High-strength fluorine-containing polyimide foam material and preparation method thereof

Abstract

The invention relates to the technical field of preparation of high-strength fluorine-containing polyimide foam materials, in particular to a high-strength fluorine-containing polyimide foam material and a preparation method thereof. In the preparation process, bismaleimide resin is added, and the bismaleimide resin comprises the following components: a fluorine-containing monomer, bismaleimide, isocyanate, an initiator, a foam stabilizer and a foaming agent. The preparation method comprises the following steps: respectively weighing the fluorine-containing dianhydride, the fluorine-containing diamine, the bismaleimide, the solvent and the low-molecular alcohol according to the mass ratio, reacting to form a prepolymer solution, adding the initiator, the foaming agent and the stabilizer to form a mixed solution, stirring the mixed solution with the isocyanate at a high speed, injecting the mixed solution into a mold, and carrying out foaming molding at room temperature to obtain the fluorine-containing polyurethane foam material. And performing high-temperature curing to obtain the high-strength fluorine-containing polyimide foam. Compared with common polyimide foam, the mechanical strength and toughness of the polyimide foam are remarkably improved in an interpenetrating network enhancement mode.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of high-strength fluorine-containing polyimide foam material, in particular to a high-strength fluorine-containing polyimide foam material and a preparation method thereof. Background Art

[0002] Foam material is an ideal lightweight structural material with good vibration reduction, energy absorption, sound insulation, heat insulation and other properties. With the progress of society, modern industry has an increasing demand for high-performance foams with high temperature resistance and high strength. Some common foams can no longer meet the needs of modern industry. Polyimide foam has high heat resistance and weather resistance, but its strength is not high, which limits its use scenarios.

[0003] With respect to the above-mentioned related technologies, the inventors found that the existing polyimide foam materials have low strength, poor mechanical properties and toughness, and cannot meet the requirements of existing lightweight structural materials for their mechanical properties. Summary of the invention

[0004] In order to improve the defect of poor mechanical properties of the currently produced copper foam, the present application provides a high-strength fluorine-containing polyimide foam material and a preparation method thereof.

[0005] In the first aspect, the present application provides a high-strength fluorinated polyimide foam material, which adopts the following technical solution: A high-strength fluorine-containing polyimide foam material comprises the following substances in parts by weight: 20-50 parts of fluorine-containing monomer, 10-20 parts of bismaleimide, 20-40 parts of polymeric MDI, 10-40 parts of solvent, 1-5 parts of low molecular alcohol, 0.1-1.0 parts of initiator, 3-8 parts of foam stabilizer, 0.1-3.0 parts of catalyst and 3-10 parts of foaming agent.

[0006] Through the above technical scheme, the present application first introduces a fluorine-containing monomer to further improve its heat resistance, and then introduces a bismaleimide resin. By making an interpenetrating network foam material with fluorine-containing polyimide and bismaleimide, the mechanical properties of the fluorine-containing polyimide foam are greatly improved, and its heat resistance is also improved.

[0007] Further, the fluorine-containing monomer includes one or more of hexafluorodianhydride, 4,4'-oxybis[3-(trifluoromethyl)aniline], 4,4'-oxybis[3-(oxytrifluoromethyl)aniline], 4,4'-oxybis[3-fluoroaniline], 2-(trifluoromethyl)-1,4-p-phenylenediamine, 2-(oxytrifluoromethyl)-1,4-p-phenylenediamine, 2-fluoro-1,4-p-phenylenediamine, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 2,2'-bis(oxytrifluoromethyl)diaminobiphenyl and 2,2'-bis(fluoro)diaminobiphenyl.

[0008] Through the above technical solution, the present application optimizes the components of fluorinated monomers, wherein the addition of fluorinated monomers improves the high temperature resistance of the material. The combination of these monomers not only improves the structural integrity of the foam, but also increases the relative inertness of the material, thereby significantly improving the stability of use in extreme environments. Through the synergistic effect of multiple fluorinated monomers, the prepared foam material can effectively resist the erosion of high temperature, solvents and chemical reagents in practical applications, extending the service life of the material.

[0009] Furthermore, the bismaleimide resin includes one or more of N,N'-(4,4-methylenediphenyl)bismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane.

