CN102276563A - Bisphenol F tetracarboxylic dianhydride and preparation method thereof - Google Patents

Abstract

The present invention provides bisphenol F tetra-acid dianhydride represented by formula (I), bisphenol F tetra-acid dianhydride represented by formula (II) and bisphenol F tetra-acid dianhydride represented by formula (III). The present invention prepares three kinds of isomerized bisphenol F tetraacid dianhydrides with bisphenol F and phthalimide having the structure of formula (IV) and/or formula (V) as raw materials. The bisphenol F tetraacid dianhydride provided by the invention Diether type polyimide obtained by reacting phenol F tetraacid dianhydride with diamine has good solvent resistance and processability. The present invention uses phthalimide having the structure of formula (IV) and/or formula (V) as raw material, the raw material is simple and easy to obtain, the process flow is simple, the by-products are less, and no complicated post-treatment process can be obtained Bisphenol F tetraacid dianhydride. In addition, the method provided by the invention has low cost and high yield when preparing bisphenol F tetraacid dianhydride, and is suitable for industrial production.

Description

Bisphenol F tetraacid dianhydride and preparation method thereof

technical field

The invention belongs to the technical field of polyimide, and in particular relates to a bisphenol F tetraacid dianhydride and a preparation method thereof.

Background technique

Polyimide is a special engineering plastic with excellent electrical properties, mechanical properties, thermal stability, thermal oxidation stability, chemical stability, solvent resistance and dimensional stability. It is widely used in aviation, aerospace, electronics, In the nuclear power and automobile industries, bis-ether polyimide has become one of the research hotspots because of its good comprehensive performance.

Diether type polyimide is generally prepared by polycondensation reaction of bisether type dianhydride and diamine, and bisether type dianhydride has an important influence on the performance of bisether type polyimide. The prior art discloses a variety of bis-ether dianhydrides and preparation methods thereof for the preparation of bis-ether polyimides, such as the bisphenol A bis-ether dianhydride disclosed by GE in the 1970s, substituted with nitro Or chlorine-substituted phthalimide and bisphenol A are used as raw materials to carry out nucleophilic substitution reaction to obtain bisphenol A bisphthalimide; after hydrolyzing and dehydrating the bisphenol A biseth Obtain bis-ether type dianhydride, this dianhydride can be used as the monomer (US.Patent 3787364) of synthetic bisphenol A bis-ether type polyimide Ultem. The Changchun Institute of Applied Chemistry of the Chinese Academy of Sciences also disclosed a method of using chlorophthalimide as a raw material in the 1970s to react with bisphenol A in the presence of sodium carbonate to synthesize bis-ether dianhydrides (J.Appl.Polym . Sci. 59:923-930). Bisphenol A is widely used in the synthesis of diether polyimide, but the solvent resistance of bisphenol A diether polyimide is poor, which limits its further application.

Bisphenol F, also known as 4,4-dihydroxydiphenylmethane, methylene bisphenol or bis-(hydroxyphenyl)methane, has a molecular formula of C ₁₃ H ₁₂ O ₂ , a molecular weight of 200.24, and a CAS registration number of 620- 92-8, is an important chemical raw material. The bis-ether polyimide prepared with bisphenol F as a raw material has good solvent resistance and processability, as disclosed by Sek et al. using 4-nitrophthalonitrile as a raw material to synthesize 4,4-bisphenol The method of F dianhydride (Polymer 41: 49-56), this 4,4-bisphenol F dianhydride can be reacted with diamine to obtain bis-ether polyimide, but, this method is based on 4-nitrophthalate Formaldehyde is used as a raw material, and the cost is high, and the yield is low, so it is difficult to realize industrial production.

Contents of the invention

In view of this, the technical problem to be solved in the present invention is to provide a kind of bisphenol F tetra-acid dianhydride and preparation method thereof, the method raw material provided by the present invention is simple and easy to get, and technological process is simple, does not need complicated post-treatment process, and yield higher.

