CN108148029B

CN108148029B - Preparation method of bisphenol A diether dianhydride

Info

Publication number: CN108148029B
Application number: CN201711442043.5A
Authority: CN
Inventors: 刘少华
Original assignee: Shanghai Guchuang New Chemical Materials Co ltd
Current assignee: Shanghai Guchuang New Chemical Materials Co ltd
Priority date: 2017-12-27
Filing date: 2017-12-27
Publication date: 2021-06-08
Anticipated expiration: 2037-12-27
Also published as: CN108148029A

Abstract

The invention relates to a preparation method of bisphenol A diether dianhydride, which comprises the following steps; the molar ratio of sodium hydroxide to bisphenol A is 2.1-2.3: 1, the molar ratio of 4-chlorophthalic anhydride to bisphenol A is 2-2.1: 1, the weight of a catalyst benzyltriethylammonium chloride is 15 wt% of the weight of bisphenol A, and the weight of a solvent trimethylbenzene is 8 times of the weight of bisphenol A; the preparation process comprises the following steps: adding a sodium hydroxide aqueous solution and bisphenol A into a reactor, heating, stirring and dissolving, heating to 85-90 ℃, adding trimethylbenzene and benzyltriethylammonium chloride accounting for 46 wt% of the total amount, heating, refluxing, dehydrating, stirring and reacting at 172 ℃ for 15-18 hours, cooling to 130 ℃, adding 4-chlorophthalic anhydride and benzyltriethylammonium chloride accounting for 54 wt% of the total amount, heating to 140-145 ℃, refluxing and reacting for 5-6 hours, filtering while hot, cooling the filtrate to room temperature, filtering, washing precipitates with deionized water and ethanol respectively, filtering to obtain a wet material, and drying to obtain a bisphenol A diether dianhydride product, wherein the yield is 80-85%.

Description

Preparation method of bisphenol A diether dianhydride

A technical field

The invention relates to a preparation method of bisphenol A diether dianhydride, in particular to a preparation method of bisphenol A diether dianhydride for preparing polyetherimide.

Second, background Art

The polyetherimides are prepared by reacting bisphenol A diether dianhydride with 4.4 '-diaminodiphenyl ether or 4.4' -diaminodiphenylmethane or m-phenylenediamine. The polyetherimide is thermoplastic plastic resin and has wide application, and the dosage of the polyetherimide accounts for more than 50 percent of the total polyimide dosage. Polyetherimides have the following characteristic properties: high strength and high hardness at room temperature and high temperature, long-term temperature resistance, highly stable size and electrical properties, wide chemical resistance range, mass production by melt processing using a thermoplastic processing method and molding equipment, inherent flame retardancy, and low smoke during combustion. The high-temperature-resistant material is widely applied to the high-temperature technical fields of aerospace, automobiles, computers, electrical and electronic medical treatment, packaging markets and the like. Bisphenol a diether dianhydride is an indispensable important raw material for the synthesis of polyetherimides. Therefore, the preparation of bisphenol A diether dianhydride is very important. The method for preparing bisphenol A diether dianhydride requires that: the method is simple, reliable, easy to implement and high in efficiency.

In the current industrial production method, N-methyl phthalimide is used as an initial raw material, nitrified by nitrous acid, subjected to nucleophilic substitution reaction with bisphenol A disodium salt, and subjected to exchange reaction with phthalic anhydride to be converted into bisphenol A diether dianhydride. The method has long synthesis route, low total yield, and serious environmental pollution caused by a large amount of waste acid and waste alkali generated in the production process, and the improvement of the production method is really needed.

Third, the invention

The invention provides a method for preparing bisphenol A diether dianhydride, which is environment-friendly, less in pollution, simple in process, safe, reliable, easy to implement and high in efficiency. The present inventors have made intensive studies and have proposed a complete technical proposal of a process for producing bisphenol A diether dianhydride.

