4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, its preparation method and application

Abstract

This invention relates to the field of organic chemistry, and more particularly to 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, its preparation method, and its applications. The preparation method includes: styrene and butenedioic acid diester undergoing an addition reaction under the action of a polymerization inhibitor to obtain an addition product; the addition product is then subjected to a hydrolysis reaction and a dehydration reaction sequentially to obtain 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride. The preparation method of this invention features a simple synthetic route, high reaction selectivity, high product yield, and suitability for industrial production.

Description

Technical Field

[0001] This invention relates to the field of organic chemistry, and in particular to a 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, its preparation method, and its applications. Background Technology

[0002] Polyimide (PI) is a class of polymer materials known for its excellent thermal stability, mechanical strength and chemical inertness. It is an indispensable raw material in high-tech fields such as flexible printed circuit boards, aerospace composite materials, liquid crystal alignment films, high-temperature insulating varnishes and photoresists.

[0003] 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA) is an aromatic dianhydride monomer and a key precursor for the synthesis of polyimides. This dianhydride molecule contains both a rigid tetrahydronaphthalene ring and a flexible anhydride ring; this unique "rigid-flexible" structure allows polyimide materials prepared from it to achieve an ideal balance between high thermal stability and good processability. PI films synthesized using TDA are high-performance materials that combine the heat resistance of traditional aromatic PI with the high transparency of novel optical plastics. Through ingenious molecular structure design, it solves the pain points of PI being "difficult to process" and "dark in color," making it a key material supporting next-generation flat panel displays, flexible electronics, photosensitive materials, photoresist monomers, and other high-tech industries.

[0004] Currently, the main preparation method for 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride involves using maleic anhydride as the key starting material. This is achieved through a cycloaddition reaction between maleic anhydride and a suitable conjugated diene (such as a derivative of benzene or naphthalene), constructing the crucial six-membered ring skeleton and two anhydride rings in the target molecule in one step. This preparation method has the following drawbacks: the reactants are highly irritating and corrosive; the solubility of the reactants is limited; and the reaction conditions require strict anhydrous control, making operation difficult. Therefore, this preparation method is difficult to apply to industrial production.

[0005] Therefore, the search for a simple synthetic route suitable for industrial production of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride has become a research hotspot. Summary of the Invention

[0006] To solve at least one of the above-mentioned technical problems, the present invention provides 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, its preparation method and application; the preparation method has simple steps, high product selectivity and high product yield.

[0007] In one aspect, the present invention provides a method for preparing 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, comprising: styrene and butenedioic acid diester undergoing an addition reaction under the action of a polymerization inhibitor to obtain an addition product; and subjecting the addition product to a hydrolysis reaction and a dehydration reaction in sequence to obtain 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride.

[0008] In some embodiments of the present invention, the structural formula of the butenedioic acid diester is shown in Formula I: Formula I; R1 and R2 are each independently selected from any one of the C1 to C10 alkyl groups.

[0009] In some embodiments of the present invention, the C1-C10 alkyl group includes any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0010] In some embodiments of the present invention, the butenedioic acid diester includes any one of dimethyl butenedioic acid, diethyl butenedioic acid, and methyl fumarate ethyl ester; and / or, the polymerization inhibitor includes at least one of hydroquinone, 2,5-di-tert-butylhydroquinone, p-hydroxyanisole, phenothiazine, and p-tert-butylcatechol.

[0011] In some embodiments of the present invention, the addition reaction temperature is 60-80°C (e.g., 62°C, 68°C, 72°C, 76°C, 79°C, etc.); and / or the addition reaction time is 2-5 h (e.g., 2.1 h, 2.8 h, 3.3 h, 4.1 h, 4.9 h, etc.); and / or the molar ratio of styrene, butenedioic acid diester, and addition reaction solvent is 1:(4-5):(8-20), (e.g., 1:4.2:9, 1:4.3:11, 1:4.6:15, 1:4.7:17, 1:4.9:19, etc.); and / or the addition reaction solvent includes at least one of toluene, hexane, dichlorobenzene, trihydrofuran, dioxane, propylene, and 4-methyl-2-pentanone.

[0012] In some embodiments of the present invention, the hydrolysis reaction is carried out under alkaline conditions, wherein the alkaline compound providing the alkaline conditions includes at least one of lithium hydroxide, potassium hydroxide, sodium hydroxide, potassium tert-butoxide, sodium methoxide, potassium carbonate, sodium carbonate, and cesium carbonate; and / or, the hydrolysis reaction solvent includes at least one of methanol, ethanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, acetone, and ethylene glycol dimethyl ether.

