High-temperature-resistant azacyclo polyarylether resin foam material and preparation method thereof

Abstract

The invention relates to the technical field of polymer foam, in particular to a high-temperature-resistant azacyclo-polyarylether resin foam material and a preparation method thereof.The high-temperature-resistant azacyclo-polyarylether resin foam material comprises azacyclo-polyarylether resin, and the azacyclo-polyarylether resin is linear-structure polyarylether resin; the nitrogen heterocyclic polyarylether resin has a phthalazinone structure. The azacyclo-polyarylether resin foam material provided by the invention comprises a phthalazinone structure, so that the foaming ratio of the azacyclo-polyarylether resin foam material is relatively high, the linear-structure polyarylether resin foam material with relatively high foaming ratio is obtained, and polyarylether resin with a branched structure is not needed for foaming; therefore, the preparation process of the polyarylether resin foam material is simple.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer foams, in particular to a high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material and a preparation method thereof. Background Art

[0002] In numerous engineering applications, high-temperature foams become essential components when ambient temperatures soar to levels unbearable for conventional plastics (e.g., sustained temperatures exceeding 150°C, or even reaching 250°C or higher). These materials must maintain their core functions—whether insulation, shock absorption, sealing, insulation, or lightweight support—under harsh thermal conditions without softening, melting, decomposing, or losing structural integrity. Common commercial foams, such as polypropylene foam (PP foam) and polystyrene foam, typically have heat resistance limits below 100°C, far from sufficient to withstand these high-temperature challenges. They can severely deform or even flow at high temperatures. Polymethacrylimide foam (PMI) is a type of high-temperature foam with an operating temperature of around 180°C and is widely used in cutting-edge technologies such as aerospace. Another high-performance type, polyimide foam (PI foam), also offers high-temperature resistance, withstanding temperatures exceeding 200°C. However, PI foam is typically a thermoset material, making processing complex and costly. Both PMI and PI foams have relatively limited chemical resistance (particularly to strong alkalis and hydrolysis), limiting their application in certain applications.

[0003] Polyarylene ether has excellent heat resistance, low moisture absorption and mechanical properties. Thermoplastic polyarylene ether foam materials are more flexible to process and can be manufactured into complex shapes through processes such as melt extrusion, injection molding or supercritical foaming, significantly reducing production difficulty and cost. Compared with PP foam and polystyrene foam, it has rolling-grade high-temperature resistance (long-term stable use in a 250°C environment) and excellent flame retardancy (LOI>35%, self-extinguishing when away from fire); secondly, it has extremely excellent chemical corrosion resistance and can resist the erosion of various oils, solvents, acids (except concentrated sulfuric acid and nitric acid) and alkalis for a long time. This combination of high strength, high temperature resistance, excellent chemical resistance, easy processing and long-term stability makes high-temperature resistant polyarylene ether foam a necessary and irreplaceable solution in many key areas.

[0004] Conventional linear structure (without long chain branches) polyarylene ether resins (such as commercially available polyetheretherketone and polyetherketoneketone) have low melt strength and cannot be foamed or have a low foaming ratio. Therefore, branched structure (with long chain branches) polyarylene ether resins are generally used for foaming in the prior art. The synthesis of branched structure polyarylene ether resins uses a polymerization reaction of difunctional monomers and trifunctional monomers, which is prone to gelation and difficult to control the polymerization system, thereby making the preparation process of polyarylene ether resin foam materials complicated.

[0005] Therefore, how to obtain a foam material of a linear polyarylene ether resin with a high foaming ratio is a technical problem to be solved urgently in this field. Summary of the Invention

[0006] In view of the above-mentioned deficiencies in the prior art, the present invention aims to provide a high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material and a preparation method thereof. The nitrogen heterocyclic polyarylene ether resin foam material provided by the present invention includes a diazinone structure, which can make its foaming ratio higher, thereby obtaining a linear structure polyarylene ether resin foam material with a higher foaming ratio, without the need to use a branched structure polyarylene ether resin for foaming, thereby simplifying the preparation process of the polyarylene ether resin foam material.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, wherein the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material comprises a nitrogen heterocyclic polyarylene ether resin, wherein the nitrogen heterocyclic polyarylene ether resin is a linear structure polyarylene ether resin, and the nitrogen heterocyclic polyarylene ether resin has a diazinone structure.

[0009] The nitrogen heterocyclic polyarylene ether resin foam material provided by the present invention can have a higher foaming ratio by including a diazinone structure, thereby obtaining a linear polyarylene ether resin foam material with a higher foaming ratio. There is no need to use a branched polyarylene ether resin for foaming, thereby simplifying the preparation process of the polyarylene ether resin foam material.

[0010] Furthermore, the chemical structural formula of the diazonone is as follows:

[0011]

[0012] And / or, the nitrogen heterocyclic polyaryl ether resin includes at least one of phthalazinone polyaryl ether sulfone, phthalazinone polyaryl ether ketone, phthalazinone polyaryl ether sulfone ketone, phthalazinone polyaryl ether sulfone ketone ketone, fluorenyl phthalazinone-containing polyaryl ether sulfone, fluorenyl phthalazinone-containing polyaryl ether ketone, fluorenyl phthalazinone-containing polyaryl ether sulfone ketone, fluorenyl phthalazinone-containing polyaryl ether sulfone ketone, fluorenyl phthalazinone-containing polyaryl ether nitrile ketone, dimethyl phthalazinone-containing polyaryl ether sulfone, dimethyl phthalazinone-containing polyaryl ether ketone, dimethyl phthalazinone-containing polyaryl ether sulfone ketone, dimethyl phthalazinone-containing polyaryl ether sulfone ketone, and polyaryl ether containing a dimethyl phthalazinone structure.

[0013] Furthermore, the poly(phenylene ether sulfone) has a chemical structure shown in Formula A:

[0014]

[0015] Where n ≥ 1 and is an integer;

[0016] And / or, the poly(aryletherketone) has a chemical structure shown in Formula B:

[0017]

[0018] Where n ≥ 1 and is an integer;

[0019] And / or, the poly(phenylene ether sulfone ketone) has a chemical structure shown in Formula C: (sulfone to ketone molar ratio 100:1 to 1:100):

[0020]

[0021] Wherein, n≥1, m≥1 and are integers, and the ratio of n to m is 100:1 to 1:100;

[0022] And / or, the poly(phenylene ether sulfone ketone ketone) has a chemical structure shown in Formula D:

[0023]

[0024] Wherein, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of n to m is 100:1 to 1:100;

[0025] And / or, the fluorenyl-containing poly(aryl ether sulfone) has a chemical structure shown in Formula E:

[0026]

[0027] Wherein, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of m to n is 100:1 to 1:100;

[0028] And / or, the fluorenyl-containing poly(aryl ether ketone) has a chemical structure shown in Formula F:

[0029]

[0030] Wherein, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of m to n is 100:1 to 1:100;