A preparation method of bisphenol A diether dianhydride comprises the following steps; in the presence of a catalyst benzyltriethylammonium chloride, in a trimethylbenzene solvent, firstly, carrying out salt-forming reaction on bisphenol A and a sodium hydroxide aqueous solution to generate bisphenol A disodium salt, and then carrying out nucleophilic reaction desalting on the bisphenol A disodium salt and 4-chlorophthalic anhydride to prepare bisphenol A diether dianhydride; the feeding ratio is that the molar ratio of sodium hydroxide to bisphenol A is 2.1-2.3: 1, the molar ratio of 4-chlorophthalic anhydride to bisphenol A is 2-2.1: 1, the weight of the benzyltriethylammonium chloride catalyst is 15 wt% of the weight of bisphenol A, benzyltriethylammonium chloride accounting for 46 wt% of the total amount of the catalyst is added into a reaction system in a salt forming stage, benzyltriethylammonium chloride accounting for 54 wt% of the total amount of the catalyst is added in a nucleophilic reaction stage, and the addition amount of the trimethylbenzene solvent is 8 times of the weight of bisphenol A; the preparation process comprises the following steps: adding sodium hydroxide aqueous solution and bisphenol A into a reactor according to a ratio, heating, stirring and dissolving, when the temperature is raised to 85-90 ℃, the solution is in a transparent state, adding trimethylbenzene as a solvent and benzyltriethylammonium chloride accounting for 46 wt% of the total amount of the catalyst, heating, refluxing, dehydrating, then, keeping the temperature at 172 ℃, stirring and reacting for 15-18 hours, cooling to 130 ℃, adding 4-chlorophthalic anhydride and benzyltriethylammonium chloride accounting for 54 wt% of the total amount of the catalyst according to a ratio, heating to 140-145 ℃, refluxing and reacting for 5-6 hours, then filtering while hot, pumping the filtrate into a crystallization kettle, cooling the filtrate to room temperature, crystallizing for 12 hours, filtering, washing the obtained crystal with deionized water to obtain a wet material, filtering again, washing the obtained crystal with ethanol for 2 hours, filtering to obtain a bisphenol A diether dianhydride wet material, drying to obtain a bisphenol A diether dianhydride product, the yield is 80-85%.

The sodium hydroxide content of the sodium hydroxide aqueous solution in the invention is 30-50 wt%.

It is stated here that the catalysts suitable for use in the present invention, in addition to benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriphenylphosphonium chloride, are also suitable for use in the present invention, with benzyltriethylammonium chloride being the choice for the present invention.

The bisphenol A diether dianhydride wet material prepared according to the invention is dried to obtain the bisphenol A diether dianhydride product with the yield of 80-85%, the melting point of 185-186 ℃, the appearance of white powder and the purity of more than 99.5%.

The invention provides a method for preparing bisphenol A diether dianhydride, which is environment-friendly, less in pollution, simple in process, safe, reliable, easy to implement and high in efficiency.

Detailed description of the preferred embodiments

In order to better carry out the invention, it is specifically illustrated, but the examples are in no way intended to limit the scope of protection of the invention.

Example 1

Adding 79g (0.63mol) of 32 weight percent sodium hydroxide aqueous solution and 62.4g (0.3mol) of bisphenol A into a reactor, stirring, heating to dissolve, heating to 85 ℃ to enable the solution to be in a transparent state, then adding 510g of trimethylbenzene solvent and 4.2g of benzyltriethylammonium chloride catalyst, heating, refluxing and dehydrating, heating to 172 ℃, keeping the temperature, stirring and reacting for 15 hours, then cooling to 130 ℃, adding 108g (0.6mol) of 4-chlorophthalic anhydride and 4.86g of benzyltriethylammonium chloride catalyst, heating to 140-145 ℃, refluxing and reacting for 5 hours, then filtering while hot, pumping the filtrate into a crystallization kettle, cooling the filtrate to room temperature, crystallizing for 12 hours, filtering, washing the precipitate with deionized water, filtering to obtain a precipitate, washing with 250g of ethanol, stirring and refluxing for 2 hours, filtering to obtain 125g of wet material, drying to obtain 120g (85%) of bisphenol A diether dianhydride product, the product is white powder with a melting point of 185-186 ℃ and a purity of 99.5 percent.

