituted cyclobutane derivatives (e.g., 1,3-substituted cyclobutane-1,2,3,4-tetracarboxylic acid-1,2:3,4-dianhydride) and 1,2-substituted cyclobutane derivatives (e.g., 1,2-substituted cyclobutane-1,2,3,4-tetracarboxylic acid-1,2:3,4-dianhydride). Because 1,3-substituted cyclobutane derivatives are more symmetrical than 1,2-substituted cyclobutane derivatives, when synthesized with other diamine monomers, polyimides with higher molecular weights can be obtained. Therefore, providing a method for producing high-purity 1,3-substituted cyclobutane derivatives is an urgent issue in the industry. Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above problems, an object of the present invention is to provide a method for producing a high-purity cyclobutane derivative, which can purify a 1,3-substituted cyclobutane derivative with high efficiency and high purity. [Means for solving the problem]

[0005] In one embodiment of the present invention, the present invention provides a method for producing a cyclobutane derivative mixed solution by adding a starting mixture containing cyclobutane derivatives having structures represented by the following formulas (1) and (2) (wherein R1 is an alkyl group having 1 to 20 carbon atoms) to a tetrahydrofuran derivative; [ka] [ka] and filtering the cyclobutane derivative mixed solution to obtain a solid containing a cyclobutane derivative having a structure represented by formula (1).

[0006] In one embodiment, the tetrahydrofuran derivative may include at least one selected from the group consisting of tetrahydrofuran and 2-methyltetrahydrofuran.

[0007] In one embodiment, the cyclobutane derivative mixed solution may be heated to a temperature range from 30° C. to the boiling point of the tetrahydrofuran derivative before filtering the cyclobutane derivative mixed solution.

[0008] In one embodiment, the cyclobutane derivative mixed solution may be heated to a temperature range of 30°C to 70°C.

[0009] In one embodiment, the method may further include a step of cooling the cyclobutane derivatives mixed solution between the step of heating the cyclobutane derivatives mixed solution and the step of filtering the cyclobutane derivatives mixed solution.

[0010] In one embodiment, the cyclobutane derivative mixed solution may be cooled to a temperature range of -10°C to 50°C.

[0011] In one embodiment, the method may further include a step of adding acetic anhydride in an amount 1 to 10 times the mass of the starting mixture between the step of cooling the cyclobutane derivative mixed solution and the step of filtering the cyclobutane derivative mixed solution.

[0012] In one embodiment, R1 is preferably an alkyl group having 1 to 4 carbon atoms.

[0013] In one embodiment, the cyclobutane derivative having the structure shown in formula (1) has an initial purity of >10%, where the initial purity is defined as the proportion of the cyclobutane derivative having the structure shown in formula (1) in the starting mixture relative to the total content of the cyclobutane derivative having the structure shown in formula (1) and the cyclobutane derivative having the structure shown in formula (2).

[0014] In one embodiment, the cyclobutane derivative having the structure shown in formula (1) may have a post-purification purity of between 93% and 100%, and the post-purification purity is defined as the proportion of the cyclobutane derivative having the structure shown in formula (1) in the solid obtained by filtration to the total content of the cyclobutane derivative having the structure shown in formula (1) and the cyclobutane derivative having the structure shown in formula (2).

[0015] In one embodiment, the mass of the tetrahydrofuran derivative may be 0.1 to 100 times the mass of the starting mixture containing the cyclobutane derivative having the structure represented by formula (1) and the cyclobutane derivative having the structure represented by formula (2).

[0016] In one embodiment, the mass of the tetrahydrofuran derivative may be preferably 1 to 20 times the mass of the starting mixture containing the cyclobutane derivative having the structure represented by formula (1) and the cyclobutane derivative having the structure represented by formula (2).