[0013] In some embodiments of the present invention, the dehydration reaction temperature is 80~120℃ (e.g., 82℃, 98℃, 102℃, 109℃, 118℃, etc.); and / or the dehydration reaction time is 6~15h (e.g., 6.1h, 7.8h, 9.3h, 11.1h, 13.9h, etc.).

[0014] In some embodiments of the present invention, the method further includes: recrystallizing the hydrolysis product to obtain a recrystallized product; wherein the recrystallization temperature is 5~10℃ (e.g., 5.6℃, 5.8℃, 7.2℃, 8.1℃, 9.6℃, etc.); and / or the recrystallization time is 2~3h (e.g., 2.1h, 2.3h, 2.6h, 2.8h, 2.9h, etc.).

[0015] In another aspect, the present invention provides a 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride obtained by the above-described preparation method.

[0016] In another aspect, the present invention provides the application of the above-mentioned 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride in the preparation of polyimides.

[0017] The technical solution provided by this invention has the following advantages: This invention relates to 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, its preparation method, and its applications. Using styrene and butenedioic acid diester as starting materials, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is obtained through addition, hydrolysis, and dehydration reactions. The preparation method of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride has simple reaction steps, few side reactions, high product selectivity, and high product yield. Furthermore, the preparation method of this invention also has the advantages of readily available raw materials and low cost.

[0018] Therefore, the preparation method of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride of the present invention has the following characteristics: novel method, readily available raw materials, good product selectivity, low product preparation cost, high product yield, and suitable for industrial production. Attached Figure Description

[0019] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, those skilled in the art can obtain other drawings based on these drawings without creative effort.

[0021] Figure 1 The NMR spectrum of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride prepared in Example 2 of this invention. Detailed Implementation

[0022] To better understand the above-mentioned objectives, features, and advantages of the present invention, the solutions of the present invention will be further described below. It should be noted that, unless otherwise specified, the embodiments of the present invention and the features thereof can be combined with each other.

[0023] Many specific details are set forth in the following description in order to provide a full understanding of the invention, but the invention may also be practiced in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of the invention, and not all embodiments.

[0024] According to embodiments of the present invention, a method for preparing 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is provided, comprising the following steps: Step (1): Under the action of flame retardant, styrene and butadiene diester are added to the addition reaction solvent to carry out the addition reaction and obtain the addition product; Step (2): Under alkaline conditions, the addition product obtained in step (1) is hydrolyzed in a hydrolysis solvent to obtain the hydrolysis product; Step (3): The hydrolysis product obtained in step (2) is recrystallized in a recrystallization solvent to obtain the recrystallized product; Step (4): The recrystallized product obtained in step (3) is subjected to a dehydration reaction to obtain 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride.

[0025] In some embodiments of the present invention, in step (1), the flame retardant includes at least one of hydroquinone, 2,5-di-tert-butylhydroquinone, p-hydroxyanisole, phenothiazine, and p-tert-butylcatechol, preferably hydroquinone.

[0026] In some embodiments of the present invention, in step (1), the structural formula of butenedioic acid diester is shown in Formula I. Formula I; R1 and R2 are each independently selected from any one of the C1 to C10 alkyl groups. The C1 to C10 alkyl groups include any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0027] In some embodiments of the present invention, in step (1), the butenedioic acid diester includes any one of dimethyl butenedioic acid, diethyl butenedioic acid, and methyl ethyl fumarate.

[0028] In some embodiments of the present invention, in step (1), the butenedioic acid diester includes at least one of trans-butenedioic acid diester and cis-butenedioic acid diester, preferably cis-butenedioic acid diester.

[0029] In some embodiments of the present invention, in step (1), the addition reaction solvent includes at least one of toluene, hexane, dichlorobenzene, trihydrofuran, dioxane, propylene, and 4-methyl-2-pentanone, preferably toluene.

[0030] In some embodiments of the present invention, in step (1), the molar ratio of styrene, cis / trans-butadiene diester, and addition reaction solvent is 1:(4~5):(8~20). Within this range, the reactants react most completely, and the product yield is highest. If the ratio is greater than this range, the reactants will be insufficient and the reactants will not dissolve completely, leading to a decrease in yield. If the ratio is less than this range, the raw material cost will increase and the waste liquid will increase, which is not conducive to cost control and environmental friendliness.

