The invention relates to a method for preparing 3, 3apos; 4, 4 apos, 4, 4 apos; method for preparing biphenyltetracarboxylic dianhydride

Abstract

The invention provides a method for preparing 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride, which comprises the following steps: adding biphenyl, dianhydride and a cocatalyst into an ionic liquid, adding a part of the catalyst, after the reaction is completed at low temperature, adding the rest of the catalyst, continuing the heating reaction, and after the intermediate is completely reacted, filtering the reaction liquid to obtain the 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride. And adding an oxidizing agent into the filtrate, carrying out heating reaction, adding the reaction liquid into ice water after the reaction is completed, filtering after stirring, washing a filter cake with water, and carrying out stepped drying in a vacuum drying oven to obtain the 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride. The Friedel-Crafts reaction is adopted to replace the coupling reaction, the raw materials are easy to purchase, the route is long, but the one-pot reaction can be performed, the process is simple and controllable, the yield is high, and the method is suitable for mass production.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride. Background Art

[0002] Polyimide is polymerized from diamine and dianhydride monomers. Dianhydride monomer is one of the important raw materials for preparing polyimide. The structure of dianhydride monomer determines that polyimide has different mechanical properties, such as high temperature resistance, used for thermal insulation layer, heat preservation layer. High thermal stability, used to produce solar cells with the highest efficiency and yield, and used as substrates in thin-film a-Si and CIGS photovoltaic applications. Thermoplastic thermosetting, etc., replace materials such as glass and metal. Flexibility and good dimensional stability, used for insulating circuit boards, high-temperature powder coatings and transformers.

[0003] At present, the methods reported for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride are mainly:

[0004] 1. Phthalic anhydride method

[0005] (1) 4-chlorophthalic anhydride is used as the raw material and the product is obtained through four steps of esterification, coupling, hydrolysis and anhydride formation. The total yield of the route is 61.9%.

[0006] (2) Using 4-chlorophthalic anhydride sodium salt and phthalic acid sodium salt as raw materials, it is obtained through coupling, hydrolysis, dehydration and other steps with a yield of 87%.

[0007] 2. o-Xylene method

[0008] BPDA was obtained from 4-chloro / bromo-o-xylene via coupling, oxidation, dehydration and other steps. The total yield of the three-step reaction was 72%.

[0009] 3. Other methods

[0010] (1) Patent RU2682170: Using dipropyl iodide or methyl iodide as raw material, the product is obtained through coupling, hydrolysis and dehydration with a yield of 37%.

[0011] (2) Patent CN113461646: discloses a method of obtaining BPDA by coupling hydrolysis and dehydration of N-substituted phthalimide as raw material.

[0012] The existing synthesis method of 3,3',4,4'-biphenyltetracarboxylic dianhydride has a long route and cannot be processed together, and multiple separation operations and delicate purification steps result in a low yield. Summary of the invention

[0013] In view of this, the present invention aims to provide a method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride to solve the problems of complex reaction and low yield.

[0014] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0015] A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride comprises the following steps: adding biphenyl, dianhydride and a promoter into an ionic liquid, adding a portion of the catalyst, adding the remaining catalyst after a low-temperature reaction is complete, and continuing to heat the reaction, filtering the reaction liquid after an intermediate reaction is complete, adding an oxidant to the filtrate and heating the reaction, adding the reaction liquid into ice water after the reaction is complete, stirring and filtering, washing the filter cake with water, and then step-drying in a vacuum drying oven to obtain 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0016] Furthermore, the molar ratio of biphenyl to dianhydride is 1:(2-2.05), and the mass ratio of biphenyl, ionic liquid, catalyst and co-catalyst is 1:(4-10):(1.5-6):(0.5%-5%).

[0017] Furthermore, the dianhydride is one of succinic anhydride, glutaric anhydride, maleic anhydride and adipic anhydride.

[0018] Further, the ionic liquid is one or two of 1-ethyl-3-methylimidazolium aluminum chloride, 1-ethyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium aluminum chloride, 1-butylpyridine chloroaluminate, trimethylamine chloroaluminate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium ferric chloride, 1-butyl-3-methylimidazolium aluminum bromide chloride, 1-pentyl-3-methylimidazolium tetrafluoroborate, 2-methylimidazolium quaternary phosphonium salt, 1-methyl-3-benzylimidazole hydrogensulfide, and triethylamine chloroaluminate.

[0019] Furthermore, the catalyst is one or two or more of anhydrous aluminum chloride ultrafine powder, silica gel aluminum chloride, solid super acid, trifluoromethanesulfonic acid series, polyphosphoric acid and its load or titanium tetrachloride, phosphotungstic acid, heteropoly acid, and ion exchange resin.

[0020] Furthermore, the solid superacid is SO 4 2- / Al 2 O 3 、SO 4 2- / TiO 2 or SO 4 2- / ZrO 2 .

[0021] Furthermore, the trifluoromethanesulfonic acid series is zinc trifluoromethanesulfonate, bismuth trifluoromethanesulfonate or aluminum trifluoromethanesulfonate.