The invention provides bisphenol F tetraacid dianhydride shown in a kind of formula (I):

The present invention provides bisphenol F tetraacid dianhydride shown in a kind of formula (II):

The present invention provides bisphenol F tetraacid dianhydride shown in a kind of formula (III):

The present invention also provides a kind of preparation method of bisphenol F tetraacid dianhydride, comprises the following steps:

a) Under the action of a basic compound, bisphenol F reacts with phthalimide having a structure of formula (IV) and/or formula (V) in a polar aprotic solvent to obtain N, N-bis Substituted bisphenol F bisphthalimide:

Wherein, R ₁ is halogen or nitro, R ₂ is phenyl, substituted phenyl or alkyl containing 1 to 6 carbon atoms;

b) After the N,N-disubstituted bisphenol F bisphthalimide is sequentially hydrolyzed, acidified and dehydrated, bisphenol F tetraacid dianhydride is obtained.

Preferably, said step a) specifically includes:

a1) placing the bisphenol F and the basic compound in a mixture of a polar aprotic solvent and a water-carrying solvent, carrying water at 100°C to 200°C;

a2) Add phthalimide having a structure of formula (IV) and/or formula (V) to the reactant obtained in step a1), and obtain N, N-disubstituted bisphenol F bisphthalimide after the reaction amine.

Preferably, in the step a1), the basic compound is sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate.

Preferably, in the step a1), the polar aprotic solvent is dimethylsulfoxide, sulfolane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoryl tris amine.

Preferably, in the step a1), the water-carrying solvent is benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene or chlorinated o-xylene.

Preferably, in the step a1), the molar ratio of the bisphenol F to the phthalimide having the structure of formula (IV) and/or formula (V) is 1:2 to 1:2.5 .

Preferably, said step b) specifically includes:

b1) reflux hydrolyzing the N,N-disubstituted bisphenol F bisphthalimide in an alkaline aqueous solution;

b2) adding an acid solution to the hydrolyzate obtained in the step b1) for acidification;

b3) Dehydrating or recrystallizing the acidified product obtained in the step b2) to obtain bisphenol F tetraacid dianhydride.

Compared with the prior art, the present invention uses bisphenol F and phthalimide with formula (IV) and/or formula (V) as raw materials to prepare three kinds of isomerized bisphenol F tetraacid di Anhydride, the bis-ether polyimide obtained by reacting bisphenol F tetraacid dianhydride and diamine provided by the present invention has good solvent resistance and processability. The present invention uses phthalimide having the structure of formula (IV) and/or formula (V) as raw material, the raw material is simple and easy to obtain, the process flow is simple, the by-products are less, and no complicated post-treatment process can be obtained Bisphenol F tetraacid dianhydride. In addition, the method provided by the invention has low cost and high yield when preparing bisphenol F tetraacid dianhydride, and is suitable for industrial production.

Description of drawings

Fig. 1 is the infrared spectrogram of bisphenol F tetraacid dianhydride prepared in Example 10 of the present invention;

Fig. 2 is the proton nuclear magnetic resonance spectrogram of the bisphenol F tetraacid dianhydride prepared in Example 10 of the present invention;

Fig. 3 is the infrared spectrogram of bisphenol F tetraacid dianhydride prepared in Example 11 of the present invention;

Fig. 4 is the H NMR spectrum of bisphenol F tetra-acid dianhydride prepared in Example 11 of the present invention.

Detailed ways

The invention provides bisphenol F tetraacid dianhydride shown in a kind of formula (I):

The present invention also provides bisphenol F tetraacid dianhydride shown in a kind of formula (II):

The present invention also provides bisphenol F tetraacid dianhydride shown in a kind of formula (III):

In the present invention, the chemical name of bisphenol F tetraacid dianhydride shown in formula (I) is 4,4'-bisphenol F tetraacid dianhydride, and the chemical name of bisphenol F tetraacid dianhydride shown in formula (II) The name is 3,4'-bisphenol F tetraacid dianhydride, and the chemical name of bisphenol F tetraacid dianhydride represented by formula (III) is 3,3'-bisphenol F tetraacid dianhydride. The bisphenol F tetraacid dianhydride provided by the present invention can react with diamine to generate a bisether polyimide, which has good solvent resistance and can expand the production capacity of the bisether polyimide. scope of application.

