A polyimide-polyarylate interpenetrating network porous material and its preparation method
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-07-28
- Publication Date
- 2026-08-14
AI Technical Summary
[0004]本发明的目的是提供一种聚酰亚胺与聚芳酯互穿网络多孔材料及其制备方法，解决现有技术中聚酰亚胺泡沫泡孔相对较大，强度较低，对于其应用造成较大限制的问题，本发明的多孔材料，具有互穿网络，与传统的聚酰亚胺泡沫相比，在隔热、高温收缩、强度等方面具有很大提升，具有非常高的应用价值
[0045]本发明的聚酰亚胺与聚芳酯互穿网络多孔材料的制备方法利用聚酰亚胺泡沫高开孔结构，通过酚酞与对苯二酰氯、间苯三酰氯反应，在聚酰亚胺泡沫骨架中形成聚芳酯微孔结构，利用聚酰亚胺与聚芳酯形成的互穿网络提升多孔材料结构强度的同时，结合聚芳酯形成的纳米孔，进一步提升隔热性能。经实验检测，本发明制备的多孔材料密度8~12 kg/m3，拉伸强度为60~80 kPa，具有良好的力学性能；氧指数为34 %~40 %，5 %导热系数为0.032~0.04 W/(m·K)，具有优异的阻燃和耐热性能。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of porous materials technology, specifically relating to a polyimide and polyarylate interpenetrating network porous material and its preparation method. Background Technology
[0002] Polyimide foam is a lightweight, porous material with excellent properties such as high and low temperature resistance, thermal insulation, sound absorption and noise reduction, flame retardancy, and electrical insulation. High-performance polyimide foam can withstand 250-300℃ for long periods and 400-500℃ for short periods, making it one of the most thermally stable organic polymers. High-performance polyimide foam can also withstand extremely low temperatures, remaining brittle even in liquid helium at -269℃. Due to these numerous advantages, polyimide foam has been widely used in recent years in fields such as military defense, aerospace, shipbuilding, rail transportation, electronics, and new energy.
[0003] However, polyimide foam has relatively large pores and low strength, which greatly limits its application. Summary of the Invention
[0004] The purpose of this invention is to provide a polyimide and polyarylate interpenetrating network porous material and its preparation method, which solves the problem that the polyimide foam in the prior art has relatively large pores and low strength, which greatly limits its application. The porous material of this invention has an interpenetrating network and has a significant improvement in terms of heat insulation, high temperature shrinkage and strength compared with traditional polyimide foam, and has very high application value.
[0005] The technical solution adopted by the present invention to achieve the above objectives is as follows.
[0006] The present invention provides a polyimide and polyaryl ester interpenetrating network porous material, which is composed of polyimide foam forming an interpenetrating network and polyaryl ester microporous structure;
[0007] The raw material for the polyimide foam is:
[0008] 15-60 parts by weight of aromatic dianhydride;
[0009] 10-60 parts by weight of isocyanate;
[0010] Solvent: 10-30 parts by weight;
[0011] 1-5 parts by weight of low molecular weight alcohol;
[0012] 2-8 parts by weight of foaming agent;
[0013] 5-12 parts by weight of foam stabilizer;
[0014] Catalyst: 0.1-5 parts by weight;
[0015] The micropore size of the polyarylate microporous structure is 50~500 nm, and the raw material is:
[0016] Phenolphthalein 0.2~2 parts by weight;
[0017] 0.2 to 2 parts by weight of terephthaloyl chloride;
[0018] 0.2 to 2 parts by weight of isobenzotrimethyl chloride.
[0019] Preferably, the aromatic dianhydride includes one or more of 3,3',4,4'-diphenyl ether tetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-benzophenone tetracarboxylic anhydride, pyromellitic dianhydride (PMDA), 2,2-bis[4-(3,4-phenoxyphenyl)]propane dianhydride, and 3,3',4,4'-biphenyl sulfone tetracarboxylic anhydride.
[0020] Preferably, the isocyanate includes one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate, tetramethylphenyl diisocyanate, isoflurone diisocyanate, methylcyclohexane diisocyanate, cyclohexyl diisocyanate, hexamethylene diisocyanate, and methyl formate pentamethylene diisocyanate.
[0021] Preferably, the low molecular weight alcohol includes one or more of methanol, ethanol, and propanol.
[0022] Preferably, the solvent includes one or more of N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide.
