Phosphorus-containing polyimide material and preparation method thereof

Abstract

The invention relates to a phosphorus-containing polyimide material and a preparation method thereof, and discloses a polyimide material which is obtained by taking phosphorus-containing diamine and acid anhydride as substrates and reacting in methylphenol according to a molar ratio of 1: 1: (0.01-0.03) under the catalytic condition of benzoic acid. The synthetic route has the advantages of easily available raw materials, simple operation and concise reaction conditions, and is expected to play a role in the fields of high polymer materials, aerospace and the like and provide reference significance.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials and organic synthesis technology, and specifically relates to a phosphorus-containing polyimide material and a preparation method thereof. Background Art

[0002] Polyimide film is a high-performance, high-temperature resistant, 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 hot topic in current research. However, there are few methods for using new phosphorus-containing diamine monomers to synthesize polyimide materials. Therefore, the development of a new phosphorus-containing diamine monomer is of great significance for the synthesis of new polyimide polymers. The present invention synthesizes a phosphorus-containing diamine monomer through a simple three-step reaction, and polymerizes it with different acid anhydrides to obtain a class of polyimide polymers. The synthetic method has easy-to-obtain raw materials, simple operation, simple reaction conditions, good practical value and socio-economic value, and is expected to provide reference significance in the fields of materials, transportation, aerospace and the like. Summary of the invention

[0003] The purpose of the present invention is to prepare a novel phosphorus-containing diamine monomer to react with different acid anhydrides to prepare a polyimide polymer, and to provide a method for synthesizing a series of phosphorus-containing polyimide polymers with simple and efficient reaction conditions and convenient operation.

[0004] The technical solution of the present invention is: 4a is synthesized as a raw material, and different acid anhydrides are used for polymerization to generate a type of polyimide polymer, and 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 is selected from concentrated nitric acid;

[0009] (3) The temperature used is selected from -5°C to 40°C, 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, DMF, preferably ethanol;

[0014] (2) The reagent used is 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 acid anhydride used is selected from 3,3',4,4'-biphenyltetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hexafluorodianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, DMCBDA, pyromellitic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride;

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

[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: anhydride: benzoic acid = 1:1:0.01-0.03, preferably 1:1:0.01. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0026] 3. Figure 3 is the reaction formula for preparing polyimide polymer;

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

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

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

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

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

[0032] 9. Fig. 9 is the preparation reaction formula of compound 7af;

[0033] 10. Fig.10 is the preparation reaction formula of compound 7ah;

[0034] 11. Fig.11 is the preparation reaction formula of compound 7ai;

[0035] 12. Fig.12 is the preparation reaction formula of compound 7aj;

[0036] 13. Fig.13 is the preparation reaction formula of compound 7ak;

[0037] 14. Fig.14 is the preparation reaction formula of compound 7am;

[0038] 15. Fig.15 This is the preparation reaction formula of compound 7an. DETAILED DESCRIPTION

[0039] The present invention is further described below through specific embodiments, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following embodiments, and all technologies implemented based on the above content of the present invention belong to the scope of the present invention.

[0040] Implementation Case 1

[0041]

[0042] At room temperature, the known compound 4a (1 mmol, 1 equiv.) was added to concentrated sulfuric acid and stirred to dissolve, and a pre-prepared nitric acid and sulfuric acid mixed acid solution was added dropwise and stirred to react. After the reaction, the reaction system was hydrolyzed with ice, extracted with chloroform, concentrated, and purified and separated by column chromatography (eluent: petroleum ether, ethyl acetate) to obtain 5a.

[0043] Product testing data are 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 for reaction. After the reaction, the pH value was adjusted to alkaline with sodium hydroxide solution, and the reaction system was extracted with dichloromethane several times, concentrated, and purified by column chromatography (eluent: dichloromethane, methanol) to obtain 6a.

[0047] Product testing data are 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 argon atmosphere, 6a (0.3 mmol, 1 equiv.), 3,3',4,4'-biphenyltetracarboxylic dianhydride 7a (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7aa.

[0051] Product testing data are 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] 6a and dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride 7b are used as raw materials. The synthesis method of 6a is the same as that shown in Example 1.

[0055]

[0056] At room temperature, under argon atmosphere, 6a (0.3 mmol, 1 equiv.), dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride 7b (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7ab.

[0057] Product testing data are 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] 6a and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 7c are used as raw materials. The synthesis method of 6a is the same as that shown in Example 1.

[0061]

[0062] At room temperature, under argon atmosphere, 6a (0.3 mmol, 1 equiv.), 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride 7c (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7ac.

[0063] Product testing data are 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] 6a and 1,2,4,5-cyclohexanetetracarboxylic dianhydride 7d are used as raw materials. The synthesis method of 6a is the same as that shown in Example 1.

[0067]

[0068] At room temperature, under argon atmosphere, 6a (0.3 mmol, 1 equiv.), 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride 7d (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7ad.

[0069] Product testing data are 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] 6a and hexafluorodianhydride 7e are used as raw materials. The synthesis method of 6a is the same as that shown in Example 1.

[0073]

[0074] At room temperature, under argon atmosphere, 6a (0.3 mmol, 1 equiv.), hexafluorodianhydride 7e (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7ae.