The present invention also provides a kind of preparation method of bisphenol F tetraacid dianhydride, comprises the following steps:

a) Under the action of a basic compound, bisphenol F reacts with phthalimide having a structure of formula (IV) and/or formula (V) in a polar aprotic solvent to obtain N, N-bis Substituted bisphenol F bisphthalimide:

Wherein, R ₁ is halogen or nitro, R ₂ is phenyl, substituted phenyl or alkyl containing 1 to 6 carbon atoms;

b) After the N,N-disubstituted bisphenol F bisphthalimide is sequentially hydrolyzed, acidified and dehydrated, bisphenol F tetraacid dianhydride is obtained.

The present invention prepares bisphenol F tetraacid dianhydride with bisphenol F and phthalimide having the structure of formula (IV) and/or formula (V) as raw materials. The method raw materials provided by the invention are simple and easy to obtain, and the process The process is simple, no complicated post-treatment process is required, and the yield is high.

The present invention firstly reacts bisphenol F with phthalimide having a structure of formula (IV) and/or formula (V) in a polar aprotic solvent and under the action of a basic compound to obtain N,N- Two substituted bisphenol F bisphthalimides, specifically comprising the following steps:

a1) placing the bisphenol F and the basic compound in a polar aprotic solvent and a water-carrying solvent, carrying water at 100°C to 200°C;

a2) Add phthalimide having a structure of formula (IV) and/or formula (V) to the reactant obtained in step a1), and obtain N, N-disubstituted bisphenol F bisphthalimide after the reaction amine.

First, bisphenol F and basic compound are placed in a mixture of polar aprotic solvent and water-carrying solvent, and water is brought in at 100°C to 200°C. During the process of carrying water, bisphenol F reacts with basic compound to form phenol Salt. In the present invention, the basic compound is preferably sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, more preferably sodium hydroxide or sodium carbonate; the polar aprotic solvent is preferably dimethyl sulfoxide , sulfolane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide, more preferably dimethylsulfoxide, dimethylformamide, dimethylacetamide or N-methylpyrrolidone; the water-carrying solvent is preferably benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene or chlorinated o-xylene, more preferably benzene, toluene or xylene. The molar ratio of the bisphenol F to the basic compound is preferably 1:2 to 1:3, more preferably 1:2.2 to 1.2.8; the mass of the bisphenol F to the polar aprotic solvent The ratio is preferably 1:4 to 1:10. , more preferably 1:5 to 1:8; the mass ratio of the bisphenol F to the water-carrying solvent is preferably 1:2 to 1:5, more preferably 1:2.5 to 1:4.5.

In the present invention, water is preferably carried out in nitrogen, and the time for carrying water is preferably 4h-10h, more preferably 5h-8h. After the water-carrying is completed, the water-carrying solvent is distilled off to obtain the phenoxide.

Add the phthalimide with formula (IV) and/or formula (V) structure in described phenolate, obtain N after the reaction, N-bissubstituted bisphenol F bisphthalimide, reaction formula is as follows :

In the present invention, the phthalimide has a structure of formula (IV) and/or formula (V), that is, the phthalimide can be a compound of formula (IV), a compound of formula Compounds of the structure (V) and mixtures consisting of compounds of the structure of the formula (IV) and compounds of the structure of the formula (V). When the phthalimide is a compound of formula (IV), the final product obtained is bisphenol F tetraacid dianhydride with formula (I) structure; when the phthalimide When being the compound with formula (V) structure, the final product that obtains is the bisphenol F tetraacid dianhydride with formula (III) structure; When described phthalimide is by having formula (IV) structure When compound and have the mixture that formula (V) structure compound forms, the final product that obtains is by the bisphenol F tetraacid dianhydride with formula (I) structure, the bisphenol F tetraacid dianhydride with formula (III) structure and A mixture composed of bisphenol F tetraacid dianhydride having a structure of formula (II).

The phthalimide with formula (IV) structure and the phthalimide with formula (V) structure are isomers, wherein, _R is halogen or nitro, preferably Nitro or chloro; _R2 is phenyl, substituted phenyl or alkyl containing 1 to 6 carbon atoms, preferably methyl or phenyl.

According to the present invention, the phenoxide and the phthalimide having the structure of formula (IV) and/or formula (V) are preferably reacted in a nitrogen environment, more preferably under stirring conditions, The reaction temperature is preferably 50°C-200°C, more preferably 100°C-150°C; the reaction time is preferably 4h-10h, more preferably 5h-8h. After the reaction is completed, the reaction mixture is poured into ethanol or water, filtered, washed with ethanol and water, and dried to obtain N, N-disubstituted bisphenol F bisphthalimide.