[0023] Preferably, the foaming agent includes one or more of dichlorotrifluoroethane, dichlorofluoromethane, acetone, water, methanol, ethanol, and 2-butoxyethanol.
[0024] Preferably, the foam stabilizer includes one or more of DC193, DC197, DC5000, DC5598, L560, L580, AK8805, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 and B8002.
[0025] Preferably, the catalyst comprises one or two of a metal catalyst and an amine catalyst; more preferably, the metal catalyst is one or more of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiol, potassium isooctanoate, potassium oleate, cobalt isooctanoate, and cobalt neodecanoate; the amine catalyst comprises one or more of N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, N,N,N',N'-tetramethylalkylene diamine, triethylamine, N,N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N,N'-diethylpiperazine, triethanolamine, and N,N'-dimethylpyridine.
[0026] Preferably, the mass ratio of terephthaloyl chloride to isophthaloyl chloride is 0.1~20:1.
[0027] This invention also provides a method for preparing the above-mentioned polyimide and polyarylate interpenetrating porous material, comprising the following steps:
[0028] 1) Aromatic dianhydride, low molecular weight alcohol and solvent are reacted to obtain foaming precursor solution;
[0029] 2) Mix the foaming precursor solution, catalyst, foaming agent and foam stabilizer obtained in step 1) evenly to obtain a mixture;
[0030] 3) After mixing the mixture obtained in step 2) with isocyanate evenly, pour it into a mold, and after free foaming, pre-curing and post-curing, polyimide foam is obtained;
[0031] 4) The polyimide foam prepared in step 3) is impregnated in chloroform solution or dichloromethane solution, and phenolphthalein, terephthaloyl chloride and isophthalotrimethyl chloride are added to react and polyarylate gel is prepared on the polyimide foam to form an interpenetrating network and obtain a porous material.
[0032] 5) The porous material from step 4) is first heated and dried, and then treated with supercritical carbon dioxide to remove the residual solvent, resulting in a polyimide and polyarylate interpenetrating network porous material.
[0033] Preferably, in step 1), the reaction temperature is 80~120℃ and the reaction time is 3~5h.
[0034] Preferably, in step 2), the time for uniform mixing is 1 to 10 minutes, and the stirring speed is 50 to 800 rpm.
[0035] Preferably, in step 3), the method of uniform mixing is high-speed stirring; more preferably, the high-speed stirring speed is 800~3000 r / min and the time is 10~40 s.
[0036] Preferably, in step 3), the mold includes an open-type foaming mold.
[0037] Preferably, in step 3), the free foaming molding time is 5~30 min.
[0038] Preferably, in step 3), the pre-curing method includes microwave pre-curing; more preferably, the microwave pre-curing time is 20~50 min, and the microwave power gradient of the microwave pre-curing is set to 200~800 W.
[0039] Preferably, in step 3), the temperature gradient of the post-curing is set to 160~250 ℃, and the post-curing time is 3~5 h.
[0040] Preferably, in step 3), the pre-curing process further includes demolding.
[0041] Preferably, in step 4), the reaction temperature is -20~25 ℃ and the reaction time is 3~5 h.
[0042] Preferably, in step 5), the heating and drying temperature is 160~250 ℃.
[0043] Preferably, in step 5), the temperature of the supercritical carbon dioxide treatment is 120~200 ℃ and the pressure is 2~10 MPa.
[0044] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0045] The method for preparing the polyimide-polyaryl ester interpenetrating network porous material of the present invention utilizes the high open-pore structure of polyimide foam. Through the reaction of phenolphthalein with terephthaloyl chloride and isophthalotriyl chloride, a polyaryl ester microporous structure is formed within the polyimide foam framework. The interpenetrating network formed by polyimide and polyaryl ester enhances the structural strength of the porous material, while the nanopores formed by the polyaryl ester further improve its thermal insulation performance. Experimental testing shows that the density of the porous material prepared by this invention is 8~12 kg / m³. 3 It has a tensile strength of 60~80 kPa and good mechanical properties; an oxygen index of 34%~40% and a thermal conductivity of 0.032~0.04 W / (m·K) at 5%, exhibiting excellent flame retardancy and heat resistance. Detailed Implementation
[0046] To further understand the present invention, preferred embodiments of the present invention are described below. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims of the present invention.
