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 particularly to a method for producing a high-purity cyclobutane derivative.

Background Art

[0002] Cyclobutanetetracarboxylic dianhydride is one of the important raw materials for producing polyimide polymer materials, and the same applies to its derivatives. At present, materials such as polyimide synthesized from derivatives of cyclobutanetetracarboxylic dianhydride and other diamine monomers are widely applied in various technical fields.

[0003] In the conventional technology, cyclobutanetetracarboxylic dianhydride derivatives can be synthesized by the photocycloaddition reaction of maleic anhydride derivatives. By this photopolymerization reaction, a mixture of both 1,3-substituted cyclobutane derivatives (for example, 1,3-substituted cyclobutane-1,2,3,4-tetracarboxylic acid-1,2:3,4-dianhydride) and 1,2-substituted cyclobutane derivatives (for example, 1,2-substituted cyclobutane-1,2,3,4-tetracarboxylic acid-1,2:3,4-dianhydride) can be obtained. Since the 1,3-substituted cyclobutane derivative has higher symmetry than the 1,2-substituted cyclobutane derivative, when synthesized with other diamine monomers, a polyimide with a larger molecular weight can be obtained. Therefore, how to provide a method for producing a high-purity 1,3-substituted cyclobutane derivative has become an urgent problem to be solved in this industry.

Summary of the Invention

Problems 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 that can purify a 1,3-substituted cyclobutane derivative with high efficiency and high purity.

Means for Solving the Problems

[0005] In one embodiment of the present invention, the present invention comprises the step of adding a starting mixture containing a cyclobutane derivative having the structure shown in the following formulas (1) and (2) (wherein R1 is an alkyl group having 1 to 20 carbon atoms) to a tetrahydrofuran derivative to form a cyclobutane derivative mixed solution, [ka] [ka] The present invention provides a method for producing a high-purity cyclobutane derivative, comprising the steps of: filtering the cyclobutane derivative mixed solution to obtain a solid containing a cyclobutane derivative having the structure shown in 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 mixture may be heated to a temperature range from 30°C to the boiling point of the tetrahydrofuran derivative before filtering.

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

[0009] In one embodiment, the step of cooling the cyclobutane derivative mixture may be further included between the step of heating the cyclobutane derivative mixture and the step of filtering the cyclobutane derivative mixture.

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

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

[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%, and the initial purity is defined as the proportion of the cyclobutane derivative having the structure shown in formula (1) in the starting mixture 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 purity of 93% to 100% after purification, and the purity after purification 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 a cyclobutane derivative having the structure shown in formula (1) and a cyclobutane derivative having the structure shown in formula (2).

[0016] In one embodiment, the mass of the tetrahydrofuran derivative may preferably be 1 to 20 times the mass of the starting mixture containing a cyclobutane derivative having the structure shown in formula (1) and a cyclobutane derivative having the structure shown in 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 photocyclization addition reaction of a maleic anhydride derivative. [Effects of the Invention]

[0018] Compared with the prior art, the method for producing a high-purity cyclobutane derivative of the present invention can reduce the amount of solvent used, and even when the initial purity of the cyclobutane derivative having the structure shown in formula (1) is low, a high-purity 1,3-substituted cyclobutane derivative can be obtained with high efficiency.

Embodiments for Carrying out the Invention

[0019] Before explaining at least one embodiment of the present invention in detail, it should be understood that the application of the present invention is not necessarily limited to a plurality of details exemplified in the following, such as the number of examples or the specific mixing ratios used. The present invention may be other embodiments or may be implemented or realized in various ways.