[0075] Product testing data are 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 6

[0078] 6a and 4,4'-oxydiphthalic anhydride 7f are used as raw materials. 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'-oxydiphthalic anhydride 7f (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7af.

[0081] Product testing data are 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 7

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

[0085]

[0086] At room temperature, under argon atmosphere, 6a (0.3 mmol, 1 equiv.), 3,3',4,4'-benzophenone tetracarboxylic dianhydride 7h (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7ah.

[0087] Product testing data are as follows:

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

[0089] Implementation Case 8

[0090] 6a and 1,2,3,4-cyclopentanetetracarboxylic dianhydride 7i are used as raw materials. The synthesis method of 6a is the same as that shown in Example 1.

[0091]

[0092] At room temperature, under argon atmosphere, 6a (0.3 mmol, 1 equiv.), 1,2,3,4-cyclopentanetetracarboxylic dianhydride 7i (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7ai.

[0093] Product testing data are as follows:

[0094] 1 H NMR (400MHz, DMSO) δ8.14–7.29 (m, 11H), 3.76 (d, J = 59.7Hz, 4H), 2.14 (d, J = 118.7Hz, 2H).

[0095] Implementation Case 9

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

[0097]

[0099] At room temperature, under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), DMCBDA 7j (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7aj.

[0100] Product testing data are as follows:

[0101] 1H NMR (400MHz, DMSO) δ8.15–7.30 (m, 11H), 3.62 (dd, J = 9.9, 5.0Hz, 2H), 1.49–

[0102] 1.10 (m, 6H).

[0103] Implementation Case 10

[0104] 6a and pyromellitic anhydride 7k are used as raw materials. The synthesis method of 6a is the same as that shown in Example 1.

[0105]

[0106] At room temperature, under an argon atmosphere, 6a (0.3 mmol, 1 equiv.), pyromellitic anhydride 7k (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7ak.

[0107] Product testing data are as follows:

[0108] 1 H NMR (400MHz, DMSO) δ8.34 (d, J = 8.0Hz, 2H), 7.99–7.44 (m, 11H).

[0109] Implementation Case 11

[0110] 6a and 2,3,3',4'-biphenyltetracarboxylic dianhydride 7m are used as raw materials. The synthesis method of 6a is the same as that shown in Example 1.

[0111]

[0112] At room temperature, under argon atmosphere, 6a (0.3 mmol, 1 equiv.), 2,3,3',4'-biphenyltetracarboxylic acid dianhydride 7m (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7am.

[0113] Product testing data:

[0114] 1H NMR (400MHz, DMSO) δ8.27–7.99(m,6H),7.64–7.39(m,11H).

[0115] Implementation Case 12

[0116] 6a and 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride 7n are used as raw materials. The synthesis method of 6a is the same as that shown in Example 1.

[0117]

[0118] At room temperature, under argon atmosphere, 6a (0.3 mmol, 1 equiv.), 2,3,3',4'-diphenylether tetracarboxylic dianhydride 7n (0.3 mmol, 1 equiv.) and catalyst benzoic acid (0.03 mmol, 1 equiv.) were added to m-cresol (1.5 mL) and stirred. After stirring and 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 vacuum dried to obtain a polyimide polymer 7an.

[0119] Product testing data:

[0120] 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 and a preparation method thereof, characterized in that: The polyimide material is obtained by reacting a phosphorus-containing diamine and 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 as follows:

2. A phosphorus-containing polyimide material and a preparation method thereof as claimed in claim 1, characterized in that: The acid anhydride is one or more of 3,3',4,4'-biphenyltetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hexafluorodianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, DMCBDA, pyromellitic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride.

3. A phosphorus-containing polyimide material and a preparation method thereof as claimed in claim 1, characterized in that: The phosphorus-containing diamine 6a is generated by reducing the phosphorus-containing dinitro compound 5a in the presence of stannous chloride and concentrated hydrochloric acid. The structural formula of the reaction is shown below.

4. A phosphorus-containing polyimide material and a preparation method thereof as claimed 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. A phosphorus-containing polyimide material and a preparation method thereof as claimed in claims 1 to 4, characterized in that: The steps include: Preparation of S1 and 5a: At room temperature, add the known compound 4a to concentrated sulfuric acid and stir, then add the prepared nitric acid and sulfuric acid mixed acid solution and stir to react. After the reaction, the reaction system is hydrolyzed with ice, extracted with chloroform, concentrated, and purified and separated by column chromatography (eluent: petroleum ether, ethyl acetate) to obtain 5a. Preparation of S2 and 6a: 5a and stannous chloride were added to ethanol and stirred for reaction at room temperature. After the reaction, the pH value was adjusted to alkaline with sodium hydroxide solution, and the reaction system was extracted with dichloromethane for multiple times, concentrated, and purified and separated by column chromatography (eluent: dichloromethane, methanol) to obtain 6a. S3. Preparation of phosphorus-containing polyimide: At room temperature, under argon environment, add 6a, acid anhydride and catalyst benzoic acid to m-cresol and stir. After stirring and dissolving at 80°C, raise the temperature to 180°C and react. After the reaction is completed, pour the reaction system into ethanol, filter, wash the solid with ethanol three times, and vacuum dry to obtain phosphorus-containing polyimide.

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