CN110218173B

CN110218173B - Preparation method of bar-shaped bisphenol A type diether diphthalimide

Info

Publication number: CN110218173B
Application number: CN201910525353.6A
Authority: CN
Inventors: 屈亚青; 张鑫; 陈海波
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2019-06-18
Filing date: 2019-06-18
Publication date: 2020-11-20
Anticipated expiration: 2039-06-18
Also published as: CN110218173A

Abstract

The invention relates to a preparation method of bar-shaped bisphenol A type diether diphthalimide, which comprises the steps of (A) reacting bisphenol A with strong base in a non-polar solvent to prepare bisphenol A salt; (B) carrying out nucleophilic reaction on bisphenol A salt and phthalimide in a polar aprotic solvent; (C) the reaction liquid is separated out in hot alcohol solvent containing additive, filtered to obtain coarse filter cake of diether diphthalic imide, heated, refluxed and washed several times in alcohol solvent, filtered and dried to obtain high purity rod bisphenol A type diether diphthalic imide. The invention solves the problems that the diether diphthalimide is easy to agglomerate when being separated out and the crystal particles are small and difficult to filter in the prior production technology, obtains the rod-shaped product with good dispersion and large particles, greatly improves the filtering efficiency, has high purity of the rod-shaped diether diphthalimide and is convenient for downstream use.

Description

Preparation method of bar-shaped bisphenol A type diether diphthalimide

Technical Field

The invention relates to a preparation method of a bisphenol A type diether diphthalimide crystal, belonging to the technical field of fine chemical synthesis.

Background

Bisphenol A type diether diphthalimide is an important intermediate for synthesizing polyetherimide materials, and the structure of the bisphenol A type diether diphthalimide is as follows:

the material can be further hydrolyzed, acidified and dehydrated to prepare bisphenol A dianhydride monomer. The dianhydride and diamine are further polymerized to produce polyetherimide, which is the most important intermediate in the synthesis process of polyetherimide.

A number of documents report the preparation of diether diphthalimides (see: CN 1336364A; CN 1634904A; US4017511A, US 4247464A). The prior art is as follows: bisphenol A and alkali react to produce bisphenol A salt, and bisphenol A type diether diphthalimide is prepared through nucleophilic reaction in polar non-proton solvent, and the treating process includes cooling the reaction liquid, separating out product, filtering and acid washing with water/dilute hydrochloric acid several times to eliminate the salt.

The inventor of the present application found in practical studies that this method has a great problem: in the process of separating out the reaction liquid, product particles are easy to agglomerate, and especially when the conversion rate is low and the number of byproducts is large, the separated out products can form a large sticky object on a stirring paddle, so that the subsequent treatment is difficult. When the conversion rate is higher, the caking phenomenon is lighter, but the product particles are small, the filter is easy to block, the filter efficiency is very low, the energy consumption is high, and the product loss is large because the fine products are filtered in a leakage way. The side product is usually a unilateral product, one end of the side product is an unreacted sodium phenolate group, and the other end of the side product is a phthalimide group generated by nucleophilic reaction. In order to overcome the above technical problems, a novel process for preparing bisphenol A type diether diphthalimide crystals is required.

Disclosure of Invention

The invention aims to provide a preparation method of rod-shaped diether diphthalimide, which solves the problems of easy agglomeration, small particles, difficult filtration and large product loss in the precipitation process of a product. Meanwhile, the bisphenol A type diether diphthalimide with a rod-shaped structure also solves the problem of difficult feeding when a downstream product is applied.

In order to achieve the above purpose, the invention adopts the following technical scheme:

a preparation method of rod-shaped diether diphthalimide comprises the following steps: (A) reacting bisphenol A with strong base in a non-polar solvent to prepare bisphenol A salt; (B) carrying out nucleophilic reaction on bisphenol A salt and phthalimide in a polar aprotic solvent; (C) the reaction liquid is separated out in hot alcohol solvent containing additive, filtered to obtain coarse filter cake of diether diphthalic imide, heated, refluxed and washed several times in alcohol solvent, filtered and dried to obtain high purity rod bisphenol A type diether diphthalic imide.

