Polyarylether sulphone amide as well as preparation method and application thereof

Abstract

The invention discloses a polyarylether sulphone amide and a preparation method and application thereof, the