CN108299457B - Preparation method of tetracarboxylic dianhydride with bicyclic structure - Google Patents
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Abstract
The invention discloses a preparation method of tetracarboxylic dianhydride with a bicyclic structure, belonging to the field of fine chemical preparation methods. The main technical scheme is that phthalic acid is used as an initial raw material, and the bicyclo-tetracarboxylic dianhydride with a full-exterior structure is synthesized through five-step reactions of electrolytic reduction, 1, 4-addition, methyl esterification reaction, hydrogenation reduction, ester exchange dehydration ring closure and the like. Compared with the traditional preparation process, the method has the advantages of few operation steps, mild reaction conditions, high yield and the like, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of fine chemical preparation methods, and particularly relates to a preparation method of tetracarboxylic dianhydride with a bicyclic structure.
Background
Since Du Pont applied for the first patent of Polyimide (PI) in the world in the 50 th 20 th century, the materials have been widely used due to their excellent heat resistance, insulation and dielectric properties, mechanical and mechanical properties, and chemical resistance. The early polyimide is mainly synthesized by aromatic dianhydride and aromatic diamine monomers, and the aromatic PI is influenced by PI electron cloud and is easy to form a Charge Transfer Complex (CTC) between an electron donor and an electron acceptor, so that the PI material has dark color and poor light transmittance, and is influenced by a large PI bond, so that the PI material is insoluble and infusible, has high molding temperature and difficult recycling, and is difficult to meet the application of high-performance PI materials in specific fields.
In the initial studies, for example, T M and T Kurosaki in Macromolecules 1997, 30 (4): 993-1000 reports that a PI material prepared by mainly synthesizing bicyclo [2.2.2] octa-7-ene-2, 3,5, 6-tetracarboxylic dianhydride which is unsaturated dianhydride containing carbon-carbon double bonds and reacting the dianhydride monomer with different diamines has poor thermal stability, and thermal decomposition occurs at a temperature higher than 360 ℃ under a nitrogen atmosphere. It has further been demonstrated that such unsaturated dianhydride monomers are susceptible to the reverse 1, 4-addition reaction at elevated temperatures (greater than 350 c), see equation 1.
In order to improve the thermal stability of PI materials, attempts have been made to solve the above problems by reducing the unsaturated dianhydride by hydrogenation to obtain a saturated dianhydride. T M and T Kurosaki et al tried direct hydrogenation reduction of bicyclo [2.2.2] oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride to bicyclo [2.2.2] octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride, but without success. Because the catalytic hydrogenation reaction is a two-phase reaction, reactants are all carried out on the surface of the catalyst, the dianhydride monomer has poor solubility, and a common low-boiling point solvent is almost in an insoluble state, so that the hydrogenation reduction reaction is difficult to carry out. Although a small amount of the dianhydride can be dissolved in the high-boiling-point solvent, the high-boiling-point solvent has poor hydrogen absorption effect, and meanwhile, due to the influence of four carbonyl groups on pi electron cloud in carbon-carbon double bonds in bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, the steric hindrance of the solvent is large, and the hydrogenation reduction reaction in the high-boiling-point solvent is difficult to perform due to the combination of the two points.
According to T Matsumoto and T Kurosaki in Reactive & Functional Polymers 1996, 30 (1): 55-59, and Japanese patent JP2008100979A, proposes a preparation method for synthesizing bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic dianhydride, see reaction formula 2. In the scheme, in the process of reacting (+/-) -trans-1, 2-dimethyl dihydrogen phthalate (2) with dimethyl fumarate, the (+/-) -trans-1, 2-dimethyl dihydrogen phthalate (2) is influenced by two ester groups, and the reaction activity is poor, so that the reaction can be smoothly carried out only by needing higher reaction temperature (more than 180 ℃). Bicyclo [2.2.2] octane-2-exo, 3-endo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester (4) is hydrolyzed under different conditions, dianhydride with different configurations is obtained finally, the dianhydride is hydrolyzed under alkaline conditions, and a bicyclo [2.2.2] octane-2-endo, 3-endo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride (6a) is obtained finally, the dianhydride with the configuration of 6a has lower melting point, the PI synthesized by the dianhydride has relatively poor thermal stability, therefore, a dianhydride monomer with an all-exo structure such as 6b is needed, 4 is difficult to hydrolyze under an acidic condition, the reaction time is long (> 18h), and the yield of the finally synthesized 6b is too low.
