Preparation method of bisphenol type phthalimide

Abstract

The invention relates to the technical field of organic synthesis, and particularly discloses a preparation method of bisphenol-type phthalimide, which comprises the following steps: adding a solvent E into a reaction flask under the protection of inert gas, then adding a raw material bisphenol compound A, a raw material halogenated or nitro substitute B, an alkali compound C and a catalyst D, and reacting for 2-4 hours; and finally, adding the solvent E again to adjust the solid content of the reaction system to be 5-40%, heating to 25-180 DEG C, reacting for 8-72 hours, and after the reaction is finished, sequentially filtering, concentrating under reduced pressure, purifying, performing rotary evaporation and drying to obtain the bisphenol phthalimide. The bisphenol-substituted phthalimide is prepared from the bisphenol monomer and the halogenated or nitro-substituted phthalimide through a one-step oxidative coupling method under the action of the catalyst, and the preparation method is simple in process operation, mild in reaction condition, mature and stable in process route and beneficial to industrial stable production.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and more specifically to a method for preparing bisphenol phthalimide. Background Art

[0002] Polyetherimide is a high-performance special engineering plastic with the advantages of high heat resistance, excellent mechanical strength, good insulation and chemical corrosion resistance. It can be used for a long time at 150°C and can maintain good mechanical properties and dimensional stability. It is widely used in high-end fields such as aerospace, microelectronics, electrical, automobile, and military industry.

[0003] Polyetherimide is usually prepared from dianhydride and diamine through functional group polycondensation reaction, in which dianhydride is an important monomer raw material. Compared with diamine monomer, there are fewer synthesis methods for dianhydride monomer, usually using bisphenol salt compounds and fluorine, bromine, chlorine, nitro and other groups for nucleophilic substitution reaction. And the reaction conditions are relatively harsh, usually need to be carried out under high temperature conditions, which not only has high requirements on equipment, but also increases energy consumption and safety risks.

[0004] At present, the general synthesis process of bisphenol phthalimide is divided into two steps: first, the bisphenol compound is reacted with a strong base to prepare the corresponding organic metal phenolate; then, the halogenated or nitro-substituted phthalimide and a phase transfer catalyst are added to the solution, and the disubstituted phthalimide is prepared in a non-polar solvent under high temperature conditions. The disadvantages of this process route are that the operation process is relatively complicated, the energy consumption is high, the catalyst is expensive, etc., which greatly increases the cost of industrial manufacturing and does not conform to the concept of industrial production. Based on the above statement, it is urgent to develop a simple, efficient, mild, stable nucleophilic substitution process route suitable for industrial production to help enterprises improve quality and efficiency. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a method for preparing bisphenol-type phthalimide, wherein bisphenol-substituted phthalimide is prepared by a one-step oxidative coupling method through a bisphenol monomer and a halogenated or nitro-substituted phthalimide under the action of a catalyst. The process of the present invention is simple to operate, the reaction conditions are mild, the process route is mature and stable, and it is conducive to stable industrial production.

[0006] In the first aspect, the present invention provides a method for preparing bisphenol phthalimide, which adopts the following technical scheme: A method for preparing bisphenol phthalimide comprises the following steps: Under the protection of inert gas, add solvent E to the reaction bottle, then add raw material bisphenol compound A, raw material halogenated or nitro substituted product B, alkaline compound C, catalyst D, and finally add solvent E again to adjust the solid content of the reaction system to 5-40%, raise the temperature to 25-180°C, react for 8-72h, and after the reaction is completed, filter, concentrate under reduced pressure, purify, rotary evaporate, and dry to obtain bisphenol phthalimide.

[0007] Preferably, the bisphenol compound A is bisphenol A, bisphenol S, bisphenol F, hexafluorobisphenol A, tetrabromobisphenol A, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 4,4'-(1-phenylethyl)bisphenol, 4,4'-dibenzhydryl bisphenol, 1,1'-bis(4-hydroxy-3-methylphenyl)cyclohexane, 5,5'-(1-methylethyl)bis[(1,1'- One or more of: 2,6-dibromo-4-[1-(3-bromo-4-hydroxyphenyl)-1-methylethyl]phenol, bisphenol fluorene, hydroquinone, resorcinol, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3,5,3',5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, and 2,7-dihydroxy-9-fluorenone.