After obtaining N, N-disubstituted bisphenol F bisphthalimide, it is hydrolyzed, acidified and dehydrated successively to obtain bisphenol F tetraacid dianhydride, which specifically includes the following steps:

b1) reflux hydrolyzing the N,N-disubstituted bisphenol F bisphthalimide in an alkaline aqueous solution;

b2) adding an acid solution to the hydrolyzate obtained in the step b1) for acidification;

b3) Dehydrating or recrystallizing the acidified product obtained in the step b2) to obtain bisphenol F tetraacid dianhydride.

The N, N-disubstituted bisphenol F bisphthalimide is added into an alkaline aqueous solution, and the condition of heating and reflux is lowered for hydrolysis to obtain bisphenol F tetracarboxylate. According to the present invention, the alkaline aqueous solution is preferably an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and the mass concentration of the alkaline aqueous solution is preferably 20%-30%, more preferably 22%-28%. The molar ratio of the N,N-disubstituted bisphenol F phthalimide to the alkali compound in the alkaline aqueous solution is preferably 1:6-1:10, more preferably 1:7-1:9. The heating and reflux time is preferably 4h-20h, more preferably 8h-15h.

After obtaining the bisphenol F tetracarboxylate, acid solution is added therein for acidification. The acid solution is preferably hydrochloric acid, and the solution is preferably acidified to a pH value of 1 to obtain bisphenol F tetracarboxylic acid.

After the bisphenol F tetracarboxylic acid is dehydrated or recrystallized, bisphenol F tetracarboxylic dianhydride is obtained. The bisphenol F tetraacid dianhydride is preferably dehydrated in a dehydration solvent, and the dehydration solvent is preferably benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene or chlorinated o-xylene, more preferably benzene, toluene or xylene. The bisphenol F is preferably recrystallized in acetic anhydride.

After bisphenol F tetraacid dianhydride is obtained, it can be reacted with diamine to obtain bis-ether polyimide. After obtaining the bis-ether polyimide, it is tested for its solvent resistance, and the results show that the bis-ether polyimide prepared from the bisphenol F tetra-acid dianhydride provided by the present invention has good solvent resistance.

The present invention uses the simple and easy-to-obtain phthalimide having the structure of formula (IV) and/or formula (V) as raw material, the process flow is simple, the by-products are less, and the bis-phthalimide can be obtained without complex post-treatment process. Phenol F tetraacid dianhydride. In addition, the method provided by the invention has low cost and high yield when preparing bisphenol F tetraacid dianhydride, and is suitable for industrial production.

In order to further illustrate the present invention, the bisphenol F tetraacid dianhydride provided by the present invention and its preparation method are described in detail below in conjunction with the examples.

The raw materials used in the following examples are purchased from the market.

Example 1

Add 20.02g (0.1mol) of bisphenol F, 8.0g (0.2mol) of sodium hydroxide, 80g of dimethyl sulfoxide and 40g of benzene into a 500mL dry round-bottomed flask, blow nitrogen into it, and reflux at 100°C with water for 4h. After distilling off the benzene, cool to room temperature; then add 39.12g (0.2mol) N-methyl-4-chlorophthalimide to it, heat up to 50°C for 10h, and cool to room temperature; The reaction mixture was slowly poured into 400 mL of water, and the resulting solid was washed with water and ethanol to obtain 41.48 g of 4,4'-(4,4'-methylenebisphenoxy)bis(N-methylphthalimide) ) with a melting point of 191°C to 193°C and a yield of 80%.

Example 2

Add 20.02g (0.1mol) of bisphenol F, 41.46g (0.3mol) of anhydrous potassium carbonate, 200g of sulfolane and 100g of toluene into a 500mL dry round-bottomed flask, pass nitrogen gas into it, reflux with water at 150°C for 10h, and distill it off Then, 48.9g (0.25mol) of N-methyl-3-chlorophthalimide was added thereto, and the temperature was raised to 200°C for 4h, and then cooled to room temperature; the obtained reaction mixture was Slowly poured into 400mL water, the obtained solid was washed with water and ethanol to obtain 46.66g 3,3'-(4,4'-methylenebisphenoxy)bis(N-methylphthalimide), the melting point It is 180°C to 182°C, and the yield is 90%.