Disclosure of Invention
In order to overcome the above difficulties, the present invention provides a method for preparing bicyclo [2.2.2] octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride, see reaction formula 3. The raw materials used in the invention have low price, the reaction condition is mild, the reaction is rapid, only bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic dianhydride with a full-exterior structure is obtained, the yield is obviously improved (the yield is more than 93 percent), and the alkyl acid methyl ester byproduct is obtained, so the atom utilization rate is high.
The preparation method of bicyclo [2.2.2] octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride comprises the following steps:
1) preparation of (+ -) -trans-1, 2-dihydrophthalic acid: placing mixed solution consisting of phthalic acid, dilute acid and organic solvent in an electrolytic cell with a diaphragm, adopting a lead electrode, controlling the electrolytic temperature to be 20-80 ℃ and the current density to be 100-600A/m2Electrolyzing and reducing to generate (+/-) -trans-1, 2-dihydrophthalic acid, distilling the reacted electrolyte under reduced pressure to separate out a white solid, filtering, recrystallizing with deionized water, and drying in vacuum to obtain the white solid with the yield of about 90%; mp: 212-213 ℃; 1H NMR (DMSO-d 6): 3.53(2H, CH), 5.81(2H, ═ CH-), 6.00(2H, — CH), 12.73(2H, COOH).
2) Bicyclo [2.2.2]Preparation of oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride: placing the white solid prepared in the step 1) and maleic anhydride in a reaction device with a condensing tube, and dehydrating the white solid and the maleic anhydride by using acetic anhydride or propionic anhydride as a solvent in a nitrogen atmosphereHeating the raw materials to 70-85 ℃ to dissolve the raw materials, continuously heating the raw materials to 85-140 ℃, reacting for 0.5-3 hours, continuously precipitating white solids in the reaction process, filtering, washing with acetone, and drying in vacuum to obtain white solid powder with the yield of about 85%; mp: 351-352 ℃;1H NMR(DMSO-d6)：3.48(2H，CH)，3.61(4H，CH)，6.38(2H，-CH＝CH-)。
3) bicyclo [2.2.2]Preparation of oct-7-en-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester: placing the white powder prepared in the step 2), a methanol solvent and concentrated sulfuric acid in a reaction device with a condensing tube, reacting for 3-7 hours at the temperature of 30-70 ℃ until the reaction is in a reflux state, cooling and crystallizing to separate out white needle crystals after the reaction is finished, and filtering and drying in vacuum to obtain the yield of about 97%; mp: 130-132 ℃;1H NMR(DMSO-d6)：3.07(2H，CH)，3.22(4H，CH)，3.48(12H，CH3)，6.14(2H，-CH＝CH-)。
4) bicyclo [2.2.2]Preparation of octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester: placing the white needle-shaped crystal prepared in the step 3), a methanol or ethanol solvent and a 5% palladium-carbon catalyst in a 500ml high-pressure reaction kettle, replacing air in the reaction kettle with hydrogen (three times), wherein the hydrogen pressure in the reaction kettle is 2-5 MPa, the reaction temperature is 60-120 ℃, the reaction time is 6-12 hours, after the reaction is finished, filtering the palladium-carbon catalyst with diatomite, distilling under reduced pressure, cooling and separating out a white granular crystal, filtering, and drying in vacuum, wherein the yield is about 85%; mp: 150 to 152 ℃;1H NMR(DMSO-d6)：1.48(4H，CH2)，2.30(2H，CH)，3.12(4H，CH)，3.56(12H，CH3)。
5) bicyclo [2.2.2]Preparation of octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride: placing the white granular crystal prepared in the step 4), alkyl acid and concentrated sulfuric acid into a reactor with a thorn fractionating column, reacting at the temperature of 80-130 ℃ for 1-3 hours, continuously separating out white powder solid in the reaction process, filtering, vacuum drying, and distilling out low-fraction byproducts with the yield of about 96%; mp: 389 to 391 ℃;1H NMR(DMSO-d6)：1.37(4H，CH2)，2.47(2H，CH)，3.52(4H，CH)。
further, the electrolysis temperature in the step (1) is 20-50 ℃, and the current density is 200-500A/m2。
Further, the reaction temperature in the step (2) of the present invention is 80 ℃ to 120 ℃.