[0031] In some embodiments of the present invention, in step (1), the conditions for the addition reaction are: reacting at a temperature of 60~80°C for 2~5 hours.

[0032] In some embodiments of the present invention, in step (2), the alkaline compound providing alkaline conditions includes at least one of lithium hydroxide, potassium hydroxide, sodium hydroxide, potassium tert-butoxide, sodium methoxide, potassium carbonate, sodium carbonate, and cesium carbonate, preferably sodium methoxide.

[0033] In some embodiments of the present invention, in step (2), the hydrolysis solvent includes at least one of methanol, ethanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, acetone, and ethylene glycol dimethyl ether, preferably methanol.

[0034] In some embodiments of the present invention, in step (3), the recrystallization solvent includes at least one of acetonitrile, diethylene glycol dimethyl ether, anhydrous xylene, toluene, diethylene glycol dimethyl ether, petroleum ether, tetrahydrofuran, anisole, phenethyl ether, xylene, and n-hexane, preferably acetonitrile.

[0035] In some embodiments of the present invention, in step (3), the recrystallization temperature is 5~10℃ and the recrystallization time is 2~3h.

[0036] In some embodiments of the present invention, step (3) of the recrystallization step further includes a deionization step. The ion exchange resin used in the deionization step includes at least one of cation exchange resin H-form (hydrogen form) and anion exchange resin OH-form (hydroxyl form), preferably cation exchange resin H-form (hydrogen form).

[0037] In some embodiments of the present invention, in step (4), the dehydration reaction temperature is 80~120℃ and the dehydration reaction time is 6~15h.

[0038] In some embodiments of the present invention, the specific synthetic routes of steps (1) to (4) in a method for preparing 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride are shown in Equation 1: Equation 1 The following detailed description and explanation are provided through specific examples.

[0039] Example 1 A method for preparing 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride includes the following steps: The molar ratio of the addition reaction solvent, butenedioic acid diester, and styrene is 8:4:1.

[0040] (1) Styrene (104g, 1.0eq) and dimethyl trans-butenedioic acid (576g, 4eq) were added to the addition reaction solvent hexane (688g, 8eq), and 5.0g of polymerization inhibitor phenothiazine was added. The mixture was kept at 80℃ and stirred for 5 h. After the reaction was completed, the wet product was obtained by filtration. (2) Add 500 mL of tert-butanol and 121.3 g of potassium tert-butoxide, the hydrolysis reaction solvents, to the wet product obtained in step (1) for hydrolysis, and then filter.

[0041] (3) Add 500 mL of recrystallization solvent petroleum ether to the sample obtained in step (2), heat to complete dissolution, add anion exchange resin OH type (hydrogen-oxygen type) and then perform hot filtration, cool to 5-10℃ to crystallize for 2 hours; (4) The sample obtained in step (3) was vacuum dried at 120℃ for 15 h to obtain 278.34 g of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride.

[0042] (5) Detection step (4) to obtain the yield and purity of the sample.

[0043] The test results are as follows: the yield of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is 90.7%, and the purity is 99.42%.

[0044] Example 2 A method for preparing 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride includes the following steps: The molar ratio of the addition reaction solvent, butenedioic acid diester, and styrene is 14:4.5:1.

[0045] (1) Styrene (104 g, 1.0 eq) and dimethyl maleate (648 g, 4.5 eq) were added to the addition reaction solvent toluene (1.29 kg, 14 eq), and 5.0 g of polymerization inhibitor hydroquinone was added. The mixture was kept at 80 ℃ and stirred for 5 h. After the reaction was completed, the wet product was obtained by filtration. (2) Add 500 mL of methanol and 60.6 g of sodium methoxide as hydrolysis solvent to the wet product obtained in step (1) and then filter.

[0046] (3) Add 500 mL of recrystallization solvent acetonitrile to the sample obtained in step (2), heat to complete dissolution, add H-type (hydrogen form) cation exchange resin and perform hot filtration, cool to 5-10℃ and crystallize for 2 hours; (4) The sample obtained in step (3) was vacuum dried at 120℃ for 15h to obtain 282.63 g of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride.

[0047] (5) Detection step (4) to obtain the yield and purity of the sample.