[0010] Through the above technical scheme, the present application optimizes the selection of bismaleimide resin, so that the foam material can achieve high crosslinking degree and excellent thermal stability. Resin components such as N, N'-(4,4-methylenediphenyl) bismaleimide and 2,2'-bis[4-(4-maleimide phenoxy) phenyl] propane can form a dense three-dimensional network structure during the reaction process, further improving the mechanical strength and heat resistance of the material. In addition, the introduction of these resins can improve the toughness of the foam material, thereby showing better stability when subjected to external impact.

[0011] Furthermore, the polymeric MDI includes one or more of PM-200, 44V20, M20S, 5005, MR-200, M200, PAPI 27, and PAPI 13.

[0012] Through the above technical solution, the present application optimizes the components of polymeric MDI. By selecting the above polymeric MDI, a stable bubble structure can be formed during the foaming process, so that the final foam has good density and elasticity. At the same time, the wide adaptability of polymeric MDI enables it to form good compatibility with other ingredients, promoting the uniformity and strength of the composite material. These characteristics enable the prepared foam material to not only meet the expected standards in terms of physical properties, but also meet the needs of long-term use in high temperature and harsh environments.

[0013] Furthermore, the solvent includes one or more of DMF, DMAC, NMP, and DMSO.

[0014] Through the above technical scheme, the present application optimizes the solvent components, and the fluorinated monomer and bismaleimide resin can be effectively dissolved by selecting a suitable solvent to ensure their full mixing and reaction during the reaction process. The polarity and volatility of the solvent affect the foam formation process, and a suitable solvent combination can improve the stability and strength of the foam. At the same time, the use of an appropriate amount of solvent can control the viscosity of the reaction system, optimize the foaming effect of the foam, and make the final material more uniform in structure. In addition, the choice of solvent also plays a key role in the post-processing and curing process of the material, ensuring that the final product has excellent physical and chemical properties.

[0015] Furthermore, the low molecular alcohol includes one or more of CH3OH, C2H5OH, and C3H7OH.

[0016] Through the above technical scheme, the present application can promote the generation and dispersion of gas by adding low molecular alcohol as a reaction medium in the foaming process, thereby forming a uniform and stable foam structure. The introduction of low molecular alcohol also helps to reduce the viscosity of the reaction system, improve the mixing performance, and enable the components to be better integrated. In addition, low molecular alcohol can also affect the phase separation behavior during the foaming process, improve the compressive strength and heat resistance of the foam, thereby enhancing the application performance of the material. Ultimately, the prepared foam material shows better mechanical properties and stability in a variety of industrial applications, meeting high performance requirements.

[0017] Further, the foam stabilizer includes one or more of OFX-0193, OFX-8417, OFX-8468, L550, L540, L580, L668, L5333 Further, the catalyst includes one or more of triethylenediamine, N-methylmorpholine, N,N'-diethylpiperazine, N,N'-diethyl-2-methylpiperazine, N-2-hydroxypropyldimethylmorpholine, triethanolamine, N,N-dimethylethanolamine, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, potassium isooctanoate, potassium oleate, and cobalt isooctanoate.

[0018] Through the above technical solution, the present application selects a suitable catalyst to play a key role in accelerating the reaction speed and improving the cross-linking degree in the preparation of the foam material.

[0019] Furthermore, the foaming agent includes one or more of acetone, water, methanol, ethanol, cyclopentane, and isopentane.

[0020] In the second aspect, the present application provides a method for preparing a high-strength fluorinated polyimide foam material, using the following technical solution: A method for preparing a high-strength fluorinated polyimide foam material comprises the following preparation steps: S1, adding a fluorine-containing monomer into a solvent, and then adding a low molecular alcohol for reflux reaction to collect a transparent solution; S2, adding bismaleimide resin into the transparent solution, keeping the temperature to react and collecting to obtain a prepolymer solution; S3, after the prepolymer solution is cooled to room temperature, a catalyst, a foaming agent, a foam stabilizer, and an initiator are added and stirred evenly to obtain a mixed solution; S4, stirring and mixing the mixed solution and polymeric MDI and injecting them into a mold, foaming and molding at room temperature, standing for treatment, and collecting the foam; S5, taking the foam body and baking and curing it to prepare the high-strength fluorine-containing polyimide foam material.

[0021] Through the above technical scheme, the present application optimizes the preparation method of high-strength fluorinated polyimide foam material, and ensures the successful synthesis of high-strength fluorinated polyimide foam material through precise operation and control conditions, thereby producing high-strength, high-temperature resistant fluorinated polyimide foam material, which is suitable for demanding industrial needs.