[0022] Furthermore, the co-catalyst is one or more of thioglycolic acid, mercaptan, citric acid, phytic acid, montmorillonite, dimethylaluminum chloride, diisobutylaluminum chloride, methylaluminum chloride, and silicomolybdic acid hydrate.

[0023] Furthermore, the oxidant is one or more of potassium permanganate, methyl ethyl ketone peroxide, tert-butyl perbenzoate, air, peracetic acid, nitric acid, and sulfuric acid.

[0024] Furthermore, the reaction temperature of the low-temperature reaction is -10°C-10°C, and the reaction temperature of the elevated-temperature reaction is 50-140°C.

[0025] The reaction formula involved in the present invention is as follows:

[0026]

[0027] Compared with the prior art, the method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride described in the present invention has the following advantages: Friedel-Crafts reaction is used instead of coupling reaction, raw materials are easy to purchase, the route is long but can be reacted in one pot, the process is simple and controllable, the yield is high, and it is suitable for mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0029] Figure 1 This is the HPLC chart of 3,3',4,4'-biphenyltetracarboxylic dianhydride prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0030] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present invention can be combined with each other. Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as those generally understood by technicians in the field to which the present invention belongs. The test reagents used in the following embodiments, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.

[0031] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0032] Scheme 1: Succinic anhydride as raw material

[0033] The reaction formula of the method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride using succinic anhydride as raw material is as follows:

[0034]

[0035] Example 1

[0036] 154g biphenyl, 202g succinic anhydride, 4860g 1-ethyl-3-methylimidazolium chloride, 3g thioglycolic acid were cooled to below 10°C under mechanical stirring, 150g anhydrous aluminum chloride superfine powder was added, and the mixture was stirred at this temperature for 3 hours. Then 150g anhydrous aluminum chloride superfine powder was added, the mixture was heated to 100°C for reaction for 5 hours, and then filtered. 1140g 20% ​​peracetic acid was added dropwise to the filtrate at 50°C, and the temperature of the reaction solution was kept not higher than 30°C during the addition process. The reaction mixture was added to ice water for crystallization, filtered, and the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours, then heated to 140°C for drying for 3 hours, and finally heated to 220°C for drying for 4 hours to obtain 273g 3,3',4,4'-biphenyltetracarboxylic anhydride as an off-white powder with a liquid content of 99.98% and a yield of 92.86%.

[0037] Example 2

[0038] 154g of biphenyl, 202g of succinic anhydride, 3600g of 1-ethyl-3-methylimidazole trifluoromethanesulfonate, and 5g of dimethylaluminum chloride were cooled to below 10°C under mechanical stirring, 182g of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at this temperature for 5 hours. Then, 182g of aluminum trifluoromethanesulfonate was added, the mixture was heated to 90°C, reacted for 7 hours, and filtered. 1350g of 20% peracetic acid was added dropwise to the filtrate at 60°C until the raw materials reacted completely. The reaction solution was added to ice water for crystallization, filtered, and the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours, then heated to 140°C and dried for 3 hours, and finally heated to 220°C and dried for 4 hours to obtain 252g of 3,3',4,4'-biphenyltetracarboxylic anhydride as an off-white powder with a liquid content of 99.91% and a yield of 85.71%.

[0039] Example 3

[0040] 154g of biphenyl, 205g of succinic anhydride, 1420g of 1-butyl-3-methylimidazolium hexafluoroantimonate, and 4.6g of methylaluminum chloride were cooled to below 10°C under mechanical stirring, 140g of polyphosphoric acid was added, and the mixture was stirred at this temperature for 5 hours. Then, 140g of polyphosphoric acid was added, the temperature was raised to 90°C, and the mixture was reacted for 7 hours and filtered. 1400g of 20% peracetic acid was added dropwise to the filtrate at 60°C until the raw materials reacted completely. The reaction solution was added to ice water for crystallization, filtered, and the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours, then heated to 140°C and dried for 3 hours, and finally heated to 220°C and dried for 4 hours to obtain 265g of 3,3',4,4'-biphenyltetracarboxylic anhydride as an off-white powder with a liquid content of 99.93% and a yield of 90.14%.

[0041] Scheme 2: Maleic anhydride as raw material

[0042] The reaction formula of the method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride using maleic anhydride as raw material is as follows:

[0043]

[0044] Example 4

[0045] 154g biphenyl, 206g maleic anhydride, 4300g 1-ethyl-3-methylimidazolium chloride aluminum, 3g thioglycolic acid, under mechanical stirring, cooled to below 10°C, added 150g anhydrous aluminum chloride superfine powder, stirred at this temperature for 3 hours, then added 150g anhydrous aluminum chloride superfine powder, heated to 105°C for reaction for 5 hours, filtered, 1100g 20% ​​peracetic acid was added dropwise to the filtrate at 30°C, and the temperature of the reaction solution was kept not higher than 30°C during the dropping process; until the raw materials reacted completely, the reaction solution was added to ice water for crystallization, filtered, the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours, then heated to 140°C for drying for 3 hours, and finally heated to 220°C for drying for 4 hours to obtain 265g 3,3',4,4'-biphenyltetracarboxylic anhydride as an off-white powder with a liquid content of 99.92% and a yield of 90.13%.