[0031] And / or, the fluorenyl-containing poly(aryl ether sulfone ketone) has a chemical structure shown in Formula G:

[0032]

[0033] wherein n ≥ 1 and is an integer, m ≥ 1 and is an integer, x ≥ 1 and is an integer, y ≥ 1 and is an integer, the ratio of m+y to n+x is 100:1 to 1:100, and the ratio of m+n to x+y is 100:1 to 1:100;

[0034] And / or, the fluorenyl-containing poly(aryl ether sulfone ketone ketone) has a chemical structure shown in Formula H:

[0035]

[0036] wherein n ≥ 1 and is an integer, m ≥ 1 and is an integer, x ≥ 1 and is an integer, y ≥ 1 and is an integer, the ratio of m+n to x+y is 100:1 to 1:100, and the ratio of x+n to m+y is 100:1 to 1:100;

[0037] And / or, the fluorenyl-containing naphthalene biphenyl poly (aryl ether nitrile ketone) has a chemical structure shown in the following formula:

[0038]

[0039] Wherein, x1 ≥ 1 and is an integer, y1 ≥ 1 and is an integer, x ≥ 1 and is an integer, y ≥ 1 and is an integer, the ratio of y+y1 to x+x1 is 100:1 to 1:100, and the ratio of x+y to x1+y1 is 100:1 to 1:100;

[0040] And / or, the dimethylphthalazinyl poly(aryl ether sulfone) containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula I, the dimethylphthalazinyl poly(aryl ether ketone) containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula J, the dimethylphthalazinyl poly(aryl ether sulfone ketone) containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula K, and the dimethylphthalazinyl poly(aryl ether sulfone ketone ketone) containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula L:

[0041]

[0042] Wherein, in the chemical structural formula I, n ≥ 1 and is an integer; in the chemical structural formula J, n ≥ 1 and is an integer; in the chemical structural formula K, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of n to m is 100:1 to 1:100; in the chemical structural formula L, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of n to m is 100:1 to 1:100;

[0043] And / or, the polyarylene ether containing a phthalazinone structure has at least one of the following chemical structures:

[0044]

[0045] In formula (1), formula (2) and formula (3), the structure of R is at least one of the following structures:

[0046] n≥1 and is an integer;

[0047] Where n ≥ 1 and is an integer;

[0048] Wherein, n≥1 and is an integer, m≥1 and is an integer, and the ratio of n to m is 100:1 to 1:100.

[0049]

[0050] In formula (4), formula (5) and formula (6), the structure of R is at least one of the following structures:

[0051]

[0052] n≥1 and is an integer.

[0053] Furthermore, the weight average molecular weight of the nitrogen heterocyclic polyarylene ether resin is 25000 to 45000 g / mol;

[0054] And / or, the density of the high temperature resistant nitrogen heterocyclic polyarylether resin foam material is 30 to 1000 kg / m 3 ;

[0055] And / or, the glass transition temperature of the high temperature resistant nitrogen heterocyclic polyarylene ether resin is 262° C. to 388° C.;

[0056] And / or, the polymerization monomers of the nitrogen heterocyclic polyarylene ether resin include a dihalogen monomer and a difunctional monomer containing a diazinone biphenyl structure, or a dihalogen monomer, a difunctional monomer containing a diazinone biphenyl structure and a bisphenol monomer containing a fluorenyl structure.

[0057] In a second aspect, the present invention provides a method for preparing the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material as described in the first aspect, the preparation method comprising the following steps:

[0058] S1. Hot-pressing and curing the nitrogen heterocyclic polyarylene ether resin powder under a protective gas atmosphere to obtain a prefabricated plate;

[0059] S2. Placing the prefabricated plate in a reactor in a mixed medium environment of supercritical carbon dioxide and nitrogen for physical foaming, and finally rapidly releasing the pressure to normal pressure to complete the foaming, thereby obtaining the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material.

[0060] Furthermore, in step S1, the protective gas includes nitrogen, and the average particle size of the nitrogen heterocyclic polyarylene ether resin powder is 25 μm-100 μm;

[0061] And / or, in step S1, the temperature of the hot pressing curing is 40-60°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylene ether resin, the pressure of the hot pressing curing is 2-6 MPa, and the heat preservation and pressure holding time of the hot pressing curing is 10-30 minutes.

[0062] Furthermore, in step S2, the volume ratio of the supercritical carbon dioxide to nitrogen is 9:1-7:3.

[0063] Furthermore, in step S2, the physical foaming in a supercritical carbon dioxide and nitrogen mixed medium environment includes: insulating and pressurizing the prefabricated board in the presence of a supercritical carbon dioxide and nitrogen mixed gas, the insulation and pressure-maintaining temperature being 15-45°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, the insulation and pressure-maintaining pressure being 15-40MPa, and the insulation and pressure-maintaining time being 60-120 minutes.

[0064] Furthermore, in step S2, the pressure relief rate is 40-85 MPa / s.

[0065] Furthermore, after rapidly releasing the pressure to normal pressure, the preparation method further comprises the following steps:

[0066] Open the kettle, take out the sample and air cool it to room temperature.

[0067] Compared with the prior art, the present invention has at least one of the following advantages:

[0068] (1) The nitrogen heterocyclic polyarylene ether resin foam material provided by the present invention can have a higher foaming ratio by including a diazinone structure, thereby obtaining a linear structure polyarylene ether resin foam material with a higher foaming ratio, without the need to use a branched structure polyarylene ether resin for foaming, thereby simplifying the preparation process of the polyarylene ether resin foam material.

[0069] (2) The nitrogen heterocyclic polyarylether resin foam material provided by the present invention belongs to a linear thermoplastic resin. The Tg of this series of resins is ≥262°C. Among them, the polyarylethersulfone with a diphenylsulfone-based phthalazinone structure has a Tg of up to 388°C and can be used above 250°C. The maximum operating temperature is 350°C. It is inherently flame retardant and has an oxygen index of ≥35, making it more suitable for extreme conditions.

[0070] (3) The nitrogen heterocyclic polyarylether resin foam material provided by the present invention has dense and uniform pores without obvious defects, has excellent pore structure stability, and can effectively resist pore collapse and deformation. The prepared foam material exhibits a highly complete closed-cell structure, with uniform pore morphology and clear boundaries, and no collapse, rupture or fusion phenomenon. The pore wall has sufficient mechanical strength and toughness, and can maintain its geometric shape and connectivity under various stresses (such as compression, impact, and thermal stress).