[0022] In summary, this application has the following beneficial effects: First, the present application firstly introduces a fluorine-containing monomer to further improve its heat resistance, and then introduces a bismaleimide resin, and makes an interpenetrating network foam material with fluorine-containing polyimide and bismaleimide, so that the mechanical properties of the fluorine-containing polyimide foam are greatly improved, and at the same time, its heat resistance is improved.

[0023] Second, the present application optimizes the components of fluorinated monomers, wherein the addition of fluorinated monomers improves the high temperature resistance of the material. The combination of these monomers not only improves the structural integrity of the foam, but also increases the relative inertness of the material, thereby significantly improving the stability of use in extreme environments. Through the synergistic effect of multiple fluorinated monomers, the prepared foam material can effectively resist the erosion of high temperature, solvents and chemical reagents in practical applications, extending the service life of the material.

[0024] Third, the present application optimizes the selection of bismaleimide resins, so that the foam material can achieve high crosslinking degree and excellent thermal stability. Resin components such as N, N'-(4,4-methylenediphenyl) bismaleimide and 2,2'-bis[4-(4-maleimide phenoxy) phenyl] propane can form a dense three-dimensional network structure during the reaction process, further improving the mechanical strength and heat resistance of the material. In addition, the introduction of these resins can improve the toughness of the foam material, thereby showing better stability when subjected to external impact. DETAILED DESCRIPTION

[0025] The present application is further described in detail below with reference to the embodiments.

[0026] In the examples of the present application, the raw materials and instruments used are as follows, but not limited thereto. Raw materials not otherwise specified are of analytical grade.

[0027] Example 1 A high-strength fluorinated polyimide foam material is prepared from the following substances: 23kg hexafluorodianhydride, 11kg 4,4'-oxybis[3-(oxytrifluoromethyl)aniline], 38kg DMAC, 1.8kg CH3OH, 15kg N,N'-(4,4-methylenediphenyl)bismaleimide, 0.3kg triethylenediamine, 0.5kg N,N-dimethylethanolamine, 0.8kg stannous octoate, 6kg water, 8kg OFX-8417, 0.2kg azobisisobutyronitrile and 8kg 44V20 polymeric MDI.

[0028] A high-strength fluorinated polyimide foam material comprises the following preparation steps: S1, add 23kg hexafluorodianhydride and 11kg 4,4'-oxybis[3-(oxytrifluoromethyl)aniline] to 38kg DMAC, then add 1.8kg CH3OH and reflux for reaction at 70°C for 3h to obtain a transparent solution; S2, adding 15 kg of N, N'-(4,4-methylenediphenyl) bismaleimide to the above transparent solution for further reaction at a temperature of 80°C for 1.5 h to obtain a prepolymer solution; S3, cooling the prepolymer solution to room temperature, adding 0.3 kg triethylenediamine, 0.5 kg N, N-dimethylethanolamine, 0.8 kg stannous octoate, 6 kg water, 8 kg OFX-8417, and 0.2 kg azobisisobutyronitrile and stirring evenly to obtain a mixed solution; S4, the mixed solution and 28kg 44V20 polymeric MDI were mixed at a high speed of 1500 rpm for 13 seconds, injected into a mold, foamed at room temperature, and allowed to stand for 20 minutes; S5. Finally, the foam is placed at a temperature of 210° C. for baking and curing for 5 hours to prepare the high-strength fluorine-containing polyimide foam material.

[0029] Example 2 A high-strength fluorinated polyimide foam material is prepared from the following substances: 25kg hexafluorodianhydride, 15kg 2-(trifluoromethyl)-1,4-p-phenylenediamine, 35kg DMF, 2kg ethanol, 10kg bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 0.2kg triethylenediamine, 0.3kg N,N-dimethylethanolamine, 0.6kg stannous octoate, 3kg water, 6kg OFX-198, 30kg M20S polymeric MDI.