Further, the catalytic amount of the concentrated sulfuric acid in the step (3) of the invention is 2-5% of the total mass of the raw materials, and the reaction temperature of methyl esterification is 50-70 ℃.
Further, the reaction temperature of the hydrogenation reaction in the step 4) is 80-120 ℃, the catalytic amount of 5% palladium-carbon accounts for 2-10% of the total mass of the raw materials, and the hydrogen pressure in the reaction kettle is 4-5 MPa.
Further, the alkyl acid solvent in step 5) of the present invention may be one or more selected from formic acid, acetic acid, and propionic acid.
Further, the molar ratio of the raw material to the concentrated sulfuric acid in the step 5) is 1: 0.5-1: 1, the reaction temperature is 100-130 ℃.
Detailed Description
In order to further illustrate the specific process of the preparation process of the bicycloalkene tetracarboxylic dianhydride, the following description lists specific experimental schemes, but the scheme is not limited to the specific numbers listed in the experimental cases, and the scheme of mass enlargement or mass reduction with the same ratio also belongs to the disclosure of the experimental cases.
Example 1
A negative plate: pb; the length is 100mm, the width is 40mm, and the thickness is 2 mm.
An anode plate: pb; length 80mm, width 40mm, thickness 2 mm.
And (3) cathode electrolyte: 300ml of 5% H2SO4Aqueous solution, 200ml dioxane, 40g (240mmol) phthalic acid.
Anolyte: 5% H2SO4The liquid level of the aqueous solution is equal to the liquid level of the catholyte.
A diaphragm: n324 cation exchange membrane
Current density: 200A/m2
Reaction temperature: 30 deg.C
Detecting the reaction process by HPLC (high performance liquid chromatography), after 17 hours, ending the reaction, distilling a part of solvent from the reaction liquid under reduced pressure, cooling and crystallizing to separate out a white solid, carrying out suction filtration, washing with distilled water for 1 to 2 times, filtering, and drying in vacuum to obtain 36.84g of a product, wherein the yield is 91%, and the purity is 99.6% by HPLC.
Placing 36.84g (220mmol) (+ -) -trans-1, 2-dihydrophthalic acid, 21.48g (220mmol) maleic anhydride and 60g acetic anhydride in a reaction device with a condensing tube, heating to 70 ℃ in a nitrogen atmosphere, dissolving the raw materials, continuously heating to 120 ℃, magnetically stirring, continuously precipitating white solids in the reaction liquid after half an hour, stopping the reaction after 2 hours, filtering, washing with acetic acid for 1-2 times, and vacuum-drying to obtain 46.27g white powder with the yield of 85%.
46.27g (190mmol) bicyclo [2.2.2] oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride, 9.25g (90mmol) concentrated sulfuric acid and 140g methanol are placed in a reaction device with a condenser tube, the temperature is raised to the reflux temperature, magnetic stirring is carried out, the reaction process is detected by a TLC point plate, the reaction is finished after 5 hours, white needle-shaped crystals are separated out by cooling crystallization, and 61.67g of products are obtained by suction filtration and vacuum drying, wherein the yield is 97%.
61.67g (180mmol) bicyclo [2.2.2] oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester, 3g (1.41mmol) 5% palladium carbon and 180g methanol are placed in a 500ml high-pressure reaction kettle, air in the reaction kettle is replaced by hydrogen (2 to 3 times), the hydrogen pressure in the reaction kettle is 5MPa, the reaction is started after the temperature is raised to 100 ℃, mechanical stirring is carried out, the reaction process is detected by TLC point plates, the reaction is finished after 6 hours, the palladium carbon in the solution is filtered by diatomite, a part of methanol solvent is distilled out under reduced pressure, white granular crystals are separated out by cooling crystallization, and 54.78g of products are obtained by suction filtration and vacuum drying, and the yield is 88%.