[0047] The present invention provides a polyimide and polyaryl ester interpenetrating network porous material, which is composed of polyimide foam forming an interpenetrating network and polyaryl ester microporous structure;
[0048] The raw materials for polyimide foam are: 15-60 parts by weight of aromatic dianhydride, 10-60 parts by weight of isocyanate, 10-30 parts by weight of solvent, 1-5 parts by weight of low molecular weight alcohol, 2-8 parts by weight of foaming agent, 5-12 parts by weight of foam stabilizer and 0.1-5 parts by weight of catalyst.
[0049] The micropore size of the polyarylate microporous structure is 50~500nm, and the raw materials are: 0.2~2 parts by weight of phenolphthalein, 0.2~2 parts by weight of terephthaloyl chloride and 0.2~2 parts by weight of isotrimethylisophthaloyl chloride.
[0050] In the above technical solution, the aromatic dianhydride includes one or more of 3,3',4,4'-diphenyl ether tetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-benzophenone tetracarboxylic anhydride, pyromellitic dianhydride, 2,2-bis[4-(3,4-phenoxyphenyl)]propane dianhydride and 3,3',4,4'-biphenyl sulfone tetracarboxylic anhydride.
[0051] In the above technical solution, the isocyanate includes one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate, tetramethylphenyl dimethylene diisocyanate, isoflurone diisocyanate, methylcyclohexane diisocyanate, cyclohexyl dimethylene diisocyanate, hexamethylene diisocyanate, and methyl formate pentamethylene diisocyanate.
[0052] In the above technical solution, the low molecular weight alcohol includes one or more of methanol, ethanol and propanol.
[0053] In the above technical solution, the solvent includes one or more of N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide.
[0054] In the above technical solution, the foaming agent includes one or more of dichlorotrifluoroethane, dichlorofluoromethane, acetone, water, methanol, ethanol and 2-butoxyethanol.
[0055] In the above technical solution, the foam stabilizer includes one or more of DC193, DC197, DC5000, DC5598, L560, L580, AK8805, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 and B8002.
[0056] In the above technical solutions, the catalyst includes one or two of metal catalysts and amine catalysts; more preferably, the metal catalyst is one or more of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiol, potassium isooctanoate, potassium oleate, cobalt isooctanoate, and cobalt neodecanoate; the amine catalyst includes one or more of N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, N,N,N',N'-tetramethylalkylene diamine, triethylamine, N,N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N,N'-diethylpiperazine, triethanolamine, and N,N'-dimethylpyridine.
[0057] In the above technical solution, the preferred mass ratio of terephthaloyl chloride to isophthaloyl chloride is 0.1~20:1.
[0058] The present invention discloses a method for preparing a polyimide-polyarylate interpenetrating porous material, comprising the following steps:
[0059] 1) Aromatic dianhydride, low molecular weight alcohol and solvent are reacted to obtain foaming precursor solution;
[0060] 2) Mix the foaming precursor solution, catalyst, foaming agent and foam stabilizer obtained in step 1) evenly to obtain a mixture;
[0061] 3) After mixing the mixture obtained in step 2) with isocyanate evenly, pour it into a mold, and after free foaming, pre-curing and post-curing, polyimide foam is obtained;
[0062] 4) The polyimide foam prepared in step 3) is impregnated in chloroform solution or dichloromethane solution, and phenolphthalein, terephthaloyl chloride, isophthaloyl chloride and triethylamine are added to react and polyarylate gel is prepared on the polyimide foam to form an interpenetrating network and obtain a porous material.
[0063] 5) The porous material from step 4) is first heated and dried, and then treated with supercritical carbon dioxide to remove the residual solvent, resulting in a polyimide and polyarylate interpenetrating network porous material.
[0064] In the above technical solution, in step 1), the reaction temperature is 80~120 ℃ and the reaction time is 3~5 h.
[0065] In the above technical solution, in step 2), the mixing time is 1~10 min and the stirring speed is 50~800 rpm.
[0066] In the above technical solution, in step 3), the method of uniform mixing is high-speed stirring; more preferably, the high-speed stirring speed is 800~3000 r / min and the time is 10~40 s.
[0067] In the above technical solution, step 3), the mold includes an open foaming mold.
[0068] In the above technical solution, step 3), the free foaming time is 5~30 min.
[0069] In the above technical solution, step 3), the pre-curing method includes microwave pre-curing; more preferably, the microwave pre-curing time is 20~50min, and the microwave power gradient of the microwave pre-curing is set to 200~800 W.
