A phosphorus-containing polyimide material and a method for preparing the same

Abstract

The present application relates to a kind of phosphorus-containing polyimide material and its preparation method, disclose the phosphorus-containing diamine and acid anhydride as substrate, under the catalysis of benzoic acid condition, according to the molar ratio 1:1:0.01-0.03 is reacted in methyl phenol and obtained polyimide material.This synthetic route raw material is easy to obtain, simple operation, reaction condition is simple, in order to its can play a role in the field of high polymer material, aerospace etc.And provide reference significance.

Description

Technical Field

[0001] This invention belongs to the fields of polymer materials and organic synthesis technology, and specifically relates to a phosphorus-containing polyimide material and its preparation method. Background Technology

[0002] Polyimide film is a high-performance, high-temperature resistant, and high-strength polymer film material with excellent physical, chemical, and mechanical properties. Due to its wide application in electronics, aerospace, optics, and medical fields, polyimide film has become a current research hotspot. However, there are currently few methods for synthesizing polyimide materials using novel phosphorus-containing diamine monomers. Therefore, developing a new phosphorus-containing diamine monomer is of great significance for the synthesis of novel polyimide polymers. This invention synthesizes a phosphorus-containing diamine monomer through a simple three-step reaction, and then polymerizes it with different acid anhydrides to obtain a class of polyimide polymers. This synthetic method uses readily available raw materials, is simple to operate, and has concise reaction conditions, possessing good practical and socio-economic value, and is expected to provide a reference for materials, transportation, and aerospace fields. Summary of the Invention

[0003] The purpose of this invention is to prepare a novel phosphorus-containing diamine monomer that reacts with different acid anhydrides to prepare polyimide polymers, and to provide a series of phosphorus-containing polyimide polymer synthesis methods with simple and efficient reaction conditions and convenient operation.

[0004] The technical solution of this invention is as follows: using 4a as raw material, a class of polyimide polymers are generated by polymerization reactions with different acid anhydrides. The reaction route is as follows: 1.

[0006]

[0007] (1) The solvent used is selected from phosphoric acid, toluenesulfonic acid, and concentrated sulfuric acid, preferably concentrated sulfuric acid;

[0008] (2) The reagent used was selected from concentrated nitric acid;

[0009] (3) The temperature used is selected from -5℃ to 40℃, preferably room temperature;

[0010] (4) The molar mass ratio of each substance in the reaction is selected from: 4a: concentrated nitric acid = 1:2-4, preferably 1:3. 2.

[0012]

[0013] (1) The organic solvent used is selected from dichloromethane, ethanol, ethyl acetate, dioxane, tetrahydrofuran, DMA, and DMF, with ethanol being preferred;

[0014] (2) The reagents used were selected from stannous chloride and concentrated hydrochloric acid;

[0015] (3) The temperature used is selected from 0°C to room temperature, preferably room temperature;

[0016] (4) The molar mass ratio of each substance in the reaction is selected from: 5a: stannous chloride = 1:13-18, preferably 1:16. 3.

[0018]

[0019] (1) The polar solvent used is selected from m-cresol, DMA, DMF, NMP, preferably m-cresol;

[0020] (2) The anhydrides used are selected from 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, hexafluoro dianhydride, 4,4'-oxobisphthalic acid anhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, DMCBDA, pyromellitic dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, and 2,3,3',4'-diphenyl ethertetracarboxylic acid dianhydride;

[0021] (3) The temperature used is selected from 80℃ and 180℃;

[0022] (4) The catalyst used is selected from benzoic acid;

[0023] (5) The molar mass ratio of each substance in the reaction is selected from: 6a: acid anhydride: benzoic acid = 1:1:0.01-0.03, preferably 1:1:0.01. Attached image description:

[0024] 1. Figure 1 The reaction formula for the preparation of compound 5a;

[0025] 2. Figure 2 The reaction formula for the preparation of compound 6a;

[0026] 3. Figure 3 The reaction formula for the preparation of polyimide polymers;

[0027] 4. Figure 4 The reaction formula for the preparation of compound 7aa;