Example 3

Add 20.02g (0.1mol) of bisphenol F, 41.46g (0.3mol) of anhydrous potassium carbonate, 120g of dimethylformamide and 60g of chlorobenzene into a 500mL dry round-bottom flask. 8h, distill off the chlorobenzene and cool to room temperature; then add 53.07g (0.22mol) N-phenyl-3-chlorophthalimide to it, heat up to 150°C for 8h, cool to room temperature ; The resulting reaction mixture is slowly poured into 400mL of water, and the solid obtained is washed with water and ethanol to obtain 54.62g3,3'-(4,4'-methylenebisphenoxy)bis(N-phenylphthaloyl imine), its melting point is 230°C-232°C, and the yield is 85%.

Example 4

Add 20.02g (0.1mol) of bisphenol F, 26.50g (0.25mol) of anhydrous sodium carbonate, 150g of dimethylacetamide and 100g of o-dichlorobenzene into a 500mL dry round-bottomed flask, blow nitrogen into it, and reflux at 200°C Take water for 6h, distill o-dichlorobenzene and cool to room temperature; then add 19.56g (0.1mol) N-methyl-3-chlorophthalimide and 19.56g (0.1mol) For N-methyl-4-chlorophthalimide, the temperature was raised to 120°C for 8 hours, and cooled to room temperature; the obtained reaction mixture was slowly poured into 400 mL of water, and the obtained solid was washed with water and ethanol to obtain 38.89 g light yellow solid, the yield is 80%. The light yellow solid was analyzed by high performance liquid chromatography, and it was 3,3'-(4,4'-methylenebisphenoxy)bis(N-methylphthalein) with a mass ratio of 27:59:14. imide), 3,4′-(4,4′-methylenebisphenoxy)bis(N-methylphthalimide) and 4,4′-(4,4′-methylene bisphenoxy)bis(N-methylphthalimide).

Example 5

Add 20.02g (0.1mol) of bisphenol F, 11.80g (0.2mol) of potassium hydroxide, 13.8g (0.1mol) of anhydrous potassium carbonate, 140g of N-methylpyrrolidone and 80g of xylene into a 500mL dry round-bottomed flask. Inject nitrogen, reflux with water at 160°C for 6 hours, distill off the xylene and cool to room temperature; then add 45.35g (0.22mol) N-methyl-3-nitrophthalimide to it, and heat up Reaction at 80°C for 4h, cooled to room temperature; the obtained reaction mixture was slowly poured into 400mL of water, and the obtained solid was washed with water and ethanol to obtain 47.7g of 3,3'-(4,4'-methylenebisphenoxy base) bis(N-methylphthalimide), the melting point is 230°C-232°C, and the yield is 95%.

Example 6

Add 20.02 g (0.1 mol) of bisphenol F, 11.80 g (0.2 mol) of potassium hydroxide, 13.8 g (0.1 mol) of anhydrous potassium carbonate, 140 g of hexamethylphosphoric triamide and 100 g of toluene into a 500 mL dry round bottom flask , feed nitrogen, reflux at 150°C with water for 5 hours, distill off the toluene and cool to room temperature; then add 59.01g (0.22mol) N-phenyl-4-nitrophthalimide to it, Raise the temperature to 100°C for 4 h, cool to room temperature; slowly pour the obtained reaction mixture into 400 mL of water, wash the obtained solid with water and ethanol to obtain 57.83 g of 4,4'-(4,4'-methylenebisphenyl Oxy)bis(N-phenylphthalimide), melting point 252°C-254°C, yield 90%.

Example 7

Add 20.02g (0.1mol) of bisphenol F, 8.0g (0.2mol) of sodium hydroxide, 13.8g (0.1mol) of anhydrous potassium carbonate, 150g of dimethylacetamide and 100g of toluene into a 500mL dry round bottom flask, Inject nitrogen, reflux with water at 140°C for 6 hours, distill off the toluene and cool to room temperature; then add 29.5g (0.11mol) N-phenyl-3-nitrophthalimide and 29.5g (0.11mol) N-phenyl-4-nitrophthalimide, heated to 80°C for 4h, cooled to room temperature; the obtained reaction mixture was slowly poured into 400mL of water, and the obtained solid was mixed with water and ethanol After washing, 46.67 g of a light yellow solid was obtained with a yield of 90%. The light yellow solid was analyzed by high performance liquid chromatography, and it was 3,3'-(4,4'-methylenebisphenoxy)bis(N-phenylphthalein) with a mass ratio of 25:55:20 imide), 3,4′-(4,4′-methylenebisphenoxy)bis(N-phenylphthalimide) and 4,4′-(4,4′-methylene bisphenoxy)bis(N-phenylphthalimide).