[0017] In one embodiment, a starting mixture containing a cyclobutane derivative having the structure shown in formula (1) and a cyclobutane derivative having the structure shown in formula (2) may be obtained by a photocycloaddition reaction of a maleic anhydride derivative. [Effects of the Invention]

[0018] Compared with conventional techniques, the method for producing a high-purity cyclobutane derivative of the present invention can reduce the amount of solvent used, and can efficiently produce a high-purity 1,3-substituted cyclobutane derivative even when the initial purity of the cyclobutane derivative having the structure represented by formula (1) is low. DETAILED DESCRIPTION OF THE INVENTION

[0019] Before describing at least one embodiment of the present invention in detail, it should be understood that the present invention is not necessarily limited in its application to the details set forth in the examples set forth below, such as the number of examples or the specific mixing ratios used. The present invention is capable of other embodiments or of being practiced or carried out in various ways.

[0020] The method for producing a high-purity cyclobutane derivative according to the present invention includes the steps of adding a starting mixture containing cyclobutane derivatives having structures represented by the following formulas (1) and (2) to a tetrahydrofuran derivative to form a cyclobutane derivative mixed solution, and filtering the cyclobutane derivative mixed solution to obtain a solid containing the cyclobutane derivative having the structure represented by formula (1). [ka] [ka]

[0021] In one embodiment, R1 is an alkyl group having 1 to 20 carbon atoms. Preferably, R1 is an alkyl group having 1 to 4 carbon atoms. For example, when R1 is a methyl group, the cyclobutane derivative represented by formula (1) is 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid-1,2:3,4-dianhydride (i.e., 1,3-DMCBDA), and the cyclobutane derivative represented by formula (2) is 1,2-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid-1,2:3,4-dianhydride (i.e., 1,2-DMCBDA).

[0022] In one embodiment, the tetrahydrofuran derivative includes at least one selected from the group consisting of tetrahydrofuran and 2-methyltetrahydrofuran. Preferably, the tetrahydrofuran derivative is tetrahydrofuran (abbreviated as "tetrahydrofuran" or "THF") or 2-methyltetrahydrofuran (abbreviated as "2-methyl-THF"). By using a tetrahydrofuran derivative as a solvent, the 1,3-substituted cyclobutane derivative represented by formula (1) can be precipitated with high efficiency due to the difference in the action of the solvent on a mixture of a 1,3-substituted cyclobutane derivative represented by formula (1) and a 1,2-substituted cyclobutane derivative represented by formula (2). Furthermore, compared to other solvents, when the initial purity of the 1,3-substituted cyclobutane derivative represented by formula (1) is the same, using a smaller amount of tetrahydrofuran derivative allows the precipitation of a high-purity 1,3-substituted cyclobutane derivative represented by formula (1), thereby reducing production costs. Even if the initial purity of the 1,3-substituted cyclobutane derivative represented by formula (1) is low, a high-purity 1,3-substituted cyclobutane derivative represented by formula (1) can be precipitated without using an excess of tetrahydrofuran derivative. Furthermore, compared with common solvents, tetrahydrofuran derivatives have the advantage of having a high boiling point, making them highly safe when used as a solvent. In one embodiment, the tetrahydrofuran derivative may simultaneously contain two compounds, THF and 2-methyl-THF, as solvents.

[0023] In one embodiment, in the method for producing a high-purity cyclobutane derivative of the present invention, the cyclobutane derivative mixed solution may be heated to a temperature range from 30°C to the boiling point of the tetrahydrofuran derivative before filtering. For example, the cyclobutane derivative mixed solution may be heated to a temperature range from 30°C to the boiling point of THF, or from 30°C to the boiling point of 2-Methyl-THF. Preferably, the cyclobutane derivative mixed solution is first heated to a temperature range from 30°C to 70°C. In another embodiment, the cyclobutane derivative mixed solution may be first heated to a temperature range from 30°C to 66°C. In actual application, the heating temperature may be adjusted depending on the actual blend ratio of each compound in the tetrahydrofuran derivative and cyclobutane derivative mixed solution, and the present invention is not limited thereto. Heating the cyclobutane derivative mixed solution helps to more effectively dissolve the 1,2-substituted cyclobutane derivative represented by formula (2).

