A kind of polyimide resin and preparation method thereof
By using diisocyanate and specific tetraacid dianhydride in an organic solvent during the synthesis of polyimide resin, the problems of long synthesis time and high temperature in the prior art are solved, and the preparation of toughened and temperature-resistant polyimide resin is realized, with excellent temperature resistance, mechanical properties and toughness.
Patent Information
- Application Number
- CN202410929634.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-11
- Publication Date
- 2025-03-07
- Estimated Expiration
- 2044-07-11
AI Technical Summary
The existing polyimide synthesis methods have problems such as long synthesis time and high reaction temperature, and it is difficult to meet the needs of improving toughness and shortening reaction time while ensuring temperature resistance and mechanical properties.
A toughening and temperature-resistant polyimide resin was prepared by polymerizing diisocyanate with 3,3',4,4'-benzophenone tetraacid dianhydride, 4,4'-diphenylene dianhydride and phenylatic dianhydride in an organic solvent. The process includes stirring at room temperature for 15 minutes and then heating to 100°C for 3.5 hours, followed by cooling and precipitation through distilled water, and finally drying in a vacuum oven.
It is achieved to improve the toughness while ensuring excellent temperature resistance and mechanical properties of the polyimide resin, shorten the reaction time of the traditional synthesis method and reduce the reaction temperature.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polymer materials, and in particular to a polyimide resin and a preparation method thereof. Background Art
[0002] The aromatic structure of polyimide makes it one of the high-performance polymers with excellent thermal stability. It has been widely studied in various applications such as electronics, automobiles, aerospace and adhesive industries. Existing polyimide is synthesized by two-step polymerization of diamine and dianhydride in polar solvent to generate polyamic acid, and then thermally or chemically imidized at 150-180°C, that is, by a two-step method. The synthesis time is long and the reaction temperature is high. Summary of the invention
[0003] The present invention provides a polyimide resin and a preparation method thereof, so as to solve the above-mentioned deficiencies in the prior art, improve the toughness of the polyimide resin, shorten the reaction time of the traditional synthesis method, and reduce the reaction temperature while ensuring the excellent temperature resistance and mechanical properties of the polyimide resin.
[0004] In order to achieve the purpose of the present invention, the following technologies are proposed:
[0005] On the one hand, a polyimide resin is provided, which has the following chemical structure:
[0006]
[0007] wherein X is a residue of a diisocyanate and Y is a residue of a tetracarboxylic dianhydride.
[0008] Further, X diisocyanate is and One or both of the chemical structures.
[0009] 3. The polyimide resin according to claim 1, characterized in that the Y tetracarboxylic dianhydride is , and
[0010] One or both of the chemical structures.
[0011] On the other hand, a method for preparing a polyimide resin is provided, comprising the steps of:
[0012] Step 001, dissolving diisocyanate in an organic solvent to obtain a diisocyanate solution;
[0013] Step 002, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 4,4′-diphenyl ether dianhydride (ODPA), and pyromellitic dianhydride (PMDA) are dissolved in an organic solvent to obtain a dianhydride mixture;
[0014] Step 003, adding the dianhydride mixed solution obtained in step 002 to the diisocyanate solution, stirring at room temperature for 15 minutes, and then heating the solution to 100° C. and stirring for 3.5 hours to carry out a reaction;
[0015] Step 004, cooling the solution obtained in step 003 at room temperature, and precipitating it with distilled water;
[0016] Step 005, filtering the precipitated product in step 004, and washing with a detergent to obtain a final product;
[0017] Step 006, drying the final product obtained in step 005 in a vacuum oven at 100° C. to obtain a toughened polyimide resin.
[0018] Furthermore, the organic solvent is one of N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP) or N,N-dimethylformamide (DMF).
[0019] Furthermore, in step 003, the molar ratio of the diisocyanate solution to the dianhydride mixed solution is 1:(0.98-1.02).
[0020] Furthermore, the detergent in step 005 is methanol, and the amount of the detergent used is 2-10 times the mass of the precipitated product to be washed.
[0021] Furthermore, the solid content of the 003 polymerization intermediate solution (the prepared polyimide resin) is 15-35% by mass.