54.78g (160mmol) bicyclo [2.2.2] octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester, 16.5g (160mmol) concentrated sulfuric acid and 160g acetic acid are placed in a reactor with a thorn fractionating column, the temperature is increased to 120 ℃ to start reaction, magnetic stirring is carried out, white solid is continuously separated out from reaction liquid after half an hour, 55 ℃ low fraction component methyl acetate is collected, the reaction is stopped after 1 hour, suction filtration is carried out, the acetic acid is washed for 1 to 2 times, 38.47g white powder is obtained by vacuum drying, the yield is 94%, the mass of the low fraction colorless liquid is 46.47g, the yield is 98%, and the purity is 99.8% by gas phase detection.
Example 2
A negative plate: pb; the length is 100mm, the width is 40mm, and the thickness is 2 mm.
An anode plate: pb; length 80mm, width 40mm, thickness 2 mm.
And (3) cathode electrolyte: 250ml 10% H2SO4Aqueous solution, 250ml of isopropanol, 60g (360mmol) of phthalic acid.
Anolyte: 10% H2SO4The liquid level of the aqueous solution is equal to the liquid level of the catholyte.
A diaphragm: n324 cation exchange membrane
Current density: 300A/m2
Reaction temperature: 25 deg.C
Detecting the reaction process by HPLC (high performance liquid chromatography), after 17 hours, ending the reaction, distilling a part of solvent from the reaction liquid under reduced pressure, cooling and crystallizing to separate out a white solid, carrying out suction filtration, washing with distilled water for 1 to 2 times, filtering, and drying in vacuum to obtain 54.05g of a product, wherein the yield is 89%, and the purity is 99.6% by HPLC.
54.05g (320mmol) (+ -) -trans-1, 2-dihydrophthalic acid, 31.52g (320mmol) maleic anhydride and 160g acetic anhydride are placed in a reaction device with a condensing tube, the temperature is raised to 70 ℃ in a nitrogen atmosphere, then the raw materials are dissolved, the temperature is continuously raised to 80 ℃, the raw materials are magnetically stirred, after 1 hour, white solid is continuously separated out from reaction liquid, after 3 hours, the reaction is stopped, the filtration is carried out, the acetic acid is washed for 1 to 2 times, and the vacuum drying is carried out to obtain 70.20g white powder, wherein the yield is 88%.
70.20g (283mmol) bicyclo [2.2.2] oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride, 14.04g (151mmol) concentrated sulfuric acid and 220g methanol are placed in a reaction device with a condenser tube, the temperature is raised to the reflux temperature, magnetic stirring is carried out, the reaction process is detected by a TLC point plate, the reaction is finished after 5 hours, white needle-shaped crystals are separated out by cooling crystallization, and 93.37g of products are obtained by suction filtration and vacuum drying, wherein the yield is 97%.
93.37g (274mmol) bicyclo [2.2.2] oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester, 2.8g (1.31mmol) 5% palladium carbon and 270g methanol are placed in a 500ml high-pressure reaction kettle, air in the reaction kettle is replaced by hydrogen (2 to 3 times), the hydrogen pressure in the reaction kettle is 5MPa, the temperature is increased to 120 ℃ to start reaction, mechanical stirring is carried out, TLC point plate detection is carried out to detect the reaction process, 3 times of hydrogen is supplemented during the reaction, after 10 hours, the reaction is finished, the palladium carbon in the solution is filtered by diatomite, a part of methanol solvent is distilled under reduced pressure, white granular crystals are separated out by cooling crystallization, suction filtration and vacuum drying are carried out to obtain 81.71g of a product, and the yield is 87%.