[0024] In one embodiment, the method for producing a high-purity cyclobutane derivative of the present invention may further include a step of cooling the cyclobutane derivative mixed solution between the step of heating the cyclobutane derivative mixed solution and the step of filtering the cyclobutane derivative mixed solution. Cooling the cyclobutane derivative mixed solution helps to more effectively precipitate a solid containing the 1,3-substituted cyclobutane derivative represented by formula (1). Preferably, the cyclobutane derivative mixed solution is cooled to a temperature range of -10°C to 50°C. In actual application, the cooling temperature may be adjusted depending on the actual blend ratio of each compound in the tetrahydrofuran derivative and the cyclobutane derivative mixed solution, and the present invention is not limited thereto.

[0025] In one embodiment, the method for producing a high-purity cyclobutane derivative of the present invention may further include a step of adding acetic anhydride in an amount 1 to 10 times the mass of the starting mixture between the step of cooling the cyclobutane derivative mixed solution and the step of filtering the cyclobutane derivative mixed solution. The addition of acetic anhydride helps to improve the purity of the cyclobutane derivative having the structure represented by formula (1) after purification. In actual application, the actual amount of acetic anhydride added may be adjusted depending on the actual blend ratio of each compound in the tetrahydrofuran derivative and the cyclobutane derivative mixed solution, and the present invention is not limited thereto.

[0026] In one embodiment, the content of the cyclobutane derivative having the structure represented by formula (1) in the starting mixture may be greater than 10%, preferably 25% to 99%, of the total content of the cyclobutane derivative having the structure represented by formula (1) and the cyclobutane derivative having the structure represented by formula (2). In another embodiment, the content is less than or equal to 25%. For example, the content may be a positive integer ratio between 10% and 99%, but the present invention is not limited thereto.

[0027] In one embodiment, in the method for producing a high-purity cyclobutane derivative of the present invention, the cyclobutane derivative having the structure represented by formula (1) may have a post-purification purity of 93% to 100%, where the post-purification purity is defined as the ratio of the cyclobutane derivative having the structure represented by formula (1) in the solid obtained by filtering a cyclobutane derivative mixed solution to the total content of the cyclobutane derivative having the structure represented by formula (1) and the cyclobutane derivative having the structure represented by formula (2). Preferably, the post-purification purity may be >99%. Specifically, even when the ratio of the cyclobutane derivative having the structure represented by formula (1) in the starting mixture is low, the method for producing a high-purity cyclobutane derivative of the present invention can still produce a high-purity cyclobutane derivative having the structure represented by formula (1). For example, the cyclobutane derivative having the structure represented by formula (1) may have a post-purification purity of 93% to 100%, where the purity may be a positive integer between 93% and 100%, but the present invention is not limited thereto.

[0028] In one embodiment, the mass of the tetrahydrofuran derivative may be 0.1 to 100 times the mass of the starting mixture containing the cyclobutane derivative having the structure shown in Formula (1) and the cyclobutane derivative having the structure shown in Formula (2). Preferably, the mass of the tetrahydrofuran derivative is 1 to 20 times, and more preferably 1 to 10 times, the mass of the starting mixture containing the cyclobutane derivative having the structure shown in Formula (1) and the cyclobutane derivative having the structure shown in Formula (2). For example, the mass multiple may be a positive integer between 0.1 and 100, but the present invention is not limited thereto.

[0029] In one embodiment, a starting mixture containing a cyclobutane derivative having the structure shown in formula (1) and a cyclobutane derivative having the structure shown in formula (2) may be obtained by a photocycloaddition reaction of a maleic anhydride derivative. For example, as shown in the following reaction scheme, the maleic anhydride derivative may be citraconic anhydride, but the present invention is not limited thereto. [ka]

[0030] In one embodiment, when producing the starting mixture, the maleic anhydride derivative may be irradiated with energy rays to cause a photocycloaddition reaction, and the energy rays may be emitted from a light source having a wavelength of 200 nm to 600 nm. Preferably, the energy rays are ultraviolet rays. In one embodiment, the irradiation time is 1 to 60 hours. In actual application, the irradiation time may be determined depending on the wavelength of the energy rays, and the present invention is not limited thereto.