[0071] (4) In the foaming step, the present invention adopts a CO2 / N2 mixed gas to synergistically optimize the key steps of the foaming process - nucleation, growth and stabilization: CO2 exerts its high solubility and strong plasticizing effect to effectively plasticize the polymer matrix, laying the foundation for foaming. N2, with its low solubility and low diffusion coefficient, acts as a high-efficiency nucleating agent to promote the formation of high-density, small-sized initial cell nuclei. It acts as a growth regulator and stabilizer to slow down the cell growth rate, inhibit gas diffusion and bubble formation, and ensure that the cell structure remains uniform, fine, and closed before solidification. This synergistic effect directly leads to a significant improvement in the quality of the cell structure (higher density, smaller size, more uniform distribution) and the mechanical properties of the final foam material (higher strength and modulus). At the same time, it significantly broadens the range of feasible process parameters, making the production process more stable and easier to control, which is conducive to industrial application. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0073] Figure 1 The infrared spectrum of PPESK prepared in Example 1 of the present invention;

[0074] Figure 2 This is the H NMR spectrum of the PPESK prepared in Example 1 of the present invention;

[0075] Figure 3 This is the DSC test chart of the PPESK prepared in Example 1 of the present invention;

[0076] Figure 4 This is a sample image of the PPESK foam material prepared in Example 1 of the present invention;

[0077] Figure 5 This is a scanning electron microscope image of the PPESK foam material prepared in Example 1 of the present invention;

[0078] Figure 6 This is the infrared spectrum of PPFENK prepared in Example 2 of the present invention;

[0079] Figure 7 This is the H NMR spectrum of the PPFENK prepared in Example 2 of the present invention;

[0080] Figure 8 This is the DSC test chart of PPFENK prepared in Example 2 of the present invention;

[0081] Figure 9 This is a sample image of the PPFENK foam material prepared in Example 2 of the present invention;

[0082] Figure 10 This is a scanning electron microscope image of the PPFENK foam material prepared in Example 2 of the present invention;

[0083] Figure 11 This is the infrared spectrum of PPESKK prepared in Example 3 of the present invention;

[0084] Figure 12 This is the H NMR spectrum of PPESKK prepared in Example 3 of the present invention;

[0085] Figure 13 This is the DSC test chart of PPESKK prepared in Example 3 of the present invention;

[0086] Figure 14 This is a sample image of the PPESKK foam material prepared in Example 3 of the present invention;

[0087] Figure 15 This is a scanning electron microscope image of the PPESK foam material prepared in Example 3 of the present invention;

[0088] Figure 16 This is the infrared spectrum of PBPENK prepared in Example 4 of the present invention;

[0089] Figure 17 This is the H NMR spectrum of PBPENK prepared in Example 4 of the present invention;

[0090] Figure 18 This is the DSC test chart of PBPENK prepared in Example 4 of the present invention;

[0091] Figure 19 This is a sample image of the PBPENK foam material prepared in Example 4 of the present invention;

[0092] Figure 20 This is a scanning electron microscope image of the PBPENK foam material prepared in Example 4 of the present invention. DETAILED DESCRIPTION

[0093] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Those skilled in the art should understand that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. The process parameters for which specific conditions are not specified in the following examples are generally based on conventional conditions. Unless otherwise specified, all raw materials can be purchased from the market or are commonly used materials in this industry.

[0094] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to form one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed in the present invention.

[0095] In a first aspect, the present invention provides a high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, wherein the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material comprises a nitrogen heterocyclic polyarylene ether resin, wherein the nitrogen heterocyclic polyarylene ether resin is a linear structure polyarylene ether resin, and the nitrogen heterocyclic polyarylene ether resin has a diazinone structure.

[0096] The nitrogen heterocyclic polyarylene ether resin foam material provided by the present invention includes a diazinone structure. The twisted non-coplanar structure of the diazinone makes the molecular chains of the polymer highly entangled, so that the polymer melt strength is high, and the foaming ratio can be high. The linear structure polyarylene ether resin foam material with a high foaming ratio is obtained, and there is no need to use a branched structure polyarylene ether resin for foaming, thereby simplifying the preparation process of the polyarylene ether resin foam material.

[0097] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, the chemical structural formula of the diazonone is as follows:

[0098] In the above-mentioned high temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the nitrogen heterocyclic polyarylether resin includes phthalazinone polyarylether sulfone, phthalazinone polyarylether ketone, phthalazinone polyarylether sulfoneketone, phthalazinone polyarylether sulfoneketoneketone, fluorenyl phthalazinone polyarylether sulfone, fluorenyl phthalazinone polyarylether ketone, fluorenyl phthalazinone polyarylether sulfoneketone, fluorenyl phthalazinone polyarylether sulfoneketone, fluorenyl phthalazinone polyarylether sulfoneketone, fluorenyl phthalazinone polyarylether nitrile ketone, dimethyl ... At least one of polyaryl ether sulfone containing naphthalene biphenyl, polyaryl ether ketone containing dimethyl naphthalene biphenyl, polyaryl ether sulfone ketone containing dimethyl naphthalene biphenyl, polyaryl ether sulfone ketone ketone containing dimethyl naphthalene biphenyl, and polyaryl ether containing a dimethyl naphthalene biphenyl structure; in order to further significantly improve the foaming ratio, polyaryl ether sulfone containing fluorenyl naphthalene biphenyl, polyaryl ether ketone containing fluorenyl naphthalene biphenyl, polyaryl ether sulfone ketone containing fluorenyl naphthalene biphenyl, polyaryl ether sulfone ketone containing fluorenyl naphthalene biphenyl, or polyaryl ether nitrile ketone containing fluorenyl naphthalene biphenyl is preferred.

[0099] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the polyarylethersulfone phthalazinone has a chemical structure shown in Formula A:

[0100]

[0101] Wherein, n≥1 and is an integer.

[0102] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the polyaryletherketone phthalazinone has a chemical structure shown in Formula B:

[0103]

[0104] Wherein, n≥1 and is an integer.

[0105] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the polyarylethersulfoneketone phthalazinone has a chemical structure shown in Formula C: (sulfoneketone molar ratio 100:1 to 1:100):

[0106]

[0107] Wherein, n≥1, m≥1 and are integers, and the ratio of n to m is 100:1 to 1:100, for example, it can be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100.

[0108] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the polyarylethersulfoneketoneketone of phthalazinone has a chemical structure shown in Formula D (the molar ratio of sulfone to ketoneketone is 100:1 to 1:100):

[0109]

[0110] Wherein, n≥1 and is an integer, m≥1 and is an integer, and the ratio of n to m is 100:1 to 1:100, for example, it can be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100.

[0111] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the fluorenyl-containing phthalazinone polyarylether sulfone has a chemical structure shown in Formula E (the molar ratio of diazinone structural monomer to bisphenol fluorene is 100:1 to 1:100):

[0112]

[0113] Wherein, n≥1 and is an integer, m≥1 and is an integer, and the ratio of m to n is 100:1 to 1:100, for example, it can be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100.

[0114] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the fluorenyl-containing phthalazinone polyaryletherketone has a chemical structure shown in Formula F (the molar ratio of diazinone structural monomer to bisphenol fluorene is 100:1 to 1:100):

[0115]

[0116] Wherein, n≥1 and is an integer, m≥1 and is an integer, and the ratio of m to n is 100:1 to 1:100, for example, it can be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100.