81.71g (239mmol) bicyclo [2.2.2] octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester, 36.9g (358mmol) concentrated sulfuric acid and 240g formic acid are placed in a reactor with a thorn fractionating column, the temperature is increased to 100 ℃ to start reaction, magnetic stirring is carried out, white solid is continuously separated out from reaction liquid after 1 hour, low fraction component methyl formate at 30 ℃ is collected, the reaction is stopped after 2 hours, suction filtration is carried out, acetic acid is washed for 1 to 2 times, vacuum drying is carried out to obtain 54.34g of white powder, the yield is 91%, the mass of low fraction colorless liquid is 55.61g, the yield is 97%, and the purity is 99.9% by gas phase detection.
Example 3
A negative plate: pb; the length is 100mm, the width is 40mm, and the thickness is 2 mm.
An anode plate: pb; length 80mm, width 40mm, thickness 2 mm.
And (3) cathode electrolyte: 400ml 15% H2SO4Aqueous solution, 200ml DMF, 80g (480mmol) phthalic acid.
Anolyte: 15% H2SO4The liquid level of the aqueous solution is equal to the liquid level of the catholyte.
A diaphragm: n324 cation exchange membrane
Current density: 400A/m2
Reaction temperature: 50 deg.C
Detecting the reaction process by HPLC (high performance liquid chromatography), after 17 hours, ending the reaction, distilling a part of solvent from the reaction liquid under reduced pressure, cooling and crystallizing to separate out a white solid, carrying out suction filtration, washing with distilled water for 1 to 2 times, filtering, and drying in vacuum to obtain 75.30g of a product, wherein the yield is 93 percent, and the purity is 99.8 percent by HPLC.
75.30g (448mmol) (+ -) -trans-1, 2-dihydrophthalic acid, 43.91g (448mmol) maleic anhydride and 220g acetic anhydride are placed in a reaction device with a condensing tube, the temperature is raised to 70 ℃ in a nitrogen atmosphere, then the raw materials are dissolved, the temperature is continuously raised to 140 ℃ in a reflux state, the magnetic stirring is carried out, white solid is continuously separated out from reaction liquid after 10 minutes, the reaction is stopped after half an hour, the suction filtration is carried out, acetone is washed for 1 to 2 times, 86.69g white powder is obtained after vacuum drying, and the yield is 78%.
86.69g (350mmol) bicyclo [2.2.2] oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride, 13g (140mmol) concentrated sulfuric acid and 250g methanol are placed in a reaction device with a condenser tube, the temperature is raised to the reflux temperature, magnetic stirring is carried out, a TLC point plate is used for detecting the reaction process, the reaction is finished after 7 hours, white needle-shaped crystals are separated out by cooling crystallization, and 114.12g of products are obtained by suction filtration and vacuum drying, wherein the yield is 96%.
114.12g (335mmol) bicyclo [2.2.2] oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester, 11.4g (5.36mmol) 5% palladium carbon and 230g ethanol are placed in a 500ml high-pressure reaction kettle, air in the reaction kettle is replaced by hydrogen (2 to 3 times), the hydrogen pressure in the reaction kettle is 5MPa, the temperature is increased to 110 ℃ to start reaction, mechanical stirring is carried out, TLC point plate detection is carried out to detect the reaction process, 5 times of hydrogen is supplemented during the reaction, after 3 hours, the reaction is finished, the palladium carbon in the solution is filtered by diatomite, a part of ethanol solvent is distilled out under reduced pressure, white granular crystals are separated out by cooling crystallization, and suction filtration and vacuum drying are carried out to obtain 103.31g of a product, and the yield is 90%.
103.31g (300mmol) bicyclo [2.2.2] octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester, 15.56g (150mmol) concentrated sulfuric acid and 200g propionic acid are placed in a reactor with a thorn fractionating column, the temperature is increased to 130 ℃ to start reaction, magnetic stirring is carried out, white solid is continuously separated out from reaction liquid after half an hour, 78 ℃ low fraction component methyl propionate is collected, the reaction is stopped after 1 hour, suction filtration is carried out, acetic acid is washed for 1 to 2 times, 72.48g white powder is obtained by vacuum drying, the yield is 96%, the mass of the low fraction colorless liquid is 98.9g, the yield is 93%, and the gas phase detection purity is 98.9%.