[0070] In the above technical solution, step 3), the temperature gradient for post-curing is set to 160~250 ℃, and the curing time is 3~5 h.
[0071] In the above technical solution, step 3) includes demolding after pre-curing.
[0072] In the above technical solution, step 4) involves a reaction temperature of -20 to 25 ℃ and a reaction time of 3 to 5 h.
[0073] In the above technical solution, step 5), the heating and drying temperature is 160~250 ℃.
[0074] In the above technical solution, step 5), the temperature of the supercritical carbon dioxide treatment is 120~200 ℃ and the pressure is 2~10 MPa.
[0075] The terminology used in this invention generally has the meanings commonly understood by those skilled in the art, unless otherwise stated.
[0076] To enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further described in detail below with reference to embodiments.
[0077] In the following embodiments, various processes and methods not described in detail are conventional methods known in the art. Unless otherwise specified, the materials, reagents, apparatus, instruments, equipment, etc., used in the following embodiments are commercially available. All parts are by weight.
[0078] Example 1
[0079] 1) Dissolve 18 parts PMDA and 5 parts methanol in 25 parts DMF, heat to 80 °C, and react for 3 h until a clear and transparent solution is obtained;
[0080] 2) Cool the above clear and transparent solution to room temperature, add 0.05 parts dibutyltin dilaurate, 0.08 parts triethylamine, 0.11 parts N-methylmorpholine, 1.8 parts water, 0.5 parts dichlorofluoromethane, 5 parts DC193 and 1 part B4900, mix well to obtain a mixed solution;
[0081] 3) The above mixture and 40 parts of 4,4'-diphenylmethane diisocyanate were stirred at high speed (1000 rpm) for 15 seconds. After being mixed evenly, the mixture was poured into a mold and foamed at room temperature. Then, microwave pre-curing was performed at 300 W for 30 minutes. During the setting process, the temperature was further increased to 220°C for 3 hours to prepare polyimide foam.
[0082] 4) Impregnate polyimide foam in dichloromethane solvent, add 1 part phenolphthalein, 0.5 parts terephthaloyl chloride and 0.6 parts isophthalotrimethyl chloride, react at 10°C for 3 hours to obtain the product.
[0083] 5) After drying the product at 200℃ for 12 hours, it is treated with supercritical carbon dioxide at 150℃ and 5 MPa for 10 hours to obtain the final product.
[0084] Example 2
[0085] 1) Dissolve 18 parts PMDA and 4 parts methanol in 20 parts DMF, heat to 80 °C, and react for 3 h until a clear and transparent solution is obtained;
[0086] 2) Cool the above clear and transparent solution to room temperature, add 0.05 parts dibutyltin dilaurate, 0.08 parts triethylamine, 0.11 parts N-methylmorpholine, 1.8 parts water, 0.5 parts dichlorofluoromethane, 10 parts DC193 and 2 parts B4900, mix well to obtain a mixed solution;
[0087] 3) The above mixture and 35 parts of toluene diisocyanate were stirred at high speed (1000 rpm) for 25 seconds. After being mixed evenly, the mixture was poured into a mold and foamed at room temperature. Then, microwave pre-curing was performed at 350W for 30 minutes. During the setting process, the temperature was further increased to 220℃ for 3 hours to prepare polyimide foam.
[0088] 4) Impregnate polyimide foam in dichloromethane solvent, add 1 part phenolphthalein, 0.4 parts terephthaloyl chloride and 0.65 parts isophthalotrimethyl chloride, react at 0°C for 5 hours to obtain the product.
[0089] 5) After drying the product at 230°C for 12 hours, it is treated with supercritical carbon dioxide at 120°C and 7MPa for 10 hours to obtain the final product.
[0090] Example 3
[0091] 1) Dissolve 15 parts PMDA and 2.5 parts ethanol in 25 parts DMF, stir and heat to 45°C, add 2.5 parts methanol, continue heating to 80°C, react for 3 h until a clear and transparent solution is obtained;
[0092] 2) Cool the above clear and transparent solution to room temperature, add 0.05 parts dibutyltin dilaurate, 0.08 parts triethylamine, 0.11 parts N-methylmorpholine, 1.8 parts water, 0.5 parts dichlorofluoromethane, 5 parts DC193, and 1.8 parts B4900, mix well to obtain a mixed solution;
[0093] 3) The above mixture and 40 parts of toluene diisocyanate were mixed evenly by high-speed stirring at 1000 rpm and then injected into the mold. The mixing time was 15 s, and the mixture was foamed at room temperature. Then the foam was microwave pre-cured at 300 W for 30 min. The setting process was continued by heating to 200 ℃ for 3 h to prepare polyimide foam.