[0117] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the fluorenyl-containing phthalazinone polyarylether sulfoneketone has a chemical structure shown in Formula G (the molar ratio of diazinone structural monomer to bisphenol fluorene is 100:1 to 1:100, and the molar ratio of sulfone to ketone is 100:1 to 1:100):

[0118]

[0119] wherein n≥1 and is an integer, m≥1 and is an integer, x≥1 and is an integer, y≥1 and is an integer, the ratio of m+y to n+x is 100:1 to 1:100, for example, it may be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100, and the ratio of m+n to x+y is 100:1 to 1:100, for example, it may be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100.

[0120] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the fluorenyl-containing phthalazinone polyarylether sulfoneketoneketone has a chemical structure shown in Formula H (the molar ratio of diazinone structural monomer to bisphenol fluorene is 100:1 to 1:100, and the molar ratio of sulfone to ketoneketone is 100:1 to 1:100):

[0121]

[0122] wherein n≥1 and is an integer, m≥1 and is an integer, x≥1 and is an integer, y≥1 and is an integer, the ratio of m+n to x+y is 100:1 to 1:100, for example, it may be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100, and the ratio of x+n to m+y is 100:1 to 1:100, for example, it may be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100.

[0123] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, the fluorenyl-containing naphthalene biphenyl polyarylene ether nitrile ketone has a chemical structure shown in the following formula:

[0124]

[0125] Among them, x1≥1 and is an integer, y1≥1 and is an integer, x≥1 and is an integer, y≥1 and is an integer, the ratio of y+y1 to x+x1 is 100:1 to 1:100, for example, it can be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, 1:100, and the ratio of x+y to x1+y1 is 100:1 to 1:100, for example, it can be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, 1:100.

[0126] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, the dimethylphthalazinyl polyarylether sulfone containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula I, the dimethylphthalazinyl polyarylether ketone containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula J, the dimethylphthalazinyl polyarylether sulfoneketone containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula K (sulfone to ketone molar ratio of 100:1 to 1:100), and the dimethylphthalazinyl polyarylether sulfoneketoneketone containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula L (sulfone to ketone to ketone molar ratio of 100:1 to 1:100):

[0127]

[0128] Wherein, in the chemical structural formula I, n ≥ 1 and is an integer; in the chemical structural formula J, n ≥ 1 and is an integer; in the chemical structural formula K, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of n to m is 100:1 to 1:100, for example, it can be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100; in the chemical structural formula L, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of n to m is 100:1 to 1:100, for example, it can be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100.

[0129] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, the polyarylene ether containing a phthalazinone structure has at least one of the following chemical structures:

[0130]

[0131] In formula (1), formula (2) and formula (3), the structure of R is at least one of the following structures:

[0132] n≥1 and is an integer;

[0133] Where n ≥ 1 and is an integer;

[0134] Wherein, n≥1 and is an integer, m≥1 and is an integer, and the ratio of n to m is 100:1 to 1:100, for example, it can be 100:1, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 10:90, or 1:100.

[0135]

[0136] In formula (4), formula (5) and formula (6), the structure of R is at least one of the following structures:

[0137]

[0138] n≥1 and is an integer.

[0139] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, the weight average molecular weight of the nitrogen heterocyclic polyarylene ether resin is 25,000 to 45,000 g / mol, for example, it can be 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol or 45,000 g / mol.

[0140] In the above-mentioned high temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, the density of the high temperature resistant nitrogen heterocyclic polyarylene ether resin foam material is 30 to 1000 kg / m 3 , for example, it can be 30kg / m 3 , 100kg / m 3 , 200kg / m 3 , 400kg / m 3 、600kg / m 3 , 800kg / m 3 or 1000kg / m 3 .

[0141] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, the glass transition temperature (Tg) of the high-temperature resistant nitrogen heterocyclic polyarylene ether resin is 262°C to 388°C, for example, it can be 262°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C or 388°C.

[0142] In the aforementioned high-temperature resistant nitrogen-heterocyclic polyarylene ether resin foam material, as an optional embodiment, the polymerization monomers of the nitrogen-heterocyclic polyarylene ether resin include a dihalogen monomer and a difunctional monomer containing a phthalazinone biphenyl structure, or a dihalogen monomer, a difunctional monomer containing a phthalazinone biphenyl structure, and a bisphenol monomer containing a fluorenyl structure. The present invention does not limit the specific structures of the dihalogen monomer, the difunctional monomer containing a phthalazinone biphenyl structure, and the bisphenol monomer containing a fluorenyl structure, as long as the nitrogen-heterocyclic polyarylene ether resin of the present invention can be obtained through polymerization.

[0143] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, the preparation method of the nitrogen heterocyclic polyarylene ether resin comprises the following steps:

[0144] The polymerization monomer of the nitrogen heterocyclic polyarylene ether resin, a catalyst and a water-carrying agent are added to a reaction solvent, the water-carrying agent is used to carry out water under heating conditions, the water-carrying agent is then removed, and the reaction is carried out by heating. As the viscosity of the reaction solution increases, the solvent is gradually added dropwise. When the viscosity of the reaction solution no longer increases, the reaction solution is poured into a dilute acid solution to terminate the reaction. After post-treatment, the nitrogen heterocyclic polyarylene ether resin is obtained.

[0145] In the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, during the preparation process of the nitrogen heterocyclic polyarylene ether resin, the catalyst includes potassium carbonate; the water-carrying agent includes toluene; the reaction solvent includes NMP; the water-carrying temperature is 130-150°C, and the time is 2-5h; the reaction temperature is 170-190°C; and the post-treatment includes: crushing the obtained solid polymer, washing it with water and ethanol, and finally drying it.

[0146] In a second aspect, the present invention provides a method for preparing the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material as described in the first aspect, the preparation method comprising the following steps:

[0147] S1. Hot-pressing and curing the nitrogen heterocyclic polyarylene ether resin powder under a protective gas atmosphere to obtain a prefabricated plate;

[0148] S2. Placing the prefabricated plate in a reactor in a supercritical carbon dioxide (scCO2) and nitrogen mixed medium environment for physical foaming, and finally rapidly releasing the pressure to normal pressure to complete the foaming, thereby obtaining the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material.

[0149] In polyarylene ether foaming, the core advantage of a CO2 / N2 gas mixture over CO2 alone lies in its ability to synergistically optimize the key steps of the foaming process—nucleation, growth, and stabilization. CO2 leverages its high solubility and strong plasticizing effect to effectively plasticize the polymer matrix, laying the foundation for foaming. N2, with its low solubility and low diffusion coefficient, acts as a highly efficient nucleating agent, promoting the formation of high-density, small-sized initial cell nuclei. It also acts as a growth regulator and stabilizer, slowing cell growth and inhibiting gas diffusion and coalescence, ensuring a uniform, dense, and closed-cell structure before solidification.