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

Chemical formula

Chemical formula

[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 shown in 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 shown in 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 comprises at least one selected from the group consisting of tetrahydrofuran and 2-methyltetrahydrofuran, preferably the tetrahydrofuran derivative is tetrahydrofuran (abbreviated as THF) or 2-methyltetrahydrofuran (abbreviated as 2-Methyl-THF). By using the tetrahydrofuran derivative as a solvent, the 1,3-substituted cyclobutane derivative shown in formula (1) can be precipitated with high efficiency due to the difference in the solvent's action on a mixture of the 1,3-substituted cyclobutane derivative shown in formula (1) and the 1,2-substituted cyclobutane derivative shown in formula (2). Furthermore, if the initial purity of the 1,3-substituted cyclobutane derivative shown in formula (1) is equivalent to that of other solvents, a smaller amount of tetrahydrofuran derivative can be used to precipitate a high-purity 1,3-substituted cyclobutane derivative shown in formula (1), thereby reducing production costs. Furthermore, even if the initial purity of the 1,3-substituted cyclobutane derivative shown in formula (1) is low, a high-purity 1,3-substituted cyclobutane derivative shown in formula (1) can be precipitated without using an excess of tetrahydrofuran derivative. In addition, compared to general solvents, tetrahydrofuran derivatives have the advantage of a high boiling point and are highly safe when used as a solvent. In one example, 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 mixture may be heated to a temperature range from 30°C to the boiling point of the tetrahydrofuran derivative before filtering the cyclobutane derivative mixture. For example, it may be heated to a temperature range from 30°C to the boiling point of THF, and from 30°C to the boiling point of 2-Methyl-THF. Preferably, the cyclobutane derivative mixture is first heated to a temperature range of 30°C to 70°C. In another embodiment, the cyclobutane derivative mixture may be first heated to a temperature range of 30°C to 66°C. When actually applying the method, the heating temperatures may be adjusted according to the actual blending ratio of each compound in the tetrahydrofuran derivative and cyclobutane derivative mixture, and the present invention is not limited thereto. Heating the cyclobutane derivative mixture helps to more effectively dissolve the 1,2-substituted cyclobutane derivative shown in 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 mixture between the step of heating the cyclobutane derivative mixture and the step of filtering the cyclobutane derivative mixture. Cooling the cyclobutane derivative mixture helps to more effectively precipitate a solid containing the 1,3-substituted cyclobutane derivative shown in formula (1). Preferably, the cyclobutane derivative mixture is cooled to a temperature range of -10°C to 50°C. In actual application, the above-mentioned cooling temperature may be adjusted according to the actual blending ratio of each compound in the tetrahydrofuran derivative and cyclobutane derivative mixture, 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 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. Adding acetic anhydride helps to improve the purified purity of the cyclobutane derivative having the structure shown in formula (1). In actual application, the actual amount of acetic anhydride added may be adjusted according to the actual blending ratio of each compound in the tetrahydrofuran derivative and cyclobutane derivative mixed solution, and the present invention is not limited thereto.

[0026] In one embodiment, the proportion of the cyclobutane derivative having the structure shown in formula (1) in the starting mixture 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) may be >10%, and preferably, the proportion is 25% to 99%. In another embodiment, the aforementioned proportion is ≤25%. For example, the aforementioned proportion may be a positive integer proportion between 10% and 99%, and 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 shown in formula (1) may have a post-purification purity 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 filtering the cyclobutane derivative mixed solution 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). Preferably, the aforementioned post-purification purity may be >99%. Specifically, when the proportion of the cyclobutane derivative having the structure shown in formula (1) in the starting mixture is low, a cyclobutane derivative having the structure shown in formula (1) with high purity can still be obtained by the method for producing a high-purity cyclobutane derivative of the present invention. For example, the cyclobutane derivative having the structure shown in formula (1) may have a post-purification purity between 93% and 100%, and the aforementioned 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, 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 above multiple of mass 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 formula, the maleic anhydride derivative may be citraconic anhydride, but the present invention is not limited thereto. [ka]

[0030] In one embodiment, a photocycloaddition reaction may be induced by irradiating the maleic anhydride derivative with energy rays when producing the starting mixture, and the energy rays have a light source with a wavelength of 200 nm to 600 nm. Preferably, the energy rays are ultraviolet light. In one embodiment, the irradiation time is 1 to 60 hours. When actually applying the method, the irradiation time may be determined according to the wavelength of the energy rays, and the present invention is not limited thereto.

[0031] The present invention will be further described in detail by the following examples, but these descriptions are merely illustrative of the present invention and do not limit the scope of the invention. Modifications and changes made by those skilled in the art are all included in the disclosures herein and the appended claims.

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

[0033] [Examples and comparative examples of manufacturing] (Example 1) In a 1-liter reaction flask, add citraconic anhydride (150 g, 1.34 mol), benzophenone (12 g, 0.07 mol), and isoamyl acetate (750 g). Irradiate with ultraviolet light at a wavelength of 365 nm for 8 hours, then collect the solid by suction filtration to obtain 25 g 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). 1¹H NMR analysis revealed that the ratio of 1,3-DMCBDA to 1,2-DMCBDA in the starting mixture was 92:8. The initial purity of 1,3-DMCBDA was defined as the ratio of 1,3-DMCBDA to the total content of 1,2-DMCBDA and 1,3-DMCBDA in the starting mixture. In Example 1, the initial purity of 1,3-DMCBDA was 92%.