[0094] 4) Impregnate polyimide foam in dichloromethane solvent, add 1 part phenolphthalein, 0.8 parts terephthaloyl chloride and 0.4 parts isophthalotrimethyl chloride, react at 10°C for 2 hours to obtain the product.
[0095] 5) The product was dried at 220°C for 12 hours and then treated with supercritical carbon dioxide at 150°C and 6 MPa for 10 hours to obtain the final product.
[0096] Example 4
[0097] 1) Dissolve 15 parts PMDA and 4 parts ethanol in 25 parts DMF, heat to 90 °C, and react for 3 h until a clear and transparent solution is obtained;
[0098] 2) Cool the above clear and transparent solution to room temperature, add 0.05 parts dibutyltin dilaurate, 0.08 parts triethylamine, 0.11 parts N-methylmorpholine, 1.8 parts water, 0.5 parts dichlorofluoromethane, 5.6 parts DC193 and 2.8 parts B4900, mix well to obtain a mixed solution;
[0099] 3) The above mixture and 40 parts of iso-4,4'-diphenylmethane diisocyanate were stirred at high speed (1000 rpm) for 15 seconds. After the mixture was homogeneous, it was injected into a mold and foamed at room temperature. Then, the foam was microwave pre-cured at 300 W for 40 minutes. The setting process was continued by heating to 210 °C for 3 hours to prepare polyimide foam.
[0100] 4) Impregnate polyimide foam in dichloromethane solvent, add 1 part phenolphthalein, 0.3 parts terephthaloyl chloride and 0.85 parts isophthalotrimethyl chloride, react at 0°C for 4 hours to obtain the product.
[0101] 5) The product is dried at 230°C for 12 hours, then treated with supercritical carbon dioxide at 200°C and 5MPa for 10 hours to obtain the final product.
[0102] Example 5
[0103] 1) Dissolve 17 parts PMDA and 2 parts ethanol in 25 parts DMF, heat to 100 °C, and react for 3 h until a clear and transparent solution is obtained;
[0104] 2) Cool the above clear and transparent solution to room temperature, add 0.05 parts dibutyltin dilaurate, 0.08 parts triethylamine, 0.11 parts N-methylmorpholine, 1.8 parts water, 0.5 parts dichlorofluoromethane, 5 parts DC193 and 3 parts B4900, mix well to obtain a mixed solution;
[0105] 3) The above mixture and 40 parts of polyphenyl polymethylene polyisocyanate were stirred at high speed (1000 rpm) for 15 seconds. After being mixed evenly, the mixture was poured into a mold and foamed at room temperature. Then, the foam was microwave pre-cured at 400 W for 30 minutes. During the setting process, the temperature was raised to 210 °C for 3 hours to prepare polyimide foam.
[0106] 4) Impregnate polyimide foam in dichloromethane solvent, add 1 part phenolphthalein, 0.2 parts terephthaloyl chloride and 0.9 parts isophthalotrimethyl chloride, react at 0°C for 5 hours to obtain the product.
[0107] 5) The product is dried at 210°C for 12 hours, then treated with supercritical carbon dioxide at 180°C and 10MPa for 10 hours to obtain the final product.
[0108] Example 6
[0109] 1) Dissolve 15 parts PMDA and 3 parts methanol in 25 parts DMF, heat to 80 °C, and react for 3 h until a clear and transparent solution is obtained;
[0110] 2) Cool the above clear and transparent solution to room temperature, add 0.05 parts dibutyltin dilaurate, 0.08 parts triethylamine, 0.11 parts N-methylmorpholine, 1.8 parts water, 0.5 parts dichlorofluoromethane, 12 parts DC193 and 2.8 parts B4900, mix well to obtain a mixed solution;
[0111] 3) The above mixture and 40 parts of 4,4'-diphenylmethane diisocyanate were mixed evenly by high-speed stirring at 1000 rpm and then injected into a mold. The mixing time was 15 s, and the mixture was foamed at room temperature. Then the foam was microwave pre-cured at 300 W for 45 min. The setting process was continued by heating to 220℃ for 3 h to prepare polyimide foam.