[0150] This synergistic effect directly leads to a significant improvement in the quality of the foam structure (higher density, smaller size, and more uniform distribution) and the mechanical properties of the final foam material (higher strength and modulus). At the same time, it significantly broadens the range of feasible process parameters, making the production process more stable and easier to control, which is conducive to industrial application.

[0151] In the above-mentioned method for preparing high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, in step S1, the protective gas includes nitrogen, and the average particle size of the nitrogen heterocyclic polyarylene ether resin powder is 25μm-100μm (for example, it can be 25μm, 30μm, 40μm, 45μm, 50μm, 70μm or 100μm), particularly preferably 25μm-45μm.

[0152] In the preparation method of the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, in step S1, the temperature of the hot pressing curing is 40-60°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin (for example, it can be 40°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 45°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 50°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 55°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, or 60°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin), the pressure of the hot pressing curing is 2-6MPa (for example, it can be 2MPa, 4MPa or 6MPa), and the heat preservation and pressure holding time of the hot pressing curing is 10-30 minutes (for example, it can be 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes).

[0153] In the above-mentioned method for preparing the high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, in step S2, the volume ratio of the supercritical carbon dioxide (scCO2) and nitrogen is 9:1-7:3, for example, it can be 9:1, 8:2 or 7:3. If the amount of N2 is too little (<10%), the impact is as follows: insufficient nucleation and coarse bubbles: when the amount is insufficient, the number of bubble nuclei is small, CO2 concentrates into a small number of bubbles, the average pore size increases, and the distribution is uneven (local bubble formation); the bubble stability decreases: when the amount is insufficient, the rapid diffusion of CO2 dominates, the bubble growth is too fast, the bubble wall becomes thinner, the risk of bubble formation increases, and the open porosity increases. If the amount of N2 is too much (>30%), the impact is: insufficient polymer plasticization: the polymer Tg does not drop enough, the melt viscosity is too high, which makes it difficult for the gas to diffuse, the foaming ratio is reduced, and the density of the foam material increases; the nucleation is too dense but the growth is limited: although high N2 increases the nucleation density, due to its slow diffusion characteristics, the N2 partial pressure in the pores is high, which inhibits the diffusion of CO2 into the pores, the gas release rate in the melt is slow, the pore size is too small, but the pore wall is not fully stretched, which makes the foam easy to shrink and collapse, and the specific surface area is too high, which increases the hygroscopicity.

[0154] In the preparation method of the above-mentioned high-temperature resistant nitrogen heterocyclic polyarylether resin foam material, as an optional embodiment, in step S2, the physical foaming in a supercritical carbon dioxide (scCO2) and nitrogen mixed medium environment includes: in the presence of supercritical carbon dioxide (scCO2) and nitrogen mixed gas, the prefabricated board is insulated and pressurized, and the temperature of the insulation and pressure holding is 15-45°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin (for example, it can be 15°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 25°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 30°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 45°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 50°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 60°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 70°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 80°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 90°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylether resin, 15 ... Tg) above 35 ° C, the nitrogen heterocyclic polyarylene ether resin glass transition temperature (Tg) above 40 ° C, or the nitrogen heterocyclic polyarylene ether resin glass transition temperature (Tg) above 45 ° C; if the temperature is too low, foaming cannot be achieved, if the temperature is too high, the plate will cause amorphous foaming, the internal pore structure of the foam material is highly disordered, and the size and shape are extremely uneven), the insulation and pressure holding pressure is 15-40 MPa (for example, it can be 15 MPa, 23.5 MPa, 25 MPa, 30 MPa, 35 MPa or 40 MPa), preferably in the pressure range of 15-28 MPa, and the insulation and pressure holding time is 60-120 minutes (for example, it can be 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes or 120 minutes).

[0155] In the above-mentioned method for preparing high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, in step S2, the pressure relief rate is 40-85 MPa / s, for example, it can be 40 MPa / s, 50 MPa / s, 60 MPa / s, 70 MPa / s or 85 MPa / s. If the pressure relief rate is too low, the foaming ratio will be too low.

[0156] In the above-mentioned preparation method of the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, as an optional embodiment, after rapidly releasing the pressure to normal pressure, the preparation method further comprises the following steps:

[0157] Open the kettle, take out the sample and air cool it to room temperature.

[0158] The present invention will be further described in detail below with reference to specific examples and comparative examples.

[0159] In the following examples and comparative examples:

[0160] Foaming ratio test method: Sample: Remove burrs and foreign matter from the foam surface before testing; Test conditions: Use the drainage method to test the foam density and calculate the foaming ratio.

[0161] Phthalazine biphenyl DHPZ was purchased from Dalian Poly New Materials Co., Ltd. The chemical structure is shown below:

[0162]

[0163] Dimethyl-substituted phthalazinone biphenyl monomer and bisphthalazinone biphenyl monomer were purchased from Dalian Poly New Materials Co., Ltd.

[0164] Example 1 Foaming of poly(phenylene ether sulfone ketone) (PPESK)

[0165] A three-necked flask was charged with diazinone biphenyl DHPZ (110 mmol), 4,4′-dichlorodiphenyl sulfone (50 mmol), 4,4′-difluorobenzophenone (50 mmol), K2CO3 (110 mmol), NMP (N-methylpyrrolidone, 150 mL), and toluene (60 mL). The mixture was refluxed at 130°C for 3 h with toluene as the water carrier, followed by removal of H2O. The reaction solution was then heated to 160°C to remove the toluene. The reaction system was then slowly heated to 180°C for further reaction. A typical nucleophilic substitution reaction at 180°C allowed the synthesis of poly(phenylene ether sulfone ketone) (PPESK). As the viscosity of the reaction solution increased, NMP was added to reduce it. When the viscosity of the reaction solution stopped increasing, the reaction solution was poured into a dilute hydrochloric acid solution (10% by mass) to remove the solvent, inorganic salts, and other impurities, resulting in a fibrous polymer precipitate. The precipitated fibrous polymer was crushed and washed with deionized water and ethanol, and finally dried in vacuo at 120° C. to obtain poly(phenylene ether sulfone ketone) (PPESK). PPESK has a chemical structure shown in Formula C and a weight-average molecular weight of 35,000 g / mol.

[0166]

[0167] Figure 1 The infrared spectrum of PPESK prepared in this example is: Figure 2 The H NMR spectrum of the PPESK prepared in this example, the infrared spectrum and the H NMR spectrum of PPESK can prove the successful synthesis of PPESK.

[0168] Figure 3 The DSC test chart of PPESK prepared in this embodiment is Figure 3 It can be seen that the glass transition temperature of PPESK is 287°C.