[0030] A high-strength fluorinated polyimide foam material comprises the following preparation steps: S1, add 25kg hexafluorodianhydride and 15kg 2-(trifluoromethyl)-1,4-p-phenylenediamine to 35kg DMF, then add 2kg ethanol to reflux reaction at 80°C for 4h to obtain a transparent solution; S2, adding 10 kg of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane to the above transparent solution for further reaction at a temperature of 75° C. for 2 h to obtain a prepolymer solution; S3, cooling the prepolymer solution to room temperature, adding 0.2 kg triethylenediamine, 0.3 kg N, N-dimethylethanolamine, 0.6 kg stannous octoate, 3 kg water, and 6 kg OFX-198, stirring evenly to obtain a mixed solution; S4, the mixed solution and 30kg M20S polymeric MDI were mixed at a high speed of 1200rpm for 15s, injected into a mold, foamed at room temperature, and allowed to stand for 15min; S5. Finally, the foam is placed at a temperature of 210° C. for baking and curing for 3.5 hours to prepare the high-strength fluorine-containing polyimide foam material.

[0031] Example 3 A high-strength fluorinated polyimide foam material is prepared from the following substances: 25kg hexafluorodianhydride, 15kg 2-(trifluoromethyl)-1,4-p-phenylenediamine, 35kg DMF, 2kg ethanol, 10kg bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 0.2kg triethylenediamine, 0.3kg N,N-dimethylethanolamine, 0.6kg stannous octoate, 3kg water, 6kg OFX-198, 30kg M20S polymeric MDI.

[0032] A high-strength fluorinated polyimide foam material comprises the following preparation steps: S1, add 25kg hexafluorodianhydride and 15kg 2-(trifluoromethyl)-1,4-p-phenylenediamine to 35kg DMF, then add 2kg ethanol to reflux reaction at 80°C for 4h to obtain a transparent solution; S2, adding 10 kg of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane to the above transparent solution for further reaction at a temperature of 75° C. for 2 h to obtain a prepolymer solution; S3, cooling the prepolymer solution to room temperature, adding 0.2 kg triethylenediamine, 0.3 kg N, N-dimethylethanolamine, 0.6 kg stannous octoate, 3 kg water, and 6 kg OFX-198, stirring evenly to obtain a mixed solution; S4, the mixed solution and 30kg M20S polymeric MDI were mixed at a high speed of 1200rpm for 15s, injected into a mold, foamed at room temperature, and allowed to stand for 15min; S5. Finally, the foam is placed at a temperature of 210° C. for baking and curing for 3.5 hours to prepare the high-strength fluorine-containing polyimide foam material.

[0033] It should be noted that: The fluorine-containing monomers used in the present application include, but are not limited to, one or more of hexafluorodianhydride, 4,4'-oxybis[3-(trifluoromethyl)aniline], 4,4'-oxybis[3-(oxytrifluoromethyl)aniline], 4,4'-oxybis[3-fluoroaniline], 2-(trifluoromethyl)-1,4-p-phenylenediamine, 2-(oxytrifluoromethyl)-1,4-p-phenylenediamine, 2-fluoro-1,4-p-phenylenediamine, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 2,2'-bis(oxytrifluoromethyl)diaminobiphenyl and 2,2'-bis(fluoro)diaminobiphenyl.

[0034] The bismaleimide resin used in the present application includes but is not limited to one or more of N,N'-(4,4-methylenediphenyl)bismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane.

[0035] The polymeric MDI used in this application includes but is not limited to one or more of PM-200, 44V20, M20S, 5005, MR-200, M200, PAPI 27, and PAPI 13.

[0036] The solvents used in the present application include, but are not limited to, one or more of DMF, DMAC, NMP, and DMSO.

[0037] The low molecular alcohols used in the present application include one or more of CH3OH, C2H5OH, and C3H7OH.

[0038] The foam stabilizers used in this application include but are not limited to one or more of OFX-0193, OFX-8417, OFX-8468, L550, L540, L580, L668, and L5333. The catalyst used in the present application includes, but is not limited to, one or more of triethylenediamine, N-methylmorpholine, N,N'-diethylpiperazine, N,N'-diethyl-2-methylpiperazine, N-2-hydroxypropyldimethylmorpholine, triethanolamine, N,N-dimethylethanolamine, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, potassium isooctanoate, potassium oleate, and cobalt isooctanoate.

[0039] The foaming agent used in the present application includes, but is not limited to, one or more of acetone, water, methanol, ethanol, cyclopentane, and isopentane.

[0040] Comparative Example Commercially available polyimide foam material.

[0041] Performance Testing The high-strength fluorine-containing polyimide foam material and the polyimide foam material prepared in Examples 1-7 were subjected to performance tests: (1) Density; (2) 5% thermal weight loss temperature: The test was carried out using the thermal gravimetric analysis (TGA) method.