[0112] 4) Impregnate polyimide foam in dichloromethane solvent, add 1 part phenolphthalein, 0.4 parts terephthaloyl chloride and 0.65 parts isophthalotrimethyl chloride, react at 0°C for 5 hours to obtain the product.
[0113] 5) The product is dried at 230°C for 12 hours, then treated with supercritical carbon dioxide at 200°C and 6MPa for 10 hours to obtain the final product.
[0114] Comparative Example 1
[0115] 1) Dissolve 18 parts PMDA and 5 parts methanol in 25 parts DMF, heat to 80 °C, and react for 3 h until a clear and transparent solution is obtained;
[0116] 2) Cool the above clear and transparent solution to room temperature, add 0.05 parts dibutyltin dilaurate, 0.08 parts triethylamine, 0.11 parts N-methylmorpholine, 1.8 parts water, 0.5 parts dichlorofluoromethane, 5 parts DC193 and 1 part B4900, mix well to obtain a mixed solution;
[0117] 3) The above mixture and 40 parts of 4,4'-diphenylmethane diisocyanate were stirred at high speed (1000 rpm) for 15 seconds. After being mixed evenly, the mixture was poured into a mold and foamed at room temperature. Then, microwave pre-curing was performed at 300 W for 30 minutes. During the setting process, the temperature was further increased to 220°C for 3 hours to prepare polyimide foam.
[0118] Examples 1-6 are porous materials obtained using the formulation and preparation method of the present invention, while Comparative Example 1 is a polyimide foam prepared using conventional methods.
[0119] The performance tests of the porous materials in Examples 1-6 and the polyimide foam in Comparative Example 1 are shown in Table 1. The testing standards were as follows: foam density test standard was GB / T 6343-2009, tensile strength test standard was GB / T 6344-2008, oxygen index test standard was GB / T 2406.2-2009, and room temperature thermal conductivity test standard was GB / T 10295-2008.
[0120] Table 1. Properties of porous materials in Examples 1-6 and polyimide foam prepared in Comparative Example 1
[0121]
[0122] As shown in Table 1, the density of the polyimide-polyarylate interpenetrating network porous material prepared in this invention is 8.4~10.9 kg / m³. 3 It has a tensile strength of 61.8~78.2 kPa and good mechanical properties. Its oxygen index is approximately 34%~40%, and its thermal conductivity is 0.032~0.04 W / (m·K), exhibiting excellent flame retardancy and heat resistance.
[0123] Obviously, the above embodiments are merely examples for clear illustration and are not intended to limit the embodiments. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all embodiments here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A polyimide and polyarylate interpenetrating network porous material, characterized in that, It consists of polyimide foam forming an interpenetrating network and polyarylate microporous structure; The raw material for the polyimide foam is: 15-60 parts by weight of aromatic dianhydride; 10-60 parts by weight of isocyanate; Solvent: 10-30 parts by weight; 1-5 parts by weight of low molecular weight alcohol; 2-8 parts by weight of foaming agent; 5-12 parts by weight of foam stabilizer; Catalyst: 0.1-5 parts by weight; The micropore size of the polyarylate microporous structure is 50-500 nm, and the raw material is: Phenolphthalein 0.2~2 parts by weight; 0.2 to 2 parts by weight of terephthaloyl chloride; 0.2-2 parts by weight of isobenzotrimethyl chloride; The polyimide-polyarylate interpenetrating porous material is prepared by the following method: 1) Aromatic dianhydride, low molecular weight alcohol and solvent are reacted to obtain foaming precursor solution; 2) Mix the foaming precursor solution, catalyst, foaming agent and foam stabilizer obtained in step 1) evenly to obtain a mixture; 3) After mixing the mixture obtained in step 2) with isocyanate evenly, pour it into a mold, and after free foaming, pre-curing and post-curing, polyimide foam is obtained; 4) The polyimide foam prepared in step 3) is impregnated in chloroform solution or dichloromethane solution, and phenolphthalein, terephthaloyl chloride and isophthalotrimethyl chloride are added to react and polyarylate gel is prepared on the polyimide foam to form an interpenetrating network and obtain a porous material. 5) The porous material from step 4) is first heated and dried, and then treated with supercritical carbon dioxide to remove the residual solvent, resulting in a polyimide and polyarylate interpenetrating network porous material.