[0028] 5. Figure 5 The reaction formula for the preparation of compound 7ab;

[0029] 6. Figure 6 The reaction formula for the preparation of compound 7ac;

[0030] 7. Figure 7 The reaction formula for the preparation of compound 7ad;

[0031] 8. Figure 8 The reaction formula for the preparation of compound 7ae;

[0032] 9. Figure 9 The reaction formula for the preparation of compound 7af;

[0033] 10. Figure 10 The reaction formula for the preparation of compound 7ah;

[0034] 11. Figure 11 The reaction formula for the preparation of compound 7ai;

[0035] 12. Figure 12 The reaction formula for the preparation of compound 7aj;

[0036] 13. Figure 13 The reaction formula for the preparation of compound 7ak;

[0037] 14. Figure 14 The reaction formula for the preparation of compound 7am;

[0038] 15. Figure 15 The reaction formula for the preparation of compound 7an is shown below. Detailed Implementation

[0039] The present invention will be further described below through specific embodiments, but it should not be construed as limiting the scope of the above-mentioned subject matter of the present invention to the following embodiments. All technologies implemented based on the above content of the present invention fall within the scope of the present invention.

[0040] Implementation Case 1

[0041]

[0042] Compound 4a (1 mmol, 1 equiv.) was dissolved in concentrated sulfuric acid at room temperature by stirring. A pre-prepared mixed nitric acid and sulfuric acid solution was then added dropwise while stirring. After the reaction was complete, the reaction system was hydrolyzed under ice, extracted with chloroform, concentrated, and purified by column chromatography (eluents: petroleum ether and ethyl acetate) to obtain 5a.

[0043] The product testing data is as follows:

[0044] 1 H NMR (400MHz, CDCl3) δ8.74–8.57(m,2H),8.55–8.42(m,2H),7.68–7.55(m,5H),7.55–7.47(m,2H); 13C NMR (100MHz, CDCl3) δ158.16,158.13,144.45,144.34,133.35,133.32,131.58,131.51,1 31.46,130.32,129.37,129.28,129.23,127.97,127.89,120.25,120.18,116.82,115.82.

[0045]

[0046] At room temperature, 5a (1 mmol, 1 equiv.) and stannous chloride (16 mmol, 16 equiv.) were added to ethanol and stirred. After the reaction was complete, the pH was adjusted to alkaline with sodium hydroxide solution, the reaction system was extracted multiple times with dichloromethane, concentrated, and purified by column chromatography (eluent: dichloromethane and methanol) to obtain 6a.

[0047] The product testing data is as follows:

[0048] 1 H NMR (400MHz, CDCl3) δ7.61 (ddt, J=13.3, 6.8, 1.6Hz, 2H), 7.42 (dq, J=5.0, 1.8Hz, 1H), 7.38 (d dt,J=6.9,5.3,2.4Hz,2H),7.11(dd,J=8.8,6.4Hz,2H),6.96–6.86(m,4H),3.97–3.46(m,4H); 13 C NMR (100MHz, CDCl3) δ142.19,131.50,131.39,128.46,128.33,121.90,121.88,119.14,119.06,114.50,114.44.

[0049]

[0050] At room temperature, under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride 7a (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution by stirring at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was completed, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7aa.

[0051] The product testing data is as follows:

[0052] 1H NMR (400MHz, DMSO) δ8.01–7.86 (m, 6H), 7.56 (dt, J = 48.7, 7.5Hz, 11H).

[0053] Implementation Case 2

[0054] The raw materials were 6a and dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride 7b. The synthesis method of 6a is the same as that shown in Example 1.

[0055]

[0056] At room temperature, under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride 7b (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution by stirring at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was complete, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7ab.

[0057] The product testing data is as follows:

[0058] 1 H NMR (400MHz, DMSO) δ8.05–7.21(m,11H),3.22–3.06(m,2H),2.92(s,2H),2.25–1.69(m,6H),1.55(s,4H),1.24(s,4H).