[0042] (3) Tensile strength and 180°C tensile strength: tested in accordance with GB / T 6344--2008.

[0043] The results are shown in Table 1 below: Table 1 Performance test table

[0044] From the above examples 1-3 and comparative example 1, combined with the test results in Table 1, it can be found that: The present application firstly introduces a fluorine-containing monomer to further improve its temperature resistance, and then introduces a bismaleimide resin, and makes an interpenetrating network foam material from fluorine-containing polyimide and bismaleimide, thereby greatly improving the mechanical properties of the fluorine-containing polyimide foam.

[0045] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.

[0046] All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of a conflict, the definition in this specification shall prevail.

[0047] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.

[0048] In the context of the present specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.

Claims

1. A high-strength fluorinated polyimide foam material, characterized in that: The composition includes the following materials in parts by weight: Fluorine-containing monomer: 20-50 parts; 10-20 parts of bismaleimide; 20-40 parts of polymeric MDI; 10-40 parts of solvent; 1-5 parts of low molecular weight alcohol; Initiator 0.1-1.0 part; 3-8 parts of foam stabilizer; Catalyst 0.1-3.0 parts; 3-10 parts of foaming agent.

2. A high-strength fluorinated polyimide foam material according to claim 1, characterized in that: The fluorine-containing monomer includes one or more of hexafluorodianhydride, 4,4'-oxybis[3-(trifluoromethyl)aniline], 4,4'-oxybis[3-(oxytrifluoromethyl)aniline], 4,4'-oxybis[3-fluoroaniline], 2-(trifluoromethyl)-1,4-p-phenylenediamine, 2-(oxytrifluoromethyl)-1,4-p-phenylenediamine, 2-fluoro-1,4-p-phenylenediamine, 2,2'-bis(trifluoromethyl)diaminobiphenyl, 2,2'-bis(oxytrifluoromethyl)diaminobiphenyl and 2,2'-bis(fluoro)diaminobiphenyl.

3. The high-strength fluorinated polyimide foam material according to claim 1, characterized in that: The bismaleimide resin includes one or more of N,N'-(4,4-methylenediphenyl)bismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, and bis(3-ethyl-5-methyl-4-maleimidephenyl)methane.

4. The high-strength fluorinated polyimide foam material according to claim 1, characterized in that: The polymeric MDI includes one or more of PM-200, 44V20, M20S, 5005, MR-200, M200, PAPI 27, and PAPI 13.

5. The high-strength fluorinated polyimide foam material according to claim 1, characterized in that: The solvent includes one or more of DMF, DMAC, NMP and DMSO.

6. The high-strength fluorinated polyimide foam material according to claim 1, characterized in that: The low molecular alcohol includes one or more of CH3OH, C2H5OH, and C3H7OH.

7. The high-strength fluorinated polyimide foam material according to claim 1, characterized in that: The foam stabilizer includes one or more of OFX-0193, OFX-8417, OFX-8468, L550, L540, L580, L668, and L5333.

8. The high-strength fluorinated polyimide foam material according to claim 1, characterized in that: The catalyst includes one or more of triethylenediamine, N-methylmorpholine, N,N'-diethylpiperazine, N,N'-diethyl-2-methylpiperazine, N-2-hydroxypropyldimethylmorpholine, triethanolamine, N,N-dimethylethanolamine, stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, potassium isooctanoate, potassium oleate, and cobalt isooctanoate.

9. The high-strength fluorinated polyimide foam material according to claim 1, characterized in that: The foaming agent includes one or more of acetone, water, methanol, ethanol, cyclopentane and isopentane.

10. The method for preparing a high-strength fluorinated polyimide foam material according to any one of claims 1 to 9, characterized in that: The method comprises the following preparation steps: S1, adding a fluorine-containing monomer into a solvent, and then adding a low molecular alcohol for reflux reaction to collect a transparent solution; S2, adding bismaleimide resin into the transparent solution, keeping the temperature to react and collecting to obtain a prepolymer solution; S3, after the prepolymer solution is cooled to room temperature, a catalyst, a foaming agent, a foam stabilizer, and an initiator are added and stirred evenly to obtain a mixed solution; S4, stirring and mixing the mixed solution and polymeric MDI and injecting them into a mold, foaming and molding at room temperature, standing for treatment, and collecting the foam; S5, taking the foam body and baking and curing it to prepare the high-strength fluorine-containing polyimide foam material.

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