Example 2

Adding 55.2g (0.69mol) of 50 weight percent sodium hydroxide aqueous solution and 62.4g (0.3mol) of bisphenol A into a reactor, stirring and heating to dissolve, heating to 85 ℃ to ensure that the solution is transparent, then adding 510g of trimethylbenzene solvent and 4.2g of benzyltriethylammonium chloride catalyst, heating and refluxing for dehydration, heating to 172 ℃, keeping the temperature and stirring for reaction for 18 hours, then cooling to 130 ℃, adding 114g (0.63mol) of 4-chlorophthalic anhydride and 4.86g of benzyltriethylammonium chloride catalyst, heating to 140-145 ℃, refluxing for reaction for 5 hours, then filtering while hot, pumping the filtrate into a crystallization kettle, cooling the filtrate to room temperature, crystallizing for 12 hours, filtering, washing the precipitate with deionized water, filtering to obtain the precipitate, washing with 250g of ethanol, stirring and refluxing for 2 hours, filtering to obtain 118g of wet material, drying to obtain 113g (80%) of bisphenol A diether dianhydride product, the product is white powder with a melting point of 185-186 ℃ and a purity of 99.5 percent.

Claims

1. A preparation method of bisphenol A diether dianhydride is characterized by comprising the following steps; in the presence of a catalyst benzyltriethylammonium chloride, in a trimethylbenzene solvent, firstly, carrying out salt-forming reaction on bisphenol A and a sodium hydroxide aqueous solution to generate bisphenol A disodium salt, and then carrying out nucleophilic reaction desalting on the bisphenol A disodium salt and 4-chlorophthalic anhydride to prepare bisphenol A diether dianhydride; the feeding ratio is that the molar ratio of sodium hydroxide to bisphenol A is 2.1-2.3: 1, the molar ratio of 4-chlorophthalic anhydride to bisphenol A is 2-2.1: 1, the weight of the benzyltriethylammonium chloride catalyst is 15 wt% of the weight of bisphenol A, benzyltriethylammonium chloride accounting for 46 wt% of the total amount of the catalyst is added into a reaction system in a salt forming stage, benzyltriethylammonium chloride accounting for 54 wt% of the total amount of the catalyst is added in a nucleophilic reaction stage, and the addition amount of the trimethylbenzene solvent is 8 times of the weight of bisphenol A; the preparation process comprises the following steps: adding sodium hydroxide aqueous solution and bisphenol A into a reactor according to a ratio, heating, stirring and dissolving, adding trimethylbenzene solvent and benzyltriethylammonium chloride accounting for 46 wt% of the total amount of the catalyst when the temperature is raised to 85-90 ℃ and the solution is in a transparent state, heating, refluxing, dehydrating, then, keeping the temperature at 172 ℃, stirring and reacting for 15-18 hours, cooling to 130 ℃, adding 4-chlorophthalic anhydride and benzyltriethylammonium chloride accounting for 54 wt% of the total catalyst according to the proportion, heating to 140-145 ℃, carrying out reflux reaction for 5-6 hours, then filtering while the solution is hot, pumping the filtrate into a crystallization kettle, cooling the filtrate to room temperature, crystallizing for 12 hours, filtering, washing the obtained precipitate with deionized water, filtering, washing the obtained precipitate with ethanol for 2 hr, filtering to obtain a bisphenol A diether dianhydride wet material, and drying to obtain a bisphenol A diether dianhydride product with the yield of 80-85%;

the sodium hydroxide content in the sodium hydroxide aqueous solution is 30-50 wt%.