Claims (4)
1. A preparation method of tetracarboxylic dianhydride with a bicyclic structure is characterized by comprising the following steps:
1) putting mixed solution consisting of phthalic acid, dilute acid and organic solvent into an electrolytic bath with a diaphragm, adopting a lead electrode, and carrying out electrolytic reduction to generate (+/-) -trans-1, 2-dihydrophthalic acid, wherein the product after electrolysis is a racemic mixture of two different isomers of 1S,2S and 1R, 2R;
wherein the dilute acid is a sulfuric acid aqueous solution with the mass fraction of 5-20%;
2) in the nitrogen atmosphere, acetic anhydride or propionic anhydride is used as a solvent and a dehydrating agent, and (+/-) -trans-1, 2-dihydrophthalic acid reacts with maleic anhydride to generate bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride with an all-exterior structure; the reaction temperature is 60-140 ℃;
3) methyl esterifying bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride with the full-form structure prepared in the step 2) by using methanol as a solvent and concentrated sulfuric acid as a catalyst to generate bicyclo [2.2.2] oct-7-ene-2-form, 3-form, 5-form, 6-form-tetracarboxylic acid tetramethyl ester;
wherein the dosage of the concentrated sulfuric acid is 1-10% of the total mass of the raw materials, and the reaction temperature of the methyl esterification is 30-70 ℃;
4) in a high-pressure reaction kettle, using methanol as a solvent and 5% palladium carbon as a catalyst, carrying out hydrogenation reduction on bicyclo [2.2.2] oct-7-ene-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester prepared in the step 3) to generate bicyclo [2.2.2] octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester;
5) in a fractionating reactor, alkyl acid is used as a solvent, concentrated sulfuric acid is used as a catalyst and a dehydrating agent, the bicyclo [2.2.2] octane-2-shape, 3-shape, 5-shape, 6-shape-tetracarboxylic acid tetramethyl ester prepared in the step 4) is subjected to ester exchange and dehydration ring closure to generate bicyclo [2.2.2] octane-2-shape, 3-shape, 5-shape, 6-shape-tetracarboxylic acid-2, 3:5, 6-dianhydride, and simultaneously, the low fraction component alkyl acid methyl ester is fractionated;
wherein the alkyl acid solvent is one or more of formic acid, acetic acid, propionic acid, n-butyric acid and tert-butyric acid; the mol ratio of bicyclo [2.2.2] octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid tetramethyl ester to concentrated sulfuric acid is 1: 0.5-1: 2, the reaction temperature is 80-130 ℃;
the tetracarboxylic dianhydride with a bicyclic structure is the product bicyclo [2.2.2] of the step 5)]Octane-2-exo, 3-exo, 5-exo, 6-exo-tetracarboxylic acid-2, 3:5, 6-dianhydride, having the structural formula,
2. the method according to claim 1, wherein the electrolysis temperature is 20 to 80 ℃ and the current density is 100 to 600A/m in step 1)2。
3. The preparation method according to claim 1, wherein in step 1), the organic solvent is one or more selected from dioxane, tetrahydrofuran, isopropanol, methanol, ethanol, dimethylformamide and dimethylacetamide.
4. The preparation method of claim 1, wherein in the step 4), the reaction temperature of the hydrogenation reaction is 60-120 ℃, the amount of 5% palladium carbon accounts for 2-20% of the total mass of the raw materials, and the hydrogen pressure in the reaction kettle is 2-5 MPa.
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5666076B2 (en) * | 2006-09-19 | 2015-02-12 | 和光純薬工業株式会社 | Bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, its production method, said bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic Polyimide obtained from acid dianhydride and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| Soluble and Colorless Polyimides from Bicyclo[2.2.2]octane-2，3，5，6-tetracarboxylic 2，3：5，6-Dianhydrides;Toshihiko Matsumoto，等;《Macromolecules》;19970224;第30卷(第4期);第994页图2、第998-999页实施例 * |
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| CN108299457A (en) | 2018-07-20 |
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