[0008] Preferably, the structural formula of the bisphenol compound A is as follows: .

[0009] Preferably, the halogenated or nitro-substituted compound B is N-methyl-4-nitrophthalimide, N-ethyl-4-nitrophthalimide, N-butyl-4-nitrophthalimide, N-phenyl-4-nitrophthalimide, N-methyl-3-nitrophthalimide, N-ethyl-3-nitrophthalimide, N-butyl-3-nitrophthalimide, N-phenyl-3-nitrophthalimide One or more of nitrophthalimide, 4-chloro-N-methylphthalimide, 4-bromo-N-methylphthalimide, 4-iodo-N-methylphthalimide, 4-fluoro-N-methylphthalimide, 3-chloro-N-methylphthalimide, 3-bromo-N-methylphthalimide, 3-iodo-N-methylphthalimide, and 3-fluoro-N-methylphthalimide.

[0010] Preferably, the structural formula of the halogenated or nitro-substituted compound B is as follows: .

[0011] Preferably, the alkaline compound C is one of potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium fluoride, sodium fluoride, lithium fluoride, cesium fluoride, potassium carbonate, potassium phosphate, sodium phosphate, cesium carbonate, sodium carbonate, silver carbonate, cerium carbonate, potassium tert-butoxide, and sodium tert-butoxide.

[0012] Preferably, the catalyst D is one or more of nano copper oxide, nano cuprous iodide, sodium acetate, copper acetate, palladium acetate, rhodium acetate, rhodium chloride, palladium chloride, triphenylphosphine rhodium chloride, triphenylphosphine palladium chloride, palladium carbon, dibromo[1,1'-bis(diphenylphosphino)ferrocene]palladium, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, 1,1'-bis(di-cyclohexylphosphino)ferrocene palladium dichloride, and bis(pyridine)palladium dichloride. The catalyst ligand is one or more of triphenylphosphine, tetramethylethylenediamine, proline, 2,2-bipyridine, and 1,2-bis(diphenylphosphino)ethane.

[0013] Preferably, the organic solvent E is one of benzene, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 1,4-dioxane, N-methylpyrrolidone, dichloromethane and dichloroethane.

[0014] Preferably, the molar ratio of the bisphenol compound A to the halogenated or nitro-substituted compound B is 1:1.8-1:3.5; the molar ratio of the bisphenol compound A to the alkaline compound C is 1:0.8-1:5; and the amount of the catalyst D added is 0.1-10% of the total molar amount of the reactants.

[0015] Preferably, the reaction system further comprises a catalyst ligand, and the molar ratio of the catalyst ligand to the catalyst D is 1:1 to 3:1.

[0016] Preferably, the purification is specifically: silica gel column chromatography purification, and the mobile phase used for silica gel column chromatography purification is n-hexane:ethyl acetate=20:1~3:1.

[0017] In a second aspect, the present invention provides a bisphenol phthalimide, which adopts the following technical solution: A bisphenol phthalimide is prepared by the above-mentioned preparation method of bisphenol phthalimide.

[0018] In summary, the present invention has the following beneficial effects: The invention provides a new method for preparing bisphenol phthalimide by a one-pot method, which replaces the existing high-temperature two-step synthesis method. The invention prepares bisphenol-substituted phthalimide by a one-step oxidative coupling method through a bisphenol monomer and a halogenated or nitro-substituted phthalimide under the action of a catalyst. By selecting a suitable catalyst system, the bisphenol phthalimide can be generated in one step under mild conditions. The process operation of the invention is simple, the reaction conditions are mild, the process route is mature and stable, and it is conducive to stable industrial production. High-purity monomers are provided for downstream preparation of high-performance polyetherimide, and the invention has good industrial application prospects.

[0019] The present invention provides a method for preparing bisphenol phthalimide by coupling reaction of a bisphenol compound with a halogenated or nitro-substituted phthalimide compound. Currently, there is no report on the coupling reaction of a bisphenol compound with a halogenated or nitro-substituted phthalimide. The synthesis method of the present invention provides an effective preparation method for bisphenol phthalimide and its derivatives, breaks through the complexity and harshness of the traditional reaction route, and has obvious innovation. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the 1H-NMR spectrum of the bisphenol phthalimide prepared in Example 1 of the present invention.