[0048] The test results are as follows: the yield of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride was 94.13%, and the purity was 99.95%.

[0049] The NMR characterization of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride is as follows: Figure 1 As shown, based on the NMR analysis results, it can be confirmed that 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride was synthesized.

[0050] Example 3 A method for preparing 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride includes the following steps: The molar ratio of the addition reaction solvent, butenedioic acid diester, and styrene is 20:5:1.

[0051] (1) Styrene (104 g, 1.0 eq) and dimethyl maleate (720 g, 5 eq) were added to the addition reaction solvent 4-methyl-2-pentanone (2.1 kg, 20 eq), and 5.0 g of polymerization inhibitor 2,5-di-tert-butylhydroquinone was added. The mixture was kept at 80 ℃ and stirred for 5 h. After the reaction was completed, the wet product was obtained by filtration. (2) Add 500 mL of ethanol and 155.04 g of potassium carbonate as hydrolysis solvent to the wet product obtained in step (1) for hydrolysis and then filter.

[0052] (3) Add 500 mL of recrystallization solvent n-hexane to the sample obtained in step (2), heat to complete dissolution, add H-type (hydrogen form) cation exchange resin and perform hot filtration, cool to 5-10℃ and crystallize for 2 hours; (4) The sample obtained in step (3) was vacuum dried at 120℃ for 15 h to obtain 275.79 g of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride.

[0053] (5) Detection step (4) to obtain the yield and purity of the sample.

[0054] The test results are as follows: the yield of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride was 91.85%, and the purity was 99.61%.

[0055] In summary, the present invention, concerning 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, its preparation method, and its application, improves upon the original preparation process system of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride. It features inexpensive raw materials, an environmentally friendly reaction system, safe operation, high selectivity of the synthesized product, high yield, and high quality, making it suitable for large-scale industrial production.

[0056] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0057] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments described herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, characterized in that, include: Under the action of a polymerization inhibitor, styrene and butadiene diester undergo an addition reaction to obtain an addition product; The addition product was subjected to hydrolysis and dehydration reactions in sequence to obtain 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride.

2. The preparation method according to claim 1, characterized in that, The structural formula of the butenedioic acid diester is shown in Formula I: Formula I; R1 and R2 are each independently selected from any one of the C1 to C10 alkyl groups.

3. The preparation method according to claim 2, characterized in that, The C1-C10 alkyl groups include any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The butenedioic acid diester includes any one of dimethyl butenedioic acid, diethyl butenedioic acid, and methyl ethyl fumarate. And / or, the polymerization inhibitor includes at least one of hydroquinone, 2,5-di-tert-butylhydroquinone, p-hydroxyanisole, phenothiazine, and p-tert-butylcatechol.

5. The method of any one of claims 1 to 4, wherein the method further comprises the step of: In addition reactions, The addition reaction temperature is 60~80℃; And / or, the addition reaction time is 2~5 hours; And / or, the molar ratio of styrene, butenedioic acid diester, and addition reaction solvent is 1:(4~5):(8~20); And / or, the addition reaction solvent includes at least one of toluene, hexane, dichlorobenzene, trihydrofuran, dioxane, propylene, and 4-methyl-2-pentanone.

6. The method of any one of claims 1 to 5, wherein the method further comprises the step of: In the hydrolysis reaction, The hydrolysis reaction is carried out under alkaline conditions, wherein the alkaline compound providing the alkaline conditions includes at least one of lithium hydroxide, potassium hydroxide, sodium hydroxide, potassium tert-butoxide, sodium methoxide, potassium carbonate, sodium carbonate, and cesium carbonate. And / or, the hydrolysis reaction solvent includes at least one of methanol, ethanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, acetone, and ethylene glycol dimethyl ether.

7. The method of any one of claims 1 to 6, wherein the method further comprises the step of: In the dehydration reaction, The dehydration reaction temperature is 80~120℃; And / or, the dehydration reaction time is 6~15h.

8. The method of any one of claims 1 to 7, wherein the method further comprises the step of: Also includes: ​ The hydrolysis product was recrystallized to obtain the recrystallized product; The recrystallization temperature is 5~10℃; And / or, the recrystallization time is 2~3 hours.

9. A 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride obtained by the preparation method according to any one of claims 1 to 8.

10. The use of the 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride as described in claim 9 in the preparation of polyimides.

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