[0031] The present invention will be described in more detail by the following examples, but these descriptions are merely illustrative of the present invention and do not limit the scope of the present invention, and any modifications and changes made by those skilled in the art are included in the content disclosed in this specification and the scope of the appended claims.

[0032] [ 1 H NMR analysis conditions] Equipment: BRUKER AVANCE III 400 nuclear magnetic resonance apparatus Solvent: DMSO-d6 (Aldrich)

[0033] [Manufacturing Examples and Comparative Examples] Example 1 A 1-liter reaction flask was charged with citraconic anhydride (150 grams, 1.34 moles), benzophenone (12 grams, 0.07 moles), and isoamyl acetate (750 grams), and the mixture was irradiated with ultraviolet light at a wavelength of 365 nm for 8 hours. The solid was then collected by suction filtration to obtain 25 grams of a starting mixture of 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid-1,2:3,4-dianhydride (1,3-DMCBDA) and 1,2-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid-1,2:3,4-dianhydride (1,2-DMCBDA). 1The ratio of 1,3-DMCBDA to 1,2-DMCBDA in the starting mixture was analyzed by H NMR to be 92:8. The ratio of 1,3-DMCBDA to the total content of 1,2-DMCBDA and 1,3-DMCBDA in the starting mixture is defined as the initial purity of 1,3-DMCBDA, and in Example 1, the initial purity of 1,3-DMCBDA was 92%.

[0034] 25 grams of the resulting starting mixture of 1,3-DMCBDA and 1,2-DMCBDA and 75 grams of 2-Methyl-THF (i.e., 3.0 times the mass of the starting mixture) were added to a 1-liter reaction flask and stirred to form a cyclobutane derivative mixed solution, which was then heated to 70 ° C. and stirred under reflux for 4 hours, then cooled to room temperature, and the precipitated crystals were collected. The precipitated crystals were then placed in a 1-liter reaction flask, and 125 grams of acetic anhydride (5.0 times the mass of the starting mixture) were added. The reaction temperature was controlled at 130 ° C. and the reaction was continued for 8 hours. The mixture was then cooled to room temperature, suction filtered, and dried to obtain 22.5 grams of solid matter. 1 The collected solid was analyzed by H NMR, and it was confirmed that the ratio of 1,3-DMCBDA to 1,2-DMCBDA in the solid was 99.5:0.5, i.e., the purity of 1,3-DMCBDA after purification was 99.5%.

[0035] Detailed parameters, solvent, solution, and mixture ratios for the examples and comparative examples are shown in Table 1 below. The recovery rate refers to the ratio of the mass number of 1,3-DMCBDA in the solid obtained by purification using the method for producing a high-purity cyclobutane derivative of the present invention to the mass number of 1,3-DMCBDA in the starting mixture of 1,3-DMCBDA and 1,2-DMCBDA. As is clear from Table 1 below, the recovery rate of 1,3-DMCBDA obtained using the method for producing a high-purity cyclobutane derivative of the present invention is high whether the initial purity is low or high, thereby enabling further improvement in purification efficiency.

[0036] [Table 1]

[0037] As described above, the method for producing a high-purity cyclobutane derivative of the present invention can produce a polyimide with higher symmetry and a high molecular weight after synthesis with other diamine monomers, and can produce a 1,3-substituted cyclobutane derivative with excellent physicochemical properties with higher efficiency. Furthermore, even if the initial purity of the 1,3-substituted cyclobutane derivative is low, the high-purity 1,3-substituted cyclobutane derivative represented by formula (1) can be precipitated without using an excess of tetrahydrofuran derivative (i.e., using a solvent with a low mass multiple and a small amount).

[0038] [Application areas] The method for producing a high-purity cyclobutane derivative of the present invention can be applied to technical fields in which cyclobutane derivatives are used, such as liquid crystal display elements, protective materials for semiconductors, and insulating material displays.