[0021] Figure 2 This is a high-resolution mass spectrum of the bisphenol phthalimide prepared in Example 1 of the present invention.

[0022] Figure 3 This is the infrared spectrum of the bisphenol phthalimide prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0023] The present invention is further described in detail below with reference to the embodiments.

[0024] Embodiment 1: A method for preparing bisphenol phthalimide comprises the following steps: Under N2 protection, 300 mL of N,N-dimethylformamide was first added to the reaction bottle, followed by bisphenol A (22.83 g, 0.1 mol), N-methyl-4-nitrophthalimide (41.23 g, 2 eq), cesium carbonate (81.46 g, 2.5 eq), copper acetate catalyst (1.20 g, 0.3×2 mol%), and proline ligand (0.69 g, 0.3×2 mol%). The remaining 250 mL of N,N-dimethylformamide was added for washing, and the temperature was raised to 100°C for reaction for 24 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, and purified by silica gel column chromatography. After purification, the mixture was rotary evaporated and dried to obtain 40.4 g of white bisphthalimide solid with a yield of 74%.

[0025] Embodiment 2: Under N2 protection, 300 mL of N-methylpyrrolidone was first added to the reaction bottle, followed by bisphenol F (20.0 g, 0.1 mmol), N-ethyl-4-nitrophthalimide (41.83 g, 1.9 eq), potassium carbonate (41.46 g, 3 eq), palladium acetate (1.64 g, 0.29×2.5 mol%), triphenylphosphine ligand (1.90 g, 0.29×2.5 mol%), and the remaining 400 mL of N-methylpyrrolidone was added for washing. The temperature was raised to 120°C for reaction for 36 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, and purified by silica gel column chromatography. After purification, the mixture was rotary evaporated and dried to obtain 38.2 g of bisphthalimide solid with a yield of 70%.

[0026] Embodiment 3: Under N2 protection, 150 mL of 1,4-dioxane was first added to the reaction flask, followed by 4,4'-dihydroxybenzophenone (10.71 g, 0.05 mol), 4-bromo-N-methylphthalimide (24.0 g, 2 eq), potassium tert-butoxide (11.2 g, 2 eq), triphenylphosphine rhodium chloride (2.78 g, 0.15×2 mol%), and the remaining 200 mL of 1,4-dioxane was added for washing. The temperature was raised to 110°C and the reaction was carried out for 24 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, and purified by silica gel column chromatography. After purification, it was rotary evaporated and dried to obtain 35.1 g of a powdery solid with a yield of 66%.

[0027] Embodiment 4: Under N2 protection, 150 mL of dimethyl sulfoxide was first added to the reaction bottle, followed by 2,2-bis(4-hydroxy-3-methylphenyl)propane (12.82 g, 0.05 mol), 4-iodo-N-methylphthalimide (30.1 g, 2.1 eq), potassium phosphate (23.34 g, 2.2 eq), rhodium chloride catalyst (1.62 g, 0.155×5 mol%), tetramethylethylenediamine ligand (0.9 g, 0.155×5 mol%), and the remaining 200 mL of dimethyl sulfoxide was added for washing. The temperature was raised to 150°C for reaction for 24 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, purified by silica gel column chromatography, rotary evaporated, and dried to obtain 37.4 g of a powdery solid with a yield of 65%.

[0028] Embodiment 5: Under N2 protection, 200 mL of N,N-dimethylacetamide was first added to the reaction bottle, followed by 1,1'-bis(4-hydroxy-3-methylphenyl)cyclohexane (14.82 g, 0.05 mol), N-ethyl-4-nitrophthalimide (27.5 g, 2.5 eq), sodium fluoride (5.04 g, 2.4 eq), and the catalyst triphenylphosphine palladium chloride (1.23 g, 0.175×1 mol%). The remaining 250 mL of N,N-dimethylacetamide was added for washing, and the temperature was raised to 100°C for reaction for 24 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, and purified by silica gel column chromatography. After purification, it was rotary evaporated and dried to obtain 41.8 g of a powdery solid with a yield of 68%.