[0022] The advantages of the above technical solution are:
[0023] The invention improves the toughness of the polyimide resin, shortens the reaction time of the traditional synthesis method, and reduces the reaction temperature while ensuring the excellent temperature resistance and mechanical properties of the polyimide resin. DETAILED DESCRIPTION
[0024] In general, a method for preparing a toughened heat-resistant polyimide resin is achieved by the following method. Specifically, a diisocyanate is dissolved in an organic solvent, and 3,3′,4,4′-diphenyl ether dianhydride (BTDA), 4,4′-diphenyl ether dianhydride (ODPA), and pyromellitic acid dianhydride (PMDA) are dissolved in an organic solvent to obtain a dianhydride mixture; then the dianhydride mixture is added to the diisocyanate solution, stirred at room temperature for 15 min, and then the solution is heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles are observed, indicating that the reaction is complete. The solution is cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product is filtered and washed with a detergent to obtain the final product. The sample is placed in a dryer overnight and then dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0025] The chemical structure of the toughened polyimide resin obtained is: wherein X is a residue of a diisocyanate and Y is a residue of a tetracarboxylic dianhydride.
[0026] Wherein, X diisocyanate is and One or both of the chemical structures.
[0027] Among them, Y tetracarboxylic dianhydride is , and
[0028] One or both of the chemical structures.
[0029] Example 1
[0030] A method for preparing a toughened heat-resistant polyimide resin comprises dissolving 35.28 g of 4,4′-diphenylmethane diisocyanate (MDI) in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to form a diisocyanate solution.
[0031] 15.14 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 10.25 g of 4,4′-diphenyl ether dianhydride (ODPA), and 14.58 g of pyromellitic dianhydride (PMDA) were dissolved in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to obtain a dianhydride mixed solution.
[0032] Then, the dianhydride mixture was added to the diisocyanate solution, and after stirring at room temperature for 15 min under N2 atmosphere, the solution was heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles were observed, indicating that the reaction was complete. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with methanol detergent to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0033] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 15%.
[0034] Example 2
[0035] A method for preparing a toughened heat-resistant polyimide resin comprises dissolving 58.56 g of 4,4′-diphenylmethane diisocyanate (MDI) in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to form a diisocyanate solution.
[0036] 25.13 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 17.01 g of 4,4′-diphenyl ether dianhydride (ODPA), and 24.19 g of pyromellitic dianhydride (PMDA) were dissolved in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to obtain a dianhydride mixed solution.
[0037] Then, the dianhydride mixture was added to the diisocyanate solution, and after stirring at room temperature for 15 min under N2 atmosphere, the solution was heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles were observed, indicating that the reaction was complete. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0038] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 25%.
[0039] Example 3
[0040] A method for preparing a toughened heat-resistant polyimide resin comprises dissolving 82.21 g of 4,4′-diphenylmethane diisocyanate (MDI) in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to form a diisocyanate solution.
[0041] At the same time, 35.28g of 3,3′,4,4′-benzophenone tetracarboxylic anhydride (BTDA), 41.55g of 4,4′-biphenyl ether anhydride (ODPA), and 33.96g of pyromellitic anhydride (PMDA) were dissolved in 250 ml of N-methylpyrrolidone (NMP) as an organic solvent to obtain a dianhydride mixture; then the dianhydride mixture was added to the diisocyanate solution, stirred at room temperature for 15 minutes under N2 atmosphere, and then the solution was heated to 100°C and stirred for 3.5 hours to complete the reaction. After heating for 3.5 hours, no bubbles were observed, indicating that the reaction was completed. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0042] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 35%.
[0043] Example 4
[0044] A method for preparing a toughened heat-resistant polyimide resin comprises dissolving 28.73 g of toluene diisocyanate (TDI) in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to form a diisocyanate solution.
[0045] At the same time, 17.72 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 11.99 g of 4,4′-diphenyl ether dianhydride (ODPA), and 17.06 g of pyromellitic dianhydride (PMDA) were dissolved in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to obtain a dianhydride mixed solution.
[0046] Then, the dianhydride mixture was added to the diisocyanate solution, and after stirring at room temperature for 15 min under N2 atmosphere, the solution was heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles were observed, indicating that the reaction was complete. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0047] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 15%.
[0048] Example 5
[0049] A method for preparing a toughened heat-resistant polyimide resin comprises dissolving 47.88 g of toluene diisocyanate (TDI) in 250 ml of N-methylpyrrolidone (NMP), and dissolving 29.53 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 19.98 g of 4,4′-biphenyl ether dianhydride (ODPA), and 28.43 g of pyromellitic tetracarboxylic dianhydride (PMDA) in 250 ml of N-methylpyrrolidone (NMP), to obtain a dianhydride mixed solution; then the dianhydride mixed solution is added to the diisocyanate solution, and after stirring at room temperature for 15 min under a N2 atmosphere, the solution is heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles are observed, indicating that the reaction is complete. The solution is cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product is filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100 °C to obtain toughened polyimide resin.