2. The polyimide and polyarylate interpenetrating network porous material according to claim 1, characterized in that, The aromatic dianhydride includes one or more of the following: 3,3',4,4'-diphenyl ether tetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-benzophenone tetracarboxylic anhydride, pyromellitic dianhydride, 2,2-bis[4-(3,4-phenoxyphenyl)]propane dianhydride, and 3,3',4,4'-biphenyl sulfone tetracarboxylic anhydride; The isocyanate includes one or more of toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, polyphenyl polymethylene polyisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxy-4,4'-diphenyl diisocyanate, tetramethylphenyl dimethylene diisocyanate, isoflurone diisocyanate, methylcyclohexane diisocyanate, cyclohexyl dimethylene diisocyanate, hexamethylene diisocyanate, and methyl formate pentamethylene diisocyanate; The low molecular weight alcohols include one or more of methanol, ethanol, and propanol; The solvent includes one or more of N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide; The foaming agent includes one or more of dichlorotrifluoroethane, dichlorofluoromethane, acetone, water, methanol, ethanol, and 2-butoxyethanol; The foam stabilizer includes one or more of DC193, DC197, DC5000, DC5598, L560, L580, AK8805, SF8427, KY-6035, HK-314, GT-320, B4900, B8123 and B8002; The catalyst includes one or both of the following: metal catalyst and amine catalyst.
3. The polyimide and polyarylate interpenetrating network porous material according to claim 2, characterized in that, The metal catalyst is one or more of stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin thiolate, potassium isooctanoate, potassium oleate, cobalt isooctanoate, and cobalt neodecanoate; the amine catalyst includes one or more of N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, N,N,N',N'-tetramethylalkylene diamine, triethylamine, N,N-dimethylbenzylamine, N-ethylmorpholine, N-methylmorpholine, N,N'-diethylpiperazine, triethanolamine, and N,N'-dimethylpyridine.
4. The polyimide and polyarylate interpenetrating network porous material according to claim 1, characterized in that, The mass ratio of terephthaloyl chloride to isophthaloyl chloride is 0.1~2:
1.
5. A method for preparing a polyimide and polyarylate interpenetrating porous material according to any one of claims 1 to 4, characterized in that, Includes the following steps: 1) Aromatic dianhydride, low molecular weight alcohol and solvent are reacted to obtain foaming precursor solution; 2) Mix the foaming precursor solution, catalyst, foaming agent and foam stabilizer obtained in step 1) evenly to obtain a mixture; 3) After mixing the mixture obtained in step 2) with isocyanate evenly, pour it into a mold, and after free foaming, pre-curing and post-curing, polyimide foam is obtained; 4) The polyimide foam prepared in step 3) is impregnated in chloroform solution or dichloromethane solution, and phenolphthalein, terephthaloyl chloride and isophthalotrimethyl chloride are added to react and polyarylate gel is prepared on the polyimide foam to form an interpenetrating network and obtain a porous material. 5) The porous material from step 4) is first heated and dried, and then treated with supercritical carbon dioxide to remove the residual solvent, resulting in a polyimide and polyarylate interpenetrating network porous material.
6. The method for preparing a polyimide and polyarylate interpenetrating porous material according to claim 5, characterized in that, In step 1), the reaction temperature is 80~120 ℃ and the reaction time is 3~5 h.
7. The method for preparing a polyimide and polyarylate interpenetrating porous material according to claim 4, characterized in that, In step 2), the time for mixing is 1 to 10 minutes, and the stirring speed is 50 to 800 rpm.
8. The method for preparing a polyimide and polyarylate interpenetrating porous material according to claim 5, characterized in that, In step 3), The method for achieving uniform mixing is high-speed stirring, with a stirring speed of 800~3000 r / min and a time of 10~40 s; The mold includes an open foaming mold; The free foaming molding time is 5~30 min; The pre-curing method includes microwave pre-curing, the microwave pre-curing time is 20~50 min, and the microwave power gradient of microwave pre-curing is set to 200~800 W. The temperature gradient for post-curing is set to 160~250 ℃, and the curing time is 3~5 h.
9. The method for preparing a polyimide and polyarylate interpenetrating porous material according to claim 5, characterized in that, In step 4), the reaction temperature is -20~25 ℃ and the reaction time is 3~5 h.
10. The method for preparing a polyimide and polyarylate interpenetrating porous material according to claim 5, characterized in that, In step 5), The heating and drying temperature is 160~250℃; The supercritical carbon dioxide treatment is carried out at a temperature of 120~200 ℃ and a pressure of 2~10 MPa.
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