[0059] Implementation Case 3

[0060] The raw materials were 6a and 1,2,3,4-cyclobutanediol dianhydride 7c. The synthesis method of 6a is the same as that shown in Example 1.

[0061]

[0062] At room temperature and under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), 1,2,3,4-cyclobutanetetracarboxylic dianhydride 7c (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution at 80 °C, the temperature was increased to 180 °C for reaction. After the reaction was complete, the reaction mixture was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7ac.

[0063] The product testing data is as follows:

[0064] 1 H NMR (400MHz, DMSO) δ8.17–7.33(m,11H),3.78–3.53(m,4H).

[0065] Implementation Case 4

[0066] The raw materials were 6a and 1,2,4,5-cyclohexanetetracarboxylic dianhydride 7d. The synthesis method of 6a is the same as that shown in Example 1.

[0067]

[0068] At room temperature and under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), 1,2,4,5-cyclohexanetetracarboxylic dianhydride 7d (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was complete, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7ad.

[0069] The product testing data is as follows:

[0070] 1 H NMR (400MHz, DMSO) δ7.86–7.19 (m, 11H), 3.15 (s, 4H), 2.05 (d, J = 134.0Hz, 4H).

[0071] Implementation Case 5

[0072] The raw materials are 6a and hexafluorodianhydride 7e. The synthesis method of 6a is the same as that shown in Example 1.

[0073]

[0074] At room temperature and under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), hexafluorodianhydride 7e (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution by stirring at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was complete, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7ae.

[0075] The product testing data is as follows:

[0076] 1H NMR (400MHz, DMSO) δ8.16 (d, J = 8.0Hz, 2H), 7.99–7.87 (m, 2H), 7.86–7.49 (m, 13H).

[0077] Implementation Case Six

[0078] The raw materials were 6a and 4,4'-oxophthalic anhydride 7f. The synthesis method of 6a is the same as that shown in Example 1.

[0079]

[0080] At room temperature, under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), 4,4'-oxophthalic anhydride 7f (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was complete, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7af.

[0081] The product testing data is as follows:

[0082] 1 H NMR (400MHz, DMSO) δ8.04 (d, J = 7.6Hz, 2H), 7.88–7.69 (m, 6H), 7.63–7.49 (m, 9H).

[0083] Implementation Case Seven

[0084] The raw materials were 6a and 3,3',4,4'-benzophenone tetracarboxylic dianhydride 7h. The synthesis method of 6a is the same as that shown in Example 1.

[0085]

[0086] At room temperature and under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), 3,3',4,4'-benzophenone tetracarboxylic dianhydride 7h (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was complete, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7ah.

[0087] The product testing data is as follows:

[0088] 1H NMR (400MHz, DMSO) δ8.27–7.94(m,6H),7.93–7.47(m,11H).

[0089] Implementation Case 8

[0090] The starting materials were 6a and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride 7i. The synthesis method of 6a was the same as that shown in Example 1.

[0091]

[0092] At room temperature, under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride 7i (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution by stirring at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was completed, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7ai.

[0093] The product testing data is as follows:

[0094] 1 H NMR (400MHz, DMSO) δ 8.14–7.29 (m, 11H), 3.76 (d, J = 59.7Hz, 4H), 2.14 (d, J = 118.7Hz, 2H).

[0095] Implementation Case Nine

[0096] 6a and DMCBDA 7j were used as raw materials. The synthesis method of 6a is the same as that shown in Example 1.

[0097]

[0098] At room temperature and under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), DMCBDA 7j (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution at 80 °C, the temperature was increased to 180 °C for reaction. After the reaction was complete, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7aj.

[0099] The product testing data is as follows:

[0100] 1H NMR (400MHz, DMSO) δ8.15–7.30 (m, 11H), 3.62 (dd, J = 9.9, 5.0Hz, 2H), 1.49–

[0101] 1.10(m,6H).

[0102] Implementation Case 10

[0103] The raw materials were 6a and pyromellitic dianhydride 7k. The synthesis method of 6a is the same as that shown in Example 1.