[0050] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 25%.
[0051] Example 6
[0052] A method for preparing a toughened heat-resistant polyimide resin comprises dissolving 66.61 g of toluene diisocyanate (TDI) in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to form a diisocyanate solution.
[0053] 41.08 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 27.81 g of 4,4′-diphenyl ether dianhydride (ODPA), and 39.55 g of pyromellitic dianhydride (PMDA) were dissolved in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to obtain a dianhydride mixed solution.
[0054] Then, the dianhydride mixture was added to the diisocyanate solution, and after stirring at room temperature for 15 min under N2 atmosphere, the solution was heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles were observed, indicating that the reaction was complete. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0055] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 35%.
[0056] Example 7
[0057] A method for preparing a toughened heat-resistant polyimide resin comprises dissolving 44.29 g of 4,4′-diphenylmethane diisocyanate (MDI) and 30.82 g of toluene diisocyanate (TDI) in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to form a diisocyanate solution.
[0058] Meanwhile, 38.02 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 25.73 g of 4,4′-diphenyl ether dianhydride (ODPA), and 36.60 g of pyromellitic dianhydride (PMDA) were dissolved in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to obtain a dianhydride mixed solution.
[0059] The dianhydride mixture was added to the diisocyanate solution. After stirring at room temperature for 15 min under N2 atmosphere, the solution was heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles were observed, indicating that the reaction was complete. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0060] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 35%.
[0061] Comparative Example 1
[0062] This comparative example proposes a method for preparing a toughened heat-resistant polyimide resin for Example 3, wherein 76.57 g of 4,4′-diphenylmethane diisocyanate (MDI) is dissolved in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to form a diisocyanate solution.
[0063] 98.6 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) was dissolved in 250 ml of N-methylpyrrolidone (NMP) as an organic solvent to form a dianhydride solution.
[0064] Then, dianhydride was added to the diisocyanate solution, and after stirring at room temperature for 15 min under N2 atmosphere, the solution was heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles were observed, indicating that the reaction was complete. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0065] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 35%.
[0066] Comparative Example 2
[0067] This comparative example proposes a method for preparing a toughened heat-resistant polyimide resin for Example 6, wherein 61.47 g of toluene diisocyanate (TDI) is dissolved in 250 ml of an organic solvent, N-methylpyrrolidone (NMP), to form a diisocyanate solution.
[0068] At the same time, 113.74 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) was dissolved in 250 ml of N-methylpyrrolidone (NMP) as an organic solvent to form a dianhydride solution.
[0069] Then, dianhydride was added to the diisocyanate solution, and after stirring at room temperature for 15 min under N2 atmosphere, the solution was heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles were observed, indicating that the reaction was complete. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0070] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 35%.
[0071] Comparative Example 3
[0072] This comparative example provides a method for preparing a toughened heat-resistant polyimide resin for Example 3, wherein 82.21 g of 4,4′-diphenylmethane diisocyanate (MDI) is dissolved in 250 ml of an organic solvent, N,N-dimethylacetamide (DMA), to form a diisocyanate solution.
[0073] 35.28 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 41.55 g of 4,4′-diphenyl ether dianhydride (ODPA), and 33.96 g of pyromellitic dianhydride (PMDA) were dissolved in 250 ml of an organic solvent, N,N-dimethylacetamide (DMA), to obtain a dianhydride mixed solution.
[0074] Then, the dianhydride mixture was added to the diisocyanate solution, and after stirring at room temperature for 15 min under N2 atmosphere, the solution was heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles were observed, indicating that the reaction was complete. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0075] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 35%.
[0076] Comparative Example 4
[0077] This comparative example provides a method for preparing a toughened heat-resistant polyimide resin for Example 3, wherein 82.21 g of 4,4′-diphenylmethane diisocyanate (MDI) is dissolved in 250 ml of an organic solvent, N,N-dimethylformamide (DMF), to form a diisocyanate solution.
[0078] At the same time, 35.28 g of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 41.55 g of 4,4′-diphenyl ether dianhydride (ODPA), and 33.96 g of pyromellitic dianhydride (PMDA) were dissolved in 250 ml of an organic solvent, N,N-dimethylformamide (DMF), to obtain a dianhydride mixed solution.