Example 8

Add 20.02g (0.1mol) of bisphenol F, 8.0g (0.2mol) of sodium hydroxide, 10.6g (0.1mol) of anhydrous sodium carbonate, 140g of dimethylacetamide and 80g of toluene into a 500mL dry round bottom flask, Inject nitrogen, reflux at 150°C with water for 6 hours, distill off the toluene and cool to room temperature; then add 50.41g (0.21mol) N-methyl-4-bromophthalimide to it, and heat up to React at 200°C for 4h, cool to room temperature; slowly pour the obtained reaction mixture into 400mL of water, wash the obtained solid with water and ethanol to obtain 31.11g of 4,4'-(4,4'-methylenebisphenoxy ) bis(N-methylphthalimide), with a melting point of 191° C. to 193° C. and a yield of 60%.

Example 9

Add 20.02g (0.1mol) of bisphenol F, 8.0g (0.2mol) of sodium hydroxide, 10.6g (0.1mol) of anhydrous sodium carbonate, 140g of dimethylacetamide and 80g of toluene into a 500mL dry round bottom flask, Inject nitrogen, reflux with water at 150°C for 6 hours, distill off the toluene and cool to room temperature; then add 50.41g (0.21mol) N-methyl-3-bromophthalimide to it, and heat up to React at 200°C for 4h, cool to room temperature; slowly pour the obtained reaction mixture into 400mL of water, wash the obtained solid with water and ethanol to obtain 36.30g of 3,3'-(4,4'-methylenebisphenoxy ) bis(N-methylphthalimide), with a melting point of 180° C. to 182° C. and a yield of 70%.

Example 10

51.85g of 4,4'-(4,4'-methylenebisphenoxy)bis(N-methylphthalimide) prepared in Example 1 and 400mL of 25% sodium hydroxide aqueous solution Heat to reflux for 24h, filter out solid impurities after reaction, then acidify the aqueous solution with hydrochloric acid to a pH value of 1; pour the acidified solution into a 500mL round bottom flask, add 200mL xylene, heat to reflux and separate the The water in the solution was taken out until the water was dry, and the obtained solution was filtered while it was hot. After cooling the filtrate, light yellow crystals were precipitated, and the crystals were dried to obtain 39.39 g of crystals with a melting point of 170°C to 172°C. The rate is 80%.

Carry out infrared spectrum analysis and nuclear magnetic resonance analysis to described crystal, see Fig. 1 and Fig. 2 respectively for the results, Fig. 1 is the infrared spectrogram of the bisphenol F tetraacid dianhydride prepared in Example 10 of the present invention; Fig. 2 is the infrared spectrogram of the present invention The proton nuclear magnetic resonance spectrum of the bisphenol F tetraacid dianhydride prepared in Example 10, as can be seen from Figure 1 and Figure 2, the present embodiment has prepared 4,4'-bisphenol F tetraacid with the structure of formula (I) Acid dianhydride.

Example 11

51.85g of 3,3'-(4,4'-methylenebisphenoxy)bis(N-methylphthalimide) prepared in Example 2 and 400mL of 20% potassium hydroxide aqueous solution Heat to reflux for 4h, filter out solid impurities after reaction, then acidify the aqueous solution with hydrochloric acid to a pH value of 1; pour the acidified solution into a 500mL round bottom flask, add 200mL xylene, heat to reflux and separate the The water in the solution was taken out until the water was dry, and the obtained solution was filtered while it was hot. After cooling the filtrate, light yellow crystals were precipitated. The crystals were dried to obtain 36.93 g of crystals with a melting point of 230°C to 233°C. The rate is 75%.