[0034] In a 1-liter reaction flask, 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 and stirred to form a cyclobutane derivative mixed solution. Next, the mixture was heated to 70°C, stirred under reflux for 4 hours, then cooled to room temperature, and the precipitated crystals were collected. Furthermore, the precipitated crystals were placed in a 1-liter reaction flask, 125 grams of acetic anhydride (5.0 times the mass of the starting mixture) were added, the reaction temperature was controlled to 130°C, and the mixture was reacted for 8 hours. After cooling to room temperature, the mixture was filtered by suction and dried to obtain 22.5 grams of solid. 1 By analyzing the collected solid material using 1H NMR, it was confirmed that the ratio of 1,3-DMCBDA to 1,2-DMCBDA in the solid material was 99.5:0.5, meaning that the purity of 1,3-DMCBDA after purification was 99.5%.

[0035] Table 1 below shows the detailed parameters, solvents, solutions, and mixture proportions for the examples and comparative examples. 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 high-purity cyclobutane derivatives 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 high-purity cyclobutane derivatives of the present invention is high, regardless of whether the initial purity is low or high, thus further improving the purification efficiency.

[0036] [Table 1]

[0037] As described above, the method for producing high-purity cyclobutane derivatives of the present invention allows for the production of 1,3-substituted cyclobutane derivatives with higher symmetry, higher molecular weight polyimides after synthesis with other diamine monomers, and superior physicochemical properties, with greater efficiency. Furthermore, even when the initial purity of the 1,3-substituted cyclobutane derivative is low, it is possible to precipitate a high-purity 1,3-substituted cyclobutane derivative shown in formula (1) without using an excess of tetrahydrofuran derivative (i.e., using a solvent with a low mass multiple and small quantity).

[0038] [Application Areas] The method for producing high-purity cyclobutane derivatives of the present invention can be applied to the technical fields of manufacturing methods that utilize cyclobutane derivatives, such as liquid crystal display elements, semiconductor protective materials, and insulating material displays.

[0039] While several preferred embodiments of the present invention are disclosed, they are not intended to limit the invention but rather to enable those skilled in the art to clearly understand the embodiments described herein. Since those skilled in the art can make various changes, substitutions, and modifications without departing from the spirit and scope of the invention, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. The following equations (1) and (2) (wherein R １ The steps include adding a starting mixture containing a cyclobutane derivative having the structure shown (where 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】 The step of filtering the cyclobutane derivative mixed solution to obtain a solid containing a cyclobutane derivative having the structure shown in formula (1), The tetrahydrofuran derivative is at least one selected from the group consisting of tetrahydrofuran and 2-methyltetrahydrofuran. A method for producing high-purity cyclobutane derivatives.

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

3. The cyclobutane derivative mixed solution is heated to a temperature range of 30°C to 70°C. A method for producing a high-purity cyclobutane derivative according to claim 2.

4. The steps of heating the cyclobutane derivative mixed solution and filtering the cyclobutane derivative mixed solution further include a step of cooling the cyclobutane derivative mixed solution. A method for producing a high-purity cyclobutane derivative according to claim 2.

5. The cyclobutane derivative mixed solution is cooled to a temperature range of -10°C to 50°C. A method for producing a high-purity cyclobutane derivative according to claim 4.

6. 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 is further included. A method for producing a high-purity cyclobutane derivative according to claim 4.

7. The aforementioned R １ These are alkyl groups having 1 to 4 carbon atoms. A method for producing a high-purity cyclobutane derivative according to any one of claims 1 to 6.

8. The cyclobutane derivative having the structure shown in formula (1) has an initial purity of >10%, and the initial purity is defined as the proportion of the cyclobutane derivative having the structure shown in formula (1) in the starting mixture 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). A method for producing a high-purity cyclobutane derivative according to any one of claims 1 to 6.

9. The cyclobutane derivative having the structure shown in formula (1) has a purity of 93% to 100% after purification, and the purity after purification is defined as the proportion of the cyclobutane derivative having the structure shown in formula (1) in the solid 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). A method for producing a high-purity cyclobutane derivative according to any one of claims 1 to 6.

10. 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 shown in formula (1) and the cyclobutane derivative having the structure shown in formula (2). A method for producing a high-purity cyclobutane derivative according to any one of claims 1 to 6.

11. The mass of the tetrahydrofuran derivative is 1 to 20 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). A method for producing a high-purity cyclobutane derivative according to claim 10.

12. The starting mixture comprising a cyclobutane derivative having the structure shown in formula (1) and a cyclobutane derivative having the structure shown in formula (2) is obtained by a photocyclization addition reaction of a maleic anhydride derivative. A method for producing a high-purity cyclobutane derivative according to any one of claims 1 to 6.

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