[0039] Although the present invention is disclosed by several preferred embodiments, it is not intended to limit the present invention, but to allow those skilled in the art to clearly understand the implementation contents of the specification. Those skilled in the art can make various changes, substitutions and modifications without departing from the spirit and scope of the present invention, so the protection scope of the present invention should be defined by the appended claims.

Claims

1. Formula (1) and Formula (2) below (wherein R １ is an alkyl group having 1 to 20 carbon atoms), to a tetrahydrofuran derivative to form a cyclobutane derivative mixed solution; 【Chemistry 1】 【Chemistry 2】 and filtering the cyclobutane derivative mixed solution to obtain a solid containing the cyclobutane derivative having the structure represented by formula (1). A method for producing high-purity cyclobutane derivatives.

2. The tetrahydrofuran derivative includes at least one selected from the group consisting of tetrahydrofuran and 2-methyltetrahydrofuran. A method for producing the high purity cyclobutane derivative according to claim 1.

3. Before filtering the cyclobutane derivative mixed solution, the cyclobutane derivative mixed solution is heated to a temperature range from 30° C. to the boiling point of the tetrahydrofuran derivative. A method for producing the high purity cyclobutane derivative according to claim 1.

4. heating the cyclobutane derivative mixed solution to a temperature range of 30°C to 70°C; The method for producing the high-purity cyclobutane derivative according to claim 3.

5. the method further includes a step of cooling the cyclobutane derivative mixed solution between the step of heating the cyclobutane derivative mixed solution and the step of filtering the cyclobutane derivative mixed solution. The method for producing the high-purity cyclobutane derivative according to claim 3.

6. cooling the cyclobutane derivative mixed solution to a temperature range of −10° C. to 50° C.; The method for producing the high-purity cyclobutane derivative according to claim 5.

7. the method further comprises the step of adding acetic anhydride in an amount of 1 to 10 times the mass of the starting mixture between the step of cooling the cyclobutane derivative mixed solution and the step of filtering the cyclobutane derivative mixed solution; The method for producing the high-purity cyclobutane derivative according to claim 5.

8. The R １ is an alkyl group having 1 to 4 carbon atoms; A method for producing the high-purity cyclobutane derivative according to any one of claims 1 to 7.

9. The cyclobutane derivative having the structure represented by formula (1) has an initial purity of >10%, and the initial purity is defined as the proportion of the cyclobutane derivative having the structure represented by formula (1) in the starting mixture to the total content of the cyclobutane derivative having the structure represented by formula (1) and the cyclobutane derivative having the structure represented by formula (2). A method for producing the high-purity cyclobutane derivative according to any one of claims 1 to 7.

10. The cyclobutane derivative having the structure represented by formula (1) has a post-purification purity of 93% to 100%, and the post-purification purity is defined as the ratio of the cyclobutane derivative having the structure represented by formula (1) in the solid to the total content of the cyclobutane derivative having the structure represented by formula (1) and the cyclobutane derivative having the structure represented by formula (2). A method for producing the high-purity cyclobutane derivative according to any one of claims 1 to 7.

11. the mass of the tetrahydrofuran derivative is 0.1 to 100 times the mass of the starting mixture containing the cyclobutane derivative having the structure represented by formula (1) and the cyclobutane derivative having the structure represented by formula (2); A method for producing the high-purity cyclobutane derivative according to any one of claims 1 to 7.

12. the mass of the tetrahydrofuran derivative is 1 to 20 times the mass of the starting mixture containing the cyclobutane derivative having the structure represented by formula (1) and the cyclobutane derivative having the structure represented by formula (2); The method for producing the high-purity cyclobutane derivative according to claim 11.

13. The starting mixture containing the cyclobutane derivative having the structure represented by the formula (1) and the cyclobutane derivative having the structure represented by the formula (2) is obtained by a photocycloaddition reaction of a maleic anhydride derivative, A method for producing the high-purity cyclobutane derivative according to any one of claims 1 to 7.

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