Carry out infrared spectrum analysis and nuclear magnetic resonance analysis to described crystal, see Fig. 3 and Fig. 4 respectively for the result, Fig. 3 is the infrared spectrogram of the bisphenol F tetraacid dianhydride prepared in Example 11 of the present invention; Fig. 4 is the infrared spectrogram of the present invention The proton nuclear magnetic resonance spectrum of the bisphenol F tetraacid dianhydride prepared in Example 11 can be seen from Figure 3 and Figure 4, the present embodiment has prepared 3,3'-bisphenol F tetraacid with the structure of formula (III) Acid dianhydride.

Example 12

51.85 g of 3,3'-(4,4'-methylenebisphenoxy)bis(N-methylphthalimide), 3, 4'-(4,4'-methylenebisphenoxy)bis(N-methylphthalimide) and 4,4'-(4,4'-methylenebisphenoxy)bis( The mixture of N-methylphthalimide) and 400mL mass concentration of 20% potassium hydroxide aqueous solution was heated to reflux for 8h, and the solid impurities were filtered out after the reaction, and then the aqueous solution was acidified to pH 1 with hydrochloric acid; the acidified Pour the final solution into a 500mL round bottom flask, add 200mL xylene, heat to reflux and separate the water in the solution until it is anhydrous, filter the obtained solution while it is hot, and precipitate the light yellow crystals after cooling the filtrate , the crystals were dried to obtain 36.93 g of crystals with a yield of 75%.

The crystals were subjected to high-performance liquid chromatography analysis, and it was a mixture of bisphenol F tetraacid dianhydrides having structures of formula (I), formula (II) and formula (III), and the mass ratio thereof was 28:52:30.

Example 13

64.26g of 3,3'-(4,4'-methylenebisphenoxy)bis(N-phenylphthalimide) prepared in Example 3 and 300mL of 20% potassium hydroxide aqueous solution Heat to reflux for 10 h, filter out solid impurities after the reaction, then acidify the aqueous solution with hydrochloric acid to a pH value of 1; filter the acidified solution, collect the solid tetraacid, dry the tetraacid and recrystallize it with acetic anhydride, Filtrate while hot, then cool the filtrate to precipitate pale yellow crystals, and dry the crystals to obtain 36.93 g of crystals with a melting point of 230°C to 233°C and a yield of 75%.

Infrared spectrum analysis and nuclear magnetic resonance analysis were carried out on the crystal, and the results proved that 3,3'-bisphenol F tetraacid dianhydride having the structure of formula (III) was prepared in this example.

Examples 14-17

The 4,4'-bisphenol F tetraacid dianhydride prepared in Example 10 was mixed with 4,4'-diaminodiphenyl ether (ODA), 1,4-bis(4-aminophenoxy)benzene (TPEQ ), m-phenylenediamine (m-PDA) and 3,3'-dimethyl-4,4'-diaminodiphenylmethane (DMMDA) were reacted to obtain bis-ether polyimide respectively.

Measure the glass transition temperature and the solubility thereof of the diether polyimide respectively, the results are shown in Table 1,

Table 1 shows the performance parameters of the diether polyimides prepared in the examples and comparative examples of the present invention.

Examples 18-21

The 3,3'-bisphenol F tetraacid dianhydride prepared in Example 11 was mixed with 4,4'-diaminodiphenyl ether (ODA), 1,4-bis(4-aminophenoxy)benzene (TPEQ ), m-phenylenediamine (m-PDA) and 3,3'-dimethyl-4,4'-diaminodiphenylmethane (DMMDA) were reacted to obtain bis-ether polyimide respectively.

Measure the glass transition temperature and the solubility thereof of the diether polyimide respectively, the results are shown in Table 1,

Table 1 shows the performance parameters of the diether polyimides prepared in the examples and comparative examples of the present invention.

Examples 22-25

The mixture of the bisphenol F tetraacid dianhydride prepared in Example 12 with the structure of formula (I), formula (II) and formula (III) was mixed with 4,4'-diaminodiphenyl ether (ODA), 1, 4-bis(4-aminophenoxy)benzene (TPEQ), m-phenylenediamine (m-PDA) and 3,3'-dimethyl-4,4'-diaminodiphenylmethane (DMMDA) were reacted , to obtain bis-ether polyimide respectively.