[0169] The dried PPESK resin is mechanically crushed to obtain a homogeneous powder with an average particle size of 45μm, which is then pressed into shape: in a nitrogen protective atmosphere, hot pressing and curing are carried out at a molding temperature of 330°C, a pressure of 4MPa and a holding time of 15 minutes to form a dense prefabricated board. After that, it enters the supercritical carbon dioxide and nitrogen foaming stage: the board is placed in a high-pressure reactor, and CO2 and N2 are pre-mixed in a volume ratio of 9:1 and then injected into the reactor. It is maintained at 322°C and 24MPa pressure for 90 minutes to allow supercritical CO2 and N2 to fully penetrate into the polymer matrix. Finally, the directional expansion is triggered by instantaneous pressure relief (pressure relief rate of 60MPa / s), and then the kettle is opened to take out the sample, and cooled to room temperature in the air. A high-performance PPESK foam material with a foaming ratio of 6.3 times is successfully produced, and the density of the foam material is 200kg / m 3 , the closed cell rate is 90%.

[0170] Figure 4 This is a sample picture of the PPESK foam material prepared in this example.

[0171] Figure 5 The SEM image of the PPESK foam material prepared in this embodiment is shown in FIG. Figure 5 It can be seen that the pores of the PPESK foam material prepared in this example are dense and uniform without obvious defects, showing a highly complete closed-cell structure, uniform pore morphology, clear boundaries, and no collapse, cracking or fusion phenomena.

[0172] Example 2 Foaming of Fluorenyl-Napthalene Biphenyl Poly(aryl ether nitrile ketone) (PPFENK)

[0173] A three-necked flask was charged with bisphenol fluorene monomer (55 mmol), phthalazinone biphenyl DHPZ (55 mmol), 2,6-dichlorobenzonitrile (50 mmol), 4,4′-difluorobenzophenone (50 mmol), K2CO3 (110 mmol), NMP (N-methylpyrrolidone, 150 mL), and toluene (60 mL). The mixture was refluxed at 130°C for 3 h with toluene as the water carrier, followed by removal of H2O. The reaction solution was then heated to 160°C to remove the toluene. The reaction system was then slowly heated to 180°C for further reaction. A typical nucleophilic substitution reaction at 180°C was performed to synthesize a fluorenyl-containing phthalazinone poly(aryl ether nitrile ketone) (PPFENK). As the viscosity of the reaction solution increased, NMP was added to reduce the viscosity. When the viscosity of the reaction solution stopped increasing, the reaction solution was poured into a dilute hydrochloric acid solution (10% by mass) to remove the solvent and impurities such as inorganic salts, resulting in a fibrous polymer precipitate. The precipitated fibrous polymer was crushed and washed with deionized water and ethanol, and finally dried in vacuum at 120° C. to obtain fluorenyl-containing poly(phenylene ether nitrile ketone) (PPFENK). PPFENK has the structure shown in the following formula and a weight-average molecular weight of 38,000 g / mol.

[0174]

[0175] Figure 6 This is the infrared spectrum of the PPFENK prepared in this example. Figure 7 The H NMR spectrum of the PPFENK prepared in this example, the IR spectrum and the H NMR spectrum of the PPFENK can prove the successful synthesis of the PPFENK.

[0176] Figure 8 This is the DSC test chart of PPFENK prepared in this embodiment, Figure 8 It can be seen that the glass transition temperature of PPFENK is 262°C.

[0177] The dried PPFENK resin was crushed and sieved to obtain a homogeneous powder (average particle size of 45μm), which was then pressed and solidified under a nitrogen atmosphere: a hot pressing temperature of 320°C was set, a pressure of 4MPa was applied and kept warm for 15 minutes to form a dense substrate. It was then transferred to the supercritical CO3:N2=9:1 (v:v) foaming stage: the plate was placed in a high-pressure reactor, CO2 and N2 were pre-mixed in a volume ratio of 9:1 and then injected into the reactor. The osmotic equilibrium was maintained at 303°C and 25MPa pressure for 70 minutes, and finally the directional growth of the pore structure was achieved by instantaneous pressure relief (pressure relief rate of 60MPa / s). After that, the reactor was opened to take out the sample and cooled to room temperature in the air. A high-performance PPFENK foam material with a foaming ratio of 12 times was successfully prepared, and the density of the foam material was 110kg / m 3, the closed cell rate is 86%.

[0178] Figure 9 This is a sample picture of the PPFENK foam material prepared in this example.

[0179] Figure 10 The SEM image of the PPFENK foam material prepared in this embodiment is shown in FIG. Figure 10 It can be seen that the PPFENK foam material prepared in this example has dense and uniform pores without obvious defects, showing a highly complete closed-cell structure, uniform pore morphology, clear boundaries, and no collapse, cracking or fusion.

[0180] Compared with Example 1, the resin provided in this example can significantly increase the foaming ratio by including a fluorene group.

[0181] Example 3 Foaming of poly(aryl ether sulfone ketone ketone) containing dimethyl phthalazinone (PPESKK)

[0182] A dimethyl-substituted phthalazinone biphenyl monomer was used as a copolymerized bisphenol monomer, and 4,4′-dichlorodiphenyl sulfone and 1,4-phenylbis((4-fluorophenyl)methanone) were used as copolymerized dihalogen monomers (molar ratio of 1:1). PPESKK was prepared by referring to the preparation method of phthalazinone poly(aryl ether sulfone ketone) (PPESK) in Example 1. PPESKK has the chemical structure shown in the following formula and a weight-average molecular weight of 28,000 g / mol.

[0183]

[0184] Figure 11 The infrared spectrum of PPESKK prepared in this example is: Figure 12 The H NMR spectrum of PPESKK prepared in this example, the IR spectrum and H NMR spectrum of PPESKK can prove the successful synthesis of PPESKK.

[0185] Figure 13 The DSC test chart of PPESKK prepared in this embodiment is Figure 13 It can be seen that the glass transition temperature of PPESKK is 275°C.

[0186] The dried PPESKK resin was crushed and sieved to obtain a homogeneous powder (average particle size of 45 μm), which was then pressed and solidified under a nitrogen atmosphere: a hot pressing temperature of 335°C was set, a pressure of 5 MPa was applied and kept warm for 12 minutes to form a dense substrate. It then entered the supercritical carbon dioxide and nitrogen foaming stage: the plate was placed in a high-pressure reactor, and CO2 and N2 were pre-mixed in a volume ratio of 9:1 and then injected into the reactor. The osmotic equilibrium was maintained at 315°C and 25 MPa pressure for 90 minutes, and finally the directional growth of the pore structure was achieved through instantaneous pressure relief (pressure relief rate of 60 MPa / s). After that, the reactor was opened to take out the sample and cooled to room temperature in the air. A high-performance PPESKK foam material with a foaming ratio of 5 times was successfully prepared, and the density of the foam material was 260 kg / m 3 , closed cell rate is 91%

[0187] Figure 14 This is a sample picture of the PPESKK foam material prepared in this example.