[0079] Then, the dianhydride mixture was added to the diisocyanate solution, and after stirring at room temperature for 15 min under N2 atmosphere, the solution was heated to 100°C and stirred for 3.5 h to complete the reaction. After heating for 3.5 h, no bubbles were observed, indicating that the reaction was complete. The solution was cooled at room temperature and precipitated with a large amount of distilled water. Finally, the precipitated product was filtered and washed with detergent methanol to obtain the final product. The sample was dried in a vacuum oven at 100°C to obtain a toughened polyimide resin.
[0080] The toughened heat-resistant polyimide resin product prepared according to the above method has a solid content of 35%.
[0081] In order to further verify the performance of the toughened heat-resistant polyimide resin obtained by the present invention, the performance of the toughened polyimide resin obtained in Examples 1-7 and Comparative Examples 1-4 pressed into standard test samples was tested and compared, and the test results are shown in the following table:
[0082]
[0083] The above test results are obtained by testing toughened polyimide resin particles into samples by film pressing (300°C) under standard test conditions, such as testing samples by extrusion or injection molding.
[0084] Heat deformation temperature: The heat deformation temperature was determined by DSC measurement using a differential scanning calorimeter in a nitrogen atmosphere at a heating rate of 10°C / min.
[0085] Mechanical properties: measured using a universal material testing machine in accordance with GB / T 1040.3-2006.
[0086] It can be seen from the data in the above table that in the process of preparing the toughened heat-resistant polyimide resin in the embodiment of the present invention, the toughened heat-resistant polyimide resin is obtained by polymerizing 3,3′,4,4′-dibenzophenone tetracarboxylic dianhydride, 4,4′-biphenyl ether dianhydride, isomellitic tetracarboxylic dianhydride and the diisocyanate. With the introduction of ether anhydride and keto anhydride, the ether bond improves the flexibility of the resin structure, and the secondary crosslinking of the carbonyl group in the keto anhydride under high temperature conditions improves the toughness and heat deformation temperature of the polyimide resin, so that the resin achieves a good balance in terms of heat resistance and mechanical properties, thereby effectively increasing the scope of use of the polyimide resin. In addition, the present invention improves the limitations of the one-step synthesis of polyimide, which requires a long time and high temperature, improves the mechanical properties without affecting its heat resistance, and also increases its toughness.
[0087] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.
Claims
1. A method for preparing a polyimide resin, wherein the polyimide resin has the following chemical structural formula: , wherein X is a residue of a diisocyanate and Y is a residue of a tetraacid dianhydride; X diisocyanate is and One or both of the chemical structures; Y tetracarboxylic dianhydride is , and One or both of the chemical structures; It is characterized in that Includes steps: Step 001, dissolving diisocyanate in an organic solvent to obtain a diisocyanate solution; Step 002, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 4,4′-diphenyl ether dianhydride (ODPA), and pyromellitic dianhydride (PMDA) are dissolved in an organic solvent to obtain a dianhydride mixture; Step 003, adding the dianhydride mixed solution obtained in step 002 to the diisocyanate solution, stirring at room temperature for 15 min, and then heating the solution to 100° C. and stirring for 3.5 h to carry out a reaction; The solid content mass fraction of the polymerization intermediate solution is 15-35%; In step 003, the reaction between the dianhydride mixed solution and the diisocyanate solution is carried out under a nitrogen atmosphere; Step 004, cooling the solution obtained in step 003 at room temperature, and precipitating it with distilled water; Step 005, filtering the precipitated product in step 004, and washing with a detergent to obtain a final product; Step 006, drying the final product obtained in step 005 in a vacuum oven at 100° C. to obtain a toughened polyimide resin.
2. The method for preparing a polyimide resin according to claim 1, wherein: The organic solvent is one of N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP) or N,N-dimethylformamide (DMF).
3. The method for preparing a polyimide resin according to claim 1, wherein: In step 003, the molar ratio of the diisocyanate solution to the dianhydride mixed solution is 1:(0.98-1.02).
4. The method for preparing a polyimide resin according to claim 1, wherein: In step 005, the detergent is methanol, and the amount of the detergent is 2-10 times the mass of the precipitated product to be washed.
5. The method for preparing a polyimide resin according to claim 1, wherein: The diisocyanate in step 001 is one of 4,4′-diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI), or a combination of the two.
Citation Information
Patent Citations
Preparation method of polyimide film
CN101684182A