Further, in the step (A), the bisphenol A salt is generated by reacting bisphenol A and strong base, and the molar ratio of the raw material bisphenol A to the strong base is 1: 2-4, preferably 1: 2-3. Preferably, the strong base is sodium hydroxide and/or potassium hydroxide; the nonpolar solvent is o-xylene and/or toluene, and the using amount of the nonpolar solvent is 2-10 times, for example 4-6 times, of the total mass of the raw material bisphenol A and the strong base. The reaction temperature is the boiling point temperature of the nonpolar solvent, the temperature is preferentially raised to 80-100 ℃ and is kept for a period of time (for example, 1-3 hours), and then the temperature is raised to the boiling point of the system for refluxing and water diversion (for example, 2-5 hours).

Further, in the step (B), the polar aprotic solvent is one or more of dimethyl sulfoxide, N '-dimethylformamide or N, N' -dimethylacetamide, and the solid content is 20-40%. The molar ratio of the raw material bisphenol A salt to the phthalimide is 1: 2-3. The reaction temperature is 100-150 ℃, preferably 110-140 ℃, and the reaction time is 3-10 hours, preferably 5-8 hours.

Further, the additives in step (C) are cationic surfactants and organic acids, and the cationic surfactants are: cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, and stearyl trimethyl ammonium chloride. The concentration in the alcohol solvent is 1 to 5 wt%, preferably 2 to 3 wt%. The organic acid is: one or more of formic acid, acetic acid and tartaric acid. The concentration in the alcohol solvent is 1-5 wt%.

The invention prepares rod-shaped crystals in a system with two additives (cationic surfactant and organic acid) acting together: the interaction of the cationic surfactant and the unilateral side product avoids the agglomeration and stickiness of the product, the organic acid provides a weak acid environment to avoid the inactivation of the cationic surfactant, and the combined action is similar to that of a dispersant. Meanwhile, in the process of crystallization, the bisphenol A type diether diphthalimide is used as impurity molecules or ions and interacts with solute molecules through electrostatic force van der Waals force or hydrogen bonds, so that the diffusion and interface mass transfer rate of the solute are influenced, and the precipitation appearance of the bisphenol A type diether diphthalimide is influenced finally. Several surfactants and organic acids mentioned in the paper have good solubility in alcohol solvents, and the precipitation of crystals can be controlled by adjusting the dosage of the two additives aiming at slight difference of systems after the reaction is finished (the amount of byproducts and the residual amount of alkali are different due to different conversion rates).

Further, the alcohol in the step (C) is methanol and/or ethanol, and the volume ratio of the alcohol solvent to the reaction solution during precipitation is 1-5: 1, preferably 2-3: 1. The temperature of the alcohol is 50-78 ℃ during precipitation, and preferably 60-70 ℃. The temperature of the reaction solution is 20-50 ℃. Preferably, the precipitate is precipitated under the stirring condition, and the rotating speed of the stirring paddle is 1000-2000 rpm, preferably 1800-2000 rpm. The adding speed of the reaction liquid to the alcohol is 10-20 mL/min, and after the addition is finished, the reaction liquid is continuously stirred for 10-30 min and then filtered.

Further, in the step (C), when the filter cake is heated, refluxed and washed in the alcohol solvent, the solid content is 10-40%, preferably 10-20%, the refluxing time is 1-5 hours, preferably 2-3 hours, and the washing times are 1-5 times, preferably 3-4 times.

Further, the raw material phthalimide has the following structure:

wherein R: c1-8 alkyl or C6-13 aryl;

X：-F，Cl，Br，NO₂for example selected from 3-F, Cl, Br, NO₂And 4-F, Cl, Br, NO₂。

Further, the structural formula of the prepared diether diphthalimide is as follows:

wherein R: c1-8 alkyl or C6-13 aryl;

further, the rod-like diether diphthalimide produced has an average particle size of 1 to 50 μm, preferably 10 to 30 μm.