[0188] Figure 15 The SEM image of the PPESKK foam material prepared in this embodiment is shown in FIG. Figure 15 It can be seen that the pores of the PPESKK foam material prepared in this example are dense and uniform without obvious defects, showing a highly complete closed-cell structure, uniform pore morphology, clear boundaries, and no collapse, cracking or fusion phenomena.

[0189] Example 4 Foaming of polyarylene ether resin PBPENK containing phthalazinone structure

[0190] PBPENK was prepared using a bis(phthalazinone) biphenyl monomer as a copolymerized bisphenol monomer, 2,6-dichlorobenzonitrile and 4,4′-difluorobenzophenone as copolymerized dihalogen monomers (molar ratio of 1:1), and referring to the preparation method of phthalazinone poly(aryl ether sulfone ketone) (PPESK) in Example 1. PBPENK has the chemical structure shown in the following formula and a weight-average molecular weight of 38,000 g / mol.

[0191]

[0192] Figure 16 This is the infrared spectrum of the PBPENK prepared in this example. Figure 17 The hydrogen nuclear magnetic resonance spectrum of the PBPENK prepared in this example, the infrared spectrum and the hydrogen nuclear magnetic resonance spectrum of PBPENK can prove the successful synthesis of PBPENK.

[0193] Figure 18 This is the DSC test chart of PBPENK prepared in this embodiment, Figure 18 It can be seen that the glass transition temperature of PBPENK is 301°C.

[0194] The dried PBPENK resin was crushed and sieved to obtain a homogeneous powder (average particle size of 45 μm), which was then pressed and solidified under a nitrogen atmosphere: the hot pressing temperature was set at 339°C, a pressure of 6 MPa was applied and kept warm for 10 minutes to form a dense substrate. It then entered the supercritical carbon dioxide and nitrogen foaming stage: the plate was placed in a high-pressure reactor, and CO2 and N2 were pre-mixed in a volume ratio of 9:1 and then injected into the reactor. The osmotic equilibrium was maintained at 334°C and 24 MPa pressure for 65 minutes, and finally the directional growth of the pore structure was achieved through instantaneous pressure relief (pressure relief rate of 60 MPa / s). After that, the reactor was opened to take out the sample and cooled to room temperature in the air. A high-performance PBPENK foam material with a foaming ratio of 8 times was successfully prepared, and the density of the foam material was 160 kg / m 3 , the closed cell rate is 88%.

[0195] Figure 19 This is a sample picture of the PBPENK foam material prepared in this example.

[0196] Figure 20 The SEM image of the PBPENK foam prepared in this embodiment is shown in FIG. Figure 20 It can be seen that the PBPENK foam material prepared in this example has dense and uniform pores without obvious defects, showing a highly complete closed-cell structure, uniform pore morphology, clear boundaries, and no collapse, cracking or fusion.

[0197] Example 5

[0198] The preparation method of the foam material provided in this embodiment is basically the same as that in Example 1, except that the temperature in the foaming stage is 312°C and the heat preservation and pressure holding time is 80 minutes. A high-performance PPESK foam material with a foaming ratio of 5.5 times was successfully prepared, and the foam material density was 240kg / m 3 , the closed cell rate is 91%.

[0199] The scanning electron microscope (SEM) image of the PPESK foam material prepared in this example is similar to the scanning electron microscope (SEM) image of the PPESK foam material prepared in Example 1.

[0200] Example 6

[0201] The preparation method of the foam material provided in this embodiment is basically the same as that in Example 1, except that the pressure in the foaming stage is 15 MPa and the heat preservation and pressure holding time is 120 minutes. A high-performance PPESK foam material with a foaming ratio of 5.3 times was successfully prepared, and the foam material density was 260 kg / m 3 , the closed cell rate is 90%.

[0202] The scanning electron microscope (SEM) image of the PPESK foam material prepared in this example is similar to the scanning electron microscope (SEM) image of the PPESK foam material prepared in Example 1.

[0203] Example 7

[0204] The preparation method of the foam material provided in this embodiment is basically the same as that in Example 1, except that, in the foaming stage, the volume ratio of supercritical carbon dioxide (scCO2) to nitrogen is 7:3, and the pressure relief rate is 85 MPa / s. A high-performance PPESK foam material with a foaming ratio of 5.5 times was successfully prepared, and the foam material density was 243 kg / m 3 , the closed cell rate is 93%.

[0205] Comparative Example 1

[0206] The polyarylene ether resin provided in this comparative example is a conventional linear polyarylene ether resin, and its preparation method is substantially the same as that of the polyarylene ether in Example 1, except that diazinone biphenyl DHPZ is replaced by 6F-BPA.

[0207] The polyarylene ether resin has a chemical structure shown in the following formula and a weight average molecular weight of 35,000 g / mol.

[0208]

[0209] The preparation method of the polyarylene ether resin foam material provided in this comparative example is basically the same as that in Example 1, except that the polyarylene ether resin provided in this comparative example is used instead of the polyarylene ether resin in Example 1. A foam material with a foaming ratio of 1.5 is prepared.

[0210] Comparing this comparative example with Example 1, it can be seen that the nitrogen heterocyclic polyarylene ether resin foam material provided by the present invention has a higher foaming ratio due to the inclusion of a diazinone structure, thereby obtaining a linear structure polyarylene ether resin foam material with a higher foaming ratio.

[0211] Comparative Example 2

[0212] The preparation method of the foam material provided in this comparative example is basically the same as that of Example 1, except that only carbon dioxide is used as the medium in the foaming stage, thereby obtaining a foam material with a foaming ratio of 5.5 times and a closed cell ratio of 80%.

[0213] The foam material prepared in this comparative example has sparse and uneven cells and a decreased closed cell ratio.

[0214] Comparative Example 3

[0215] The preparation method of the foam material provided in this comparative example is basically the same as that of Example 1, except that only nitrogen gas is used as the medium during the foaming stage, thereby producing a foam material with a foaming ratio of 2.

[0216] The foaming ratio of the foam material prepared in this comparative example is reduced, the density of the foam material is increased, and the cell walls of many cells are not fully stretched, resulting in the foam easily shrinking and collapsing.

[0217] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high temperature resistant nitrogen heterocyclic polyarylene ether resin foam material, characterized in that: The high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material comprises nitrogen heterocyclic polyarylene ether resin, wherein the nitrogen heterocyclic polyarylene ether resin is a linear structure polyarylene ether resin and has a phthalazinone structure.