Measure the glass transition temperature and the solubility thereof of the diether polyimide respectively, the results are shown in Table 1,

Table 1 shows the performance parameters of the diether polyimides prepared in the examples and comparative examples of the present invention.

Comparative example 1-4

4,4'-bisphenol A tetraacid dianhydride was mixed with 4,4'-diaminodiphenyl ether (ODA), 1,4-bis(4-aminophenoxy)benzene (TPEQ), m-phenylene Amine (m-PDA) and 3,3'-dimethyl-4,4'-diaminodiphenylmethane (DMMDA) were reacted to obtain bis-ether polyimide respectively.

Measure the glass transition temperature and the solubility thereof of the diether polyimide respectively, the results are shown in Table 1,

Table 1 shows the performance parameters of the diether polyimides prepared in the examples and comparative examples of the present invention.

Comparative example 5-8

3,3'-bisphenol A tetraacid dianhydride was mixed with 4,4'-diaminodiphenyl ether (ODA), 1,4-bis(4-aminophenoxy)benzene (TPEQ), m-phenylene Amine (m-PDA) and 3,3'-dimethyl-4,4'-diaminodiphenylmethane (DMMDA) were reacted to obtain bis-ether polyimide respectively.

Measure the glass transition temperature and the solubility thereof of the diether polyimide respectively, the results are shown in Table 1,

Table 1 shows the performance parameters of the diether polyimides prepared in the examples and comparative examples of the present invention.

The performance parameter of the bis-ether type polyimide prepared by the embodiment of the present invention and comparative example of table 1

In Table 1, "++" means dissolved at room temperature, "+" means dissolved under heating conditions, "±" means partially dissolved under heating conditions, and "-" means insoluble.

It can be seen from Table 1 that the polyimide prepared by the bisphenol F tetraacid dianhydride provided by the present invention has good solvent resistance, and can broaden the application environment of the bis-ether polyimide.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. the Bisphenol F tetracarboxylic dianhydride shown in the formula (I):

2. the Bisphenol F tetracarboxylic dianhydride shown in the formula (II):

3. the Bisphenol F tetracarboxylic dianhydride shown in the formula (III):

4. the preparation method of a Bisphenol F tetracarboxylic dianhydride may further comprise the steps:

A) under the effect of basic cpd, Bisphenol F is reacted in polar aprotic solvent with the phthalic imidine with formula (IV) and/or formula V structure, obtains N, the two two phthalimides of Bisphenol F that replace of N-:

Wherein, R ₁Be halogen or nitro, R ₂For phenyl, substituted-phenyl or contain the alkyl of 1～6 carbon atom;

B), after the two phthalimides of the two replacement of N-Bisphenol F pass through hydrolysis, acidifying and dehydration successively, obtain the Bisphenol F tetracarboxylic dianhydride with described N.

5. preparation method according to claim 4 is characterized in that, described step a) specifically comprises:

A1) Bisphenol F and basic cpd are placed polar aprotic solvent and the mixed solution of being with water solvent, be with water down for 100 ℃～200 ℃;

A2) to step a1) add phthalic imidine in the reactant that obtains with formula (IV) and/or formula V structure, obtain N after the reaction, the two two phthalimides of Bisphenol F that replace of N-.

6. preparation method according to claim 5 is characterized in that, described step a1) in, described basic cpd is sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood.

7. preparation method according to claim 5 is characterized in that, described step a1) in, described polar aprotic solvent is dimethyl sulfoxide (DMSO), tetramethylene sulfone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or HMPA.

8. preparation method according to claim 5 is characterized in that, described step a1) in, described band water solvent is benzene,toluene,xylene, chlorobenzene, orthodichlorobenzene or chloro-o-xylene.

9. preparation method according to claim 5 is characterized in that, described step a1) in, described Bisphenol F and described mol ratio with phthalic imidine of formula (IV) and/or formula V structure are 1: 2～1: 2.5.

10. preparation method according to claim 4 is characterized in that, described step b) specifically comprises:

B1) with described N, the two two phthalimide back hydrolysis in alkaline aqueous solution of Bisphenol F that replace of N-;

B2) to described step b1) add acid solution in the hydrolysate that obtains and carry out acidifying;

B3) with described step b2) behind the dehydration of the acidizing product that obtains or the recrystallization, obtain the Bisphenol F tetracarboxylic dianhydride.

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