[0046] Example 5

[0047] 154g of biphenyl, 206g of maleic anhydride, 3800g of 1-ethyl-3-methylimidazolium trifluoroacetate, and 3g of diisobutylaluminum chloride were cooled to below 10°C under mechanical stirring, and 139g of solid superacid SO was added. 4 2- / Al 2 O 3 , stirred at this temperature for 5 hours, then added 139 g of solid superacid SO 4 2- / Al2 O 3 The mixture was heated to 100°C and reacted for 3 hours, then filtered. 450 g of potassium permanganate was added to the filtrate at 60°C, and the reaction was continued at 100°C after the addition was completed; until the raw materials reacted completely, the reaction solution was filtered, the filtrate was added to ice water for crystallization, filtered, the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours, then heated to 140°C and dried for 3 hours, and finally heated to 220°C and dried for 4 hours to obtain 250 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride as an off-white powder with a yield of 85.03% and a liquid content of 99.74%.

[0048] Example 6

[0049] 154g of biphenyl, 206g of maleic anhydride, 4600g of 1-ethyl-3-methylimidazole methyl sulfate, and 6g of dimethylaluminum chloride were cooled to below 10°C under mechanical stirring, 152g of polyphosphoric acid was added, and the mixture was stirred at this temperature for 2 hours. Then, 152g of polyphosphoric acid was added, the mixture was heated to 100°C, and the mixture was reacted for 4 hours, and then filtered. 1380g of 20% peracetic acid was added dropwise to the filtrate at 30°C. After the addition was completed, the reaction was continued until the raw materials reacted completely. The reaction solution was added to ice water for crystallization, and the mixture was filtered. The filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours, then heated to 140°C and dried for 3 hours, and finally heated to 220°C and dried for 4 hours to obtain 238g of 3,3',4,4'-biphenyltetracarboxylic anhydride as an off-white powder with a yield of 80.95% and a liquid content of 99.92%.

[0050] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride, characterized in that: The method comprises the following steps: adding biphenyl, dianhydride and a promoter into an ionic liquid, adding a part of the catalyst, adding the remaining catalyst after the low-temperature reaction is complete, and continuing the temperature-raising reaction; after the intermediate reaction is complete, filtering the reaction liquid; adding an oxidant into the filtrate and heating the reaction; after the reaction is complete, adding the reaction liquid into ice water, stirring and filtering; washing the filter cake with water and then step-drying in a vacuum drying oven to obtain 3,3',4,4'-biphenyltetracarboxylic dianhydride.

2. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 1, characterized in that: The molar ratio of biphenyl to dianhydride is 1:(2-2.05), and the mass ratio of biphenyl, ionic liquid, catalyst and co-catalyst is 1:(4-10):(1.5-6):(0.5%-5%).

3. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 1, characterized in that: The dianhydride is one of succinic anhydride, glutaric anhydride, maleic anhydride and adipic anhydride.

4. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 1, characterized in that: The ionic liquid is one or two of 1-ethyl-3-methylimidazolium aluminum chloride, 1-ethyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium aluminum chloride, 1-butylpyridine chloroaluminate, trimethylamine chloroaluminate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium ferric chloride, 1-butyl-3-methylimidazolium aluminum bromide chloride, 1-pentyl-3-methylimidazolium tetrafluoroborate, 2-methylimidazolium quaternary phosphonium salt, 1-methyl-3-benzylimidazole hydrogensulfide, and triethylamine chloroaluminate.

5. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 1, characterized in that: The catalyst is one or two or more of anhydrous aluminum chloride ultrafine powder, silica gel aluminum chloride, solid super acid, trifluoromethanesulfonic acid series, polyphosphoric acid and its load or titanium tetrachloride, phosphotungstic acid, heteropoly acid, and ion exchange resin.

6. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 5, characterized in that: The solid superacid is SO4 2- / Al2O3、SO4 2- / TiO2 or SO4 2- / ZrO2.

7. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 5, characterized in that: The trifluoromethanesulfonic acid series is zinc trifluoromethanesulfonate, bismuth trifluoromethanesulfonate or aluminum trifluoromethanesulfonate.

8. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 1, characterized in that: The co-catalyst is one or more of thioglycolic acid, mercaptan, citric acid, phytic acid, montmorillonite, dimethylaluminum chloride, diisobutylaluminum chloride, methylaluminum chloride and silicomolybdic acid hydrate.

9. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 1, characterized in that: The oxidant is one or more of potassium permanganate, methyl ethyl ketone peroxide, tert-butyl perbenzoate, air, peracetic acid, nitric acid and sulfuric acid.

10. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 1, characterized in that: The reaction temperature of the low temperature reaction is -10°C to 10°C, and the reaction temperature of the elevated temperature reaction is 50-140°C.

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