[0029] Embodiment 6: Under N2 protection, 300 mL of N-methylpyrrolidone was first added to the reaction bottle, followed by 5,5'-(1-methylethylidene)bis[(1,1'-biphenyl)-2-phenol] (19.02 g, 0.05 mmol), 4-bromo-N-methylphthalimide (21.6 g, 1.8 eq), cerium carbonate (50.63 g, 2.2 eq), and nano-copper oxide (1.64 g, 0.56×5 mol%). The remaining 200 mL of N-methylpyrrolidone was added for washing, and the temperature was raised to 100°C for reaction for 36 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, and purified by silica gel column chromatography. After purification, the mixture was rotary evaporated and dried to obtain 40.9 g of bisphthalimide solid with a yield of 59%.

[0030] Embodiment 7: Under N2 protection, 150 mL of dimethyl sulfoxide was first added to the reaction bottle, followed by 4,4'-dihydroxydiphenyl ether (10.11 g, 0.05 mol), N-butyl-4-nitrophthalimide (24.82 g, 2.0 eq), potassium hydroxide (7.86 g, 2.8 eq), palladium chloride catalyst (1.06 g, 0.15×4 mol%), triphenylphosphine ligand (1.57 g, 0.15×4 mol%), and the remaining 150 mL of dimethyl sulfoxide was added for washing. The temperature was raised to 90°C and the reaction was carried out for 48 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, and purified by silica gel column chromatography. After purification, the mixture was rotary evaporated and dried to obtain 37.4 g of a powdery solid with a yield of 65%.

[0031] Embodiment 8: Under N2 protection, 300 mL of N-methylpyrrolidone was first added to the reaction bottle, followed by bisphenol S (25.03 g, 0.1 mmol), 4-chloro-N-methylphthalimide (37.05 g, 1.9 eq), sodium tert-butoxide (38.44 g, 4 eq), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (16.98 g, 0.29×8 mol%), and the remaining 200 mL of N-methylpyrrolidone was added for rinsing. The temperature was raised to 120°C and the reaction was carried out for 36 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, and purified by silica gel column chromatography. After purification, it was rotary evaporated and dried to obtain 31.3 g of bisphthalimide solid with a yield of 55%.

[0032] Embodiment 9: Under N2 protection, 200 mL of N-methylpyrrolidone was first added to the reaction bottle, followed by 4,4'-dibenzhydryl bisphenol (17.62 g, 0.05 mmol), N-phenyl-4-nitrophthalimide (30.85 g, 2.3 eq), lithium fluoride (2.59 g, 2.0 eq), and nano cuprous iodide (2.51 g, 0.165×8 mol%). The remaining 100 mL of N-methylpyrrolidone was added for rinsing, and the temperature was raised to 150°C for reaction for 18 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, and purified by silica gel column chromatography. After purification, the mixture was rotary evaporated and dried to obtain 28.61 g of bisphthalimide solid with a yield of 72%.

[0033] Embodiment 10: Under N2 protection, 150 mL of 1,4-dioxane was first added to the reaction bottle, followed by hexafluorobisphenol A (16.81 g, 0.05 mol), 4-iodo-N-methylphthalimide (35.88 g, 2.5 eq), potassium tert-butoxide (22.4 g, 4 eq), sodium acetate catalyst (0.57 g, 0.175×4 mol%), 2,2-bipyridine ligand (2.19 g, 0.175×8 mol%), and the remaining 200 mL of 1,4-dioxane was added for washing. The temperature was raised to 110°C and the reaction was carried out for 24 h. After the reaction was completed, the mixture was filtered, concentrated under reduced pressure, dissolved in chloroform, purified by silica gel column chromatography, rotary evaporated, and dried to obtain 44.5 g of a powdery solid with a yield of 68%.

[0034] This specific embodiment is merely an explanation of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed. However, as long as they are within the scope of the claims of the present invention, they are protected by the patent law.