[0104]

[0105] At room temperature, under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), pyromellitic dianhydride 7k (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution by stirring at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was complete, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7ak.

[0106] The product testing data is as follows:

[0107] 1 H NMR (400MHz, DMSO) δ8.34 (d, J = 8.0Hz, 2H), 7.99–7.44 (m, 11H).

[0108] Implementation Case Eleven

[0109] The raw materials were 6a and 2,3,3',4'-biphenyltetracarboxylic dianhydride 7m. The synthesis method of 6a is the same as that shown in Example 1.

[0110]

[0111] At room temperature and under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), 2,3,3',4'-biphenyltetracarboxylic dianhydride 7m (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was complete, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7am.

[0112] Product testing data:

[0113] 1H NMR (400MHz, DMSO) δ8.27–7.99(m,6H),7.64–7.39(m,11H).

[0114] Implementation Case Twelve

[0115] The raw materials were 6a and 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride 7n. The synthesis method of 6a is the same as that shown in Example 1.

[0116]

[0117] At room temperature, under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride 7n (0.3 mmol, 1 equiv.), and benzoic acid catalyst (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After dissolution by stirring at 80 °C, the temperature was raised to 180 °C for reaction. After the reaction was completed, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain the polyimide polymer 7an.

[0118] Product testing data:

[0119] 1 H NMR (400MHz, DMSO) δ7.94 (d, J = 8.3 Hz, 2H), 7.90–7.76 (m, 4H), 7.71 (q, J = 5.9 Hz, 2H), 7.63–7.46 (m, 8H), 7.44 (s, 1H).

Claims

1. A phosphorus-containing polyimide material, characterized in that, The polyimide material is obtained by reacting phosphorus-containing diamine and acid anhydride in methylphenol at a molar ratio of 1:1:0.01-0.03 under benzoic acid catalysis. The general structural formula of the polyimide is shown below:

2. The phosphorus-containing polyimide material as described in claim 1, characterized in that, The acid anhydride is one or more of the following: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, hexafluorodianhydride, 4,4'-oxobisphthalic acid anhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, DMCBDA, pyromellitic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, and 2,3,3',4'-diphenyl ethertetracarboxylic acid dianhydride.

3. The phosphorus-containing polyimide material as described in claim 1, characterized in that, The phosphorus-containing diamine 6a is generated by the reduction of phosphorus-containing dinitro compound 5a under stannous chloride and concentrated hydrochloric acid conditions. The structural formula of the reaction is shown below:

4. The phosphorus-containing polyimide material as described in claim 3, characterized in that, The phosphorus-containing dinitro compound 5a is generated by reacting 4a with concentrated sulfuric acid and concentrated nitric acid at room temperature. The structural formula of the reaction is shown below:

5. The method for preparing a phosphorus-containing polyimide material as described in claim 4, characterized in that, Includes the following steps: Preparation of S1 and 5a: At room temperature, known compound 4a was added to concentrated sulfuric acid and stirred. A pre-prepared nitric acid-sulfuric acid mixed solution was added dropwise and stirred to react. After the reaction was completed, the reaction system was hydrolyzed on ice, extracted with chloroform, concentrated, and purified by column chromatography with petroleum ether and ethyl acetate as eluents to obtain 5a. Preparation of S2 and 6a: At room temperature, 5a and stannous chloride were added to ethanol and stirred to react. After the reaction was completed, the pH value was adjusted to alkaline with sodium hydroxide solution. The reaction system was extracted with dichloromethane multiple times, concentrated, and purified and separated by column chromatography with dichloromethane and methanol as eluents to obtain 6a. S3. Preparation of phosphorus-containing polyimide: In an argon atmosphere at room temperature, 6a, acid anhydride, and catalyst benzoic acid were added to m-cresol and stirred. After dissolving at 80°C, the temperature was raised to 180°C for reaction. After the reaction was completed, the reaction system was poured into ethanol, filtered, and the solid was washed three times with ethanol and dried under vacuum to obtain phosphorus-containing polyimide.

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