2. The high temperature resistant nitrogen heterocyclic polyarylether resin foam material according to claim 1, characterized in that: The chemical structural formula of the phthalazinone is as follows: And / or, the nitrogen heterocyclic polyaryl ether resin includes at least one of phthalazinone polyaryl ether sulfone, phthalazinone polyaryl ether ketone, phthalazinone polyaryl ether sulfone ketone, phthalazinone polyaryl ether sulfone ketone ketone, fluorenyl phthalazinone-containing polyaryl ether sulfone, fluorenyl phthalazinone-containing polyaryl ether ketone, fluorenyl phthalazinone-containing polyaryl ether sulfone ketone, fluorenyl phthalazinone-containing polyaryl ether sulfone ketone, fluorenyl phthalazinone-containing polyaryl ether nitrile ketone, dimethyl phthalazinone-containing polyaryl ether sulfone, dimethyl phthalazinone-containing polyaryl ether ketone, dimethyl phthalazinone-containing polyaryl ether sulfone ketone, dimethyl phthalazinone-containing polyaryl ether sulfone ketone, and polyaryl ether containing a dimethyl phthalazinone structure.

3. The high temperature resistant nitrogen heterocyclic polyarylether resin foam material according to claim 2, characterized in that: The poly(phenylene ether sulfone) has a chemical structure shown in Formula A: Wherein, n≥1 and is an integer; And / or, the poly(aryletherketone) has a chemical structure shown in Formula B: Wherein, n≥1 and is an integer; And / or, the poly(phenylene ether sulfone ketone) has a chemical structure shown in Formula C: Wherein, n≥1, m≥1 and are integers, and the ratio of n to m is 100:1 to 1:100; And / or, the poly(phenylene ether sulfone ketone ketone) has a chemical structure shown in Formula D: wherein n≥1 and is an integer, m≥1 and is an integer, and the ratio of n to m is 100:1 to 1:100; and / or the fluorenyl-containing poly(phenylene ether sulfone) has a chemical structure shown in Formula E: Wherein, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of m to n is 100:1 to 1:100; And / or, the fluorenyl-containing poly(aryl ether ketone) has a chemical structure shown in Formula F: Wherein, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of m to n is 100:1 to 1:100; And / or, the fluorenyl-containing poly(aryl ether sulfone ketone) has a chemical structure shown in Formula G: wherein n ≥ 1 and is an integer, m ≥ 1 and is an integer, x ≥ 1 and is an integer, y ≥ 1 and is an integer, the ratio of m+y to n+x is 100:1 to 1:100, and the ratio of m+n to x+y is 100:1 to 1:100; And / or, the fluorenyl-containing poly(aryl ether sulfone ketone ketone) has a chemical structure shown in Formula H: wherein n ≥ 1 and is an integer, m ≥ 1 and is an integer, x ≥ 1 and is an integer, y ≥ 1 and is an integer, the ratio of m+n to x+y is 100:1 to 1:100, and the ratio of x+n to m+y is 100:1 to 1:100; And / or, the fluorenyl-containing naphthalene biphenyl poly (aryl ether nitrile ketone) has a chemical structure shown in the following formula: Wherein, x1 ≥ 1 and is an integer, y1 ≥ 1 and is an integer, x ≥ 1 and is an integer, y ≥ 1 and is an integer, the ratio of y+y1 to x+x1 is 100:1 to 1:100, and the ratio of x+y to x1+y1 is 100:1 to 1:100; And / or, the dimethylphthalazinyl poly(aryl ether sulfone) containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula I, the dimethylphthalazinyl poly(aryl ether ketone) containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula J, the dimethylphthalazinyl poly(aryl ether sulfone ketone) containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula K, and the dimethylphthalazinyl poly(aryl ether sulfone ketone ketone) containing dimethylphthalazinyl biphenyl has a chemical structure shown in Formula L: Wherein, in the chemical structural formula I, n ≥ 1 and is an integer; in the chemical structural formula J, n ≥ 1 and is an integer; in the chemical structural formula K, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of n to m is 100:1 to 1:100; in the chemical structural formula L, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of n to m is 100:1 to 1:100; And / or, the polyarylene ether containing a phthalazinone structure has at least one of the following chemical structures: n≥1 and is an integer; Wherein, n≥1 and is an integer; Wherein, n ≥ 1 and is an integer, m ≥ 1 and is an integer, and the ratio of n to m is 100:1 to 1:100; In formula (4), formula (5) and formula (6), the structure of R is at least one of the following structures: ， n≥1 and is an integer.

4. The high temperature resistant nitrogen heterocyclic polyarylether resin foam material according to any one of claims 1 to 3, characterized in that: The weight average molecular weight of the nitrogen heterocyclic polyarylene ether resin is 25000 to 45000 g / mol; And / or, the density of the high temperature resistant nitrogen heterocyclic polyarylether resin foam material is 30 to 1000 kg / m 3 ; And / or, the glass transition temperature of the high temperature resistant nitrogen heterocyclic polyarylene ether resin is 262° C. to 388° C.; And / or, the polymerization monomers of the nitrogen heterocyclic polyarylene ether resin include a dihalogen monomer and a difunctional monomer containing a diazinone biphenyl structure, or a dihalogen monomer, a difunctional monomer containing a diazinone biphenyl structure and a bisphenol monomer containing a fluorenyl structure.

5. A method for preparing a high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: S1. Hot-pressing and curing the nitrogen heterocyclic polyarylene ether resin powder under a protective gas atmosphere to obtain a prefabricated plate; S2. Placing the prefabricated plate in a reactor in a mixed medium environment of supercritical carbon dioxide and nitrogen for physical foaming, and finally rapidly releasing the pressure to normal pressure to complete the foaming, thereby obtaining the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material.

6. The method for preparing the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material according to claim 5, characterized in that: In step S1, the protective gas includes nitrogen, and the average particle size of the nitrogen heterocyclic polyarylene ether resin powder is 25 μm-100 μm; And / or, in step S1, the temperature of the hot pressing curing is 40-60°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylene ether resin, the pressure of the hot pressing curing is 2-6 MPa, and the heat preservation and pressure holding time of the hot pressing curing is 10-30 minutes.

7. The method for preparing the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material according to claim 5, characterized in that: In step S2, the volume ratio of the supercritical carbon dioxide to nitrogen is 9:1-7:

3.

8. The method for preparing the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material according to claim 5, characterized in that: In step S2, the physical foaming in a supercritical carbon dioxide and nitrogen mixed medium environment includes: insulating and pressurizing the prefabricated board in the presence of a supercritical carbon dioxide and nitrogen mixed gas, the insulation and pressure holding temperature being 15-45°C above the glass transition temperature (Tg) of the nitrogen heterocyclic polyarylene ether resin, the insulation and pressure holding pressure being 15-40MPa, and the insulation and pressure holding time being 60-120 minutes.

9. The method for preparing the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material according to claim 5, characterized in that: In step S2, the pressure relief rate is 40-85 MPa / s.

10. The method for preparing the high-temperature resistant nitrogen heterocyclic polyarylene ether resin foam material according to claim 5, characterized in that: After rapidly releasing the pressure to normal pressure, the preparation method further comprises the following steps: Open the kettle, take out the sample and air cool it to room temperature.

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