Claims

1. A method for preparing bisphenol phthalimide, characterized in that: The following steps are involved: Under the protection of inert gas, add solvent E to the reaction bottle, then add raw material bisphenol compound A, raw material halogenated or nitro substituted product B, alkaline compound C, catalyst D and catalyst ligand, finally add solvent E again to adjust the solid content of the reaction system to 5-40%, heat to 25-180° C., react for 8-72 hours, filter, concentrate under reduced pressure, purify, rotary evaporate and dry to obtain bisphenol phthalimide after the reaction is completed; The catalyst D is one or more of nano copper oxide, nano cuprous iodide, sodium acetate, copper acetate, palladium acetate, rhodium acetate, rhodium chloride, palladium chloride, triphenylphosphine rhodium chloride, triphenylphosphine palladium chloride, palladium carbon, dibromo[1,1'-bis(diphenylphosphino)ferrocene]palladium, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, 1,1'-bis(di-cyclohexylphosphino)ferrocenepalladium dichloride, and bis(pyridine)palladium dichloride.

2. The method for preparing bisphenol phthalimide according to claim 1, characterized in that: The bisphenol compound A is bisphenol A, bisphenol S, bisphenol F, hexafluorobisphenol A, tetrabromobisphenol A, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 4,4'-(1-phenylethyl)bisphenol, 4,4'-dibenzhydryl bisphenol, 1,1'-bis(4-hydroxy-3-methylphenyl)cyclohexane, 5,5'-(1-methylethyl)bis[(1,1'-biphenyl) )-2-phenol], 2,6-dibromo-4-[1-(3-bromo-4-hydroxyphenyl)-1-methylethyl]phenol, bisphenol fluorene, hydroquinone, resorcinol, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3,5,3',5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,7-dihydroxy-9-fluorenone or more.

3. The method for preparing bisphenol phthalimide according to claim 1, characterized in that: The halogenated or nitro-substituted compound B is N-methyl-4-nitrophthalimide, N-ethyl-4-nitrophthalimide, N-butyl-4-nitrophthalimide, N-phenyl-4-nitrophthalimide, N-methyl-3-nitrophthalimide, N-ethyl-3-nitrophthalimide, N-butyl-3-nitrophthalimide, N-phenyl-3-nitrophthalimide One or more of phthalimide, 4-chloro-N-methylphthalimide, 4-bromo-N-methylphthalimide, 4-iodo-N-methylphthalimide, 4-fluoro-N-methylphthalimide, 3-chloro-N-methylphthalimide, 3-bromo-N-methylphthalimide, 3-iodo-N-methylphthalimide, and 3-fluoro-N-methylphthalimide.

4. The method for preparing bisphenol phthalimide according to claim 1, characterized in that: The alkaline compound C is one of potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium fluoride, sodium fluoride, lithium fluoride, cesium fluoride, potassium carbonate, potassium phosphate, sodium phosphate, cesium carbonate, sodium carbonate, silver carbonate, cerium carbonate, potassium tert-butoxide, and sodium tert-butoxide.

5. The method for preparing bisphenol phthalimide according to claim 1, characterized in that: The organic solvent E is one of benzene, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 1,4-dioxane, N-methylpyrrolidone, dichloromethane and dichloroethane.

6. The method for preparing bisphenol phthalimide according to claim 1, characterized in that: The molar ratio of the bisphenol compound A to the halogenated or nitro-substituted compound B is 1:1.8-1:3.5; the molar ratio of the bisphenol compound A to the alkaline compound C is 1:0.8-1:5; and the added amount of the catalyst D is 0.1-10% of the total molar amount of the reactants.

7. The method for preparing bisphenol phthalimide according to claim 1, characterized in that: The reaction system also includes a catalyst ligand, which is one or more of triphenylphosphine, tetramethylethylenediamine, proline, 2,2-bipyridine, and 1,2-bis(diphenylphosphine)ethane, and the molar ratio of the catalyst ligand to the catalyst D is 1:1 to 3:

1.

8. The method for preparing bisphenol phthalimide according to claim 1, characterized in that: The purification specifically includes: silica gel column chromatography purification, and the mobile phase used for silica gel column chromatography purification is n-hexane:ethyl acetate=20:1~3:1.

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