The invention has the beneficial effects that:

1. solves the problems that the bisphenol A type diether diphthalimide is easy to agglomerate and agglomerate when being separated out, has small particles, is easy to block during filtration and has large product loss, and the product purity is high.

2. The rod-shaped product forms a filter cake with low moisture content and low VOC.

3. The rod-shaped product is beneficial to downstream use.

Drawings

FIG. 1 shows bisphenol A type diether diphthalimide prepared in example 1¹H NMR chart.

FIG. 2 shows bisphenol A type diether diphthalimide prepared in example 1¹³C NMR chart.

FIG. 3 is a 3D microscopic view of bisphenol A type diether diphthalimide particles prepared in example 1.

FIG. 4 shows the LC test results of bisphenol A type diether diphthalimide prepared in example 1.

FIG. 5 is a 3D microscopic view of bisphenol A type diether diphthalimide prepared in comparative example 1.

Detailed Description

The present invention is further illustrated by the following examples, which are provided only for the purpose of illustration and are not intended to limit the scope of the present invention.

The structure of the product was determined by NMR: DMSO as a solvent, using a Bruker Avance III 400MHz NMR spectrometer¹H NMR,¹³And C NMR characterization. The sample purity was measured by Shimadzu liquid chromatograph with THF as mobile phase, column temperature 40 deg.C, and sample injection 1 μ L for 10.0 min. The crystal morphology of the product was obtained by microscope photography of the Schott VHX 60003D, and the average size was obtained from counting more than 50 particles.

Example 1

150mL of o-xylene is added into a 500mL three-neck flask, stirring is started, nitrogen is introduced, then bisphenol A (22.8g, 0.1mol) and sodium hydroxide (8.8g, 0.22mol) are sequentially added, heating is started, the temperature of the system is raised to 100 ℃, heat preservation is continued for 2h, then the temperature is raised to the system reflux (about 143 ℃), water is divided for 2h until no water drops fall in a water separator, the o-xylene solvent is continuously heated and evaporated, nitrogen is continuously introduced to blow the water to powder after the heating is stopped, N-methyl-4-nitrophthalimide (4-NPI, 41.2g, 0.2mol) is added after the temperature is reduced to normal temperature, DMAC is 140mL, the temperature is raised to 150 ℃, the reaction is carried out for 3h, and then the reaction is cooled to. About 180mL of the reaction solution was slowly poured into 70 ℃ ethanol (540mL) to which cetyltrimethylammonium chloride (3 wt%) and formic acid (2 wt%) were added over 10min to precipitate, the stirring paddle rotated at 2000rpm, the stirring was continued for 10min, and the reaction solution was filtered. Adding the filter cake into a flask, adding 300mL of ethanol, stirring, heating to 78 ℃, refluxing for 2h, filtering, repeatedly adding ethanol, refluxing and washing for 3 times, collecting 70.7g of wet filter cake, and drying to obtain the rodlike diether diphthalimide (the average size of which is 17 mu m)¹The H NMR spectrum is shown in figure 1,¹³the C NMR spectrum is shown in FIG. 2, and the 3D microscope picture is shown in FIG. 3), and the total amount is 51.2 g. Calculated as moisture content 27.6%, yield 93.8%, purity 99.87% (fig. 4, LC).

Example 2

Adding 150mL of toluene into a 500mL three-neck flask, starting stirring, introducing nitrogen, then sequentially adding bisphenol A (22.8g, 0.1mol) and potassium hydroxide (12.3g, 0.22mol), starting heating, continuing to keep the temperature for 2h after the system temperature rises to 100 ℃, then heating to reflux (about 110 ℃), dividing water for 2h until no water drops fall in a water separator, continuing to heat and evaporate the toluene solvent, stopping heating, continuing to introduce nitrogen to blow dry to form powder, cooling to normal temperature, adding N-methyl-4-nitrophthalimide (4-NPI, 41.2g, 0.2mol), 140mL of DMF, heating to 140 ℃, reacting for 5h, and then cooling to 40 ℃. About 180mL of the reaction solution was poured into 540mL of methanol at 60 ℃ within 15min (the concentration of the added octadecyl trimethyl ammonium chloride was 2 wt%, and the acetic acid was 3 wt%), and the mixture was precipitated, stirred for 20min, and filtered. Adding the filter cake into a flask, adding 300mL of methanol, stirring, heating to 64 ℃ and refluxing for 3h, filtering, repeatedly adding the filtered filter cake into the methanol, refluxing and washing for 4 times, collecting the filter cake, and drying to obtain 49.8g of rodlike diether diphthalimide with the average size of 22 mu m, wherein the yield is 91.2 percent, and the purity is 99.92 percent. (the test method is the same as in example 1)

Example 3

Adding 300mL of toluene into a 1000mL three-neck flask, starting stirring, introducing nitrogen, then sequentially adding bisphenol A (45.6g, 0.2mol) and potassium hydroxide (24.6g, 0.44mol), starting heating, continuing to keep the temperature for 2h after the temperature of the system rises to 100 ℃, then heating to reflux (about 110 ℃), dividing water for 4h until no water drops fall in a water separator, continuing to heat and evaporate the toluene solvent, stopping heating, continuing to introduce nitrogen to blow the water to form powder, cooling to normal temperature, adding 280mL of N-methyl-4-bromophthalimide (96.0g, 0.4mol, TCI reagent) DMSO, heating to 150 ℃, reacting for 5h, and then cooling to 40 ℃. About 360mL of the reaction solution was poured into 1000mL of methanol at 60 ℃ within 20min (the concentration of cetyltrimethylammonium bromide was 5 wt%, and tartaric acid was 3 wt%) to precipitate, and the mixture was stirred for 20min and filtered. Adding the filter cake into a flask, adding 600mL of methanol, stirring, heating to 64 ℃ for refluxing for 4h, filtering, repeatedly adding the filtered filter cake into the methanol, refluxing and washing for 4 times, collecting the filter cake, and drying to obtain the rodlike diether diphthalimide with the average size of 28 mu m, wherein the total amount of the rodlike diether diphthalimide is 100.8g, the yield is 92.3%, and the purity is 99.90%. (the test method is the same as in example 1)

Comparative example 1

150mL of o-xylene is added into a 500mL three-neck flask, stirring is started, nitrogen is introduced, then bisphenol A (22.8g, 0.1mol) and sodium hydroxide (8.8g, 0.22mol) are added in sequence, heating is started, the temperature of the system is raised to 100 ℃, then heat preservation is continued for 2 hours, then heating to the reflux of the system (about 143 ℃), dividing water for 2h until no water drop falls in the water separator, continuing heating to evaporate the o-xylene solvent to dryness, continuing introducing nitrogen to blow the o-xylene solvent to powder after heating is stopped, cooling to normal temperature, adding N-methyl-4-nitrophthalimide (4-NPI, 41.2g, 0.2mol) and 140mL of DMAC, heating to 150 ℃, reacting for 3h, then cooling to normal temperature, pouring into 540mL of ethanol for precipitation, filtering, collecting filter cake ethanol, refluxing and washing for 3 times (300mL multiplied by 3), drying to obtain 46.3g of product, wherein the yield is 84.8%, and the appearance of the product is shown in figure 5.

Claims

1. A preparation method of rod-shaped diether diphthalimide comprises the following steps:

(A) reacting bisphenol A with strong base in a non-polar solvent to prepare bisphenol A salt;

(B) carrying out nucleophilic reaction on bisphenol A salt and phthalimide in a polar aprotic solvent;

(C) precipitating the reaction solution obtained in the step (B) in a hot alcohol solvent containing an additive, filtering to obtain a filter cake of a crude diether diphthalic imide product, heating, refluxing and washing the filter cake in the alcohol solvent, filtering and drying to obtain the rodlike bisphenol A type diether diphthalic imide;

wherein, the additives in the step (C) are cationic surfactant and organic acid;

the cationic surfactant in the step (C) is: one or more of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride; the organic acid is: one or more of formic acid, acetic acid and tartaric acid;

the addition amount of the cationic surfactant in the alcohol is 1-5 wt%; the addition amount of the organic acid is 1-5 wt%;

the raw material phthalimide has the following structure:

wherein R: c1-8 alkyl or C6-13 aryl;

X：-F，Cl，Br，NO₂；

the structural formula of the prepared diether diphthalimide is as follows:

wherein R: c1-8 alkyl or C6-13 aryl.

2. The preparation method according to claim 1, wherein in the step (A), the molar ratio of the raw material bisphenol A to the strong base is 1: 2-4.

3. The preparation method according to claim 2, wherein in the step (A), the molar ratio of the raw material bisphenol A to the strong base is 1: 2-3.

4. The production method according to claim 2, wherein the strong base is sodium hydroxide and/or potassium hydroxide.

5. The production method according to claim 2, wherein the solvent is o-xylene and/or toluene, and the amount is 2 to 10 times of the total mass of the raw material bisphenol A and the strong base.

6. The preparation method according to claim 5, wherein the amount of the solvent is 4 to 6 times of the total mass of the raw material bisphenol A and the strong base.

7. The production method according to claim 1, wherein the reaction temperature in the step (A) is a boiling temperature of the solvent.

8. The preparation method according to claim 7, wherein the reaction temperature in the step (A) is firstly increased to 80-100 ℃ and is kept for 1-3 h, and then the temperature is increased to the boiling point of the system, and the reflux water separation is carried out for 2-5 h.

9. The preparation method according to claim 1, wherein the polar aprotic solvent of step (B) is one or more of dimethylsulfoxide, N '-dimethylformamide or N, N' -dimethylacetamide, and has a solid content of 20-40%.

10. The method according to claim 9, wherein the molar ratio of the bisphenol A salt to the phthalimide is 1:2 to 3, the reaction temperature is 100 to 150 ℃, and the reaction time is 3 to 10 hours.

11. The method according to claim 10, wherein the reaction temperature is 110 to 140 ℃ and the reaction time is 5 to 8 hours.

12. The method according to claim 1, wherein the cationic surfactant is added to the alcohol in an amount of 2 to 3 wt%.

13. The production method according to claim 1, wherein the alcohol in the step (C) is methanol and/or ethanol, and the volume ratio of the alcohol solvent to the reaction solution at the time of precipitation is 1-5: 1.

14. The production method according to claim 13, wherein the volume ratio of the alcohol solvent to the reaction solution at the time of precipitation is 2 to 3: 1.

15. The production method according to claim 14, wherein the temperature of the alcohol at the time of precipitation is 50 to 78 ℃ and the temperature of the reaction solution is 20 to 50 ℃.

16. The production method according to claim 15, wherein the temperature of the alcohol at the time of precipitation is 60 to 70 ℃.

17. The process according to claim 16, wherein the precipitation is carried out under stirring conditions, the rotation speed of the stirrer is 1000 to 2000rpm, the addition rate of the reaction solution to the alcohol is 10 to 20mL/min, and the reaction solution is stirred for 10 to 30min and then filtered after the addition.

18. The preparation method according to claim 17, wherein the rotation speed of the stirring paddle is 1800-2000 rpm.

19. The production process according to any one of claims 1 to 11, wherein the solid content in the step (C) is 10 to 40% when the cake is washed by heating under reflux in an alcohol solvent, the reflux time is 1 to 5 hours, and the number of washing times is 1 to 5.

20. The preparation method according to claim 19, wherein the solid content of the filter cake in the step (C) is 10-20% when the filter cake is heated, refluxed and washed in the alcohol solvent, the refluxing time is 2-3 hours, and the washing times are 3-4 times.

21. The production method according to claim 1, wherein X: selected from 3-F, Cl, Br, NO₂Or 4-F, Cl, Br, NO₂。

22. The method according to any one of claims 1 to 11, wherein the rod-shaped diether diphthalimide is produced with an average particle size of 1 to 50 μm in length.

23. The method according to claim 22, wherein the rod-shaped diether diphthalimide has an average particle size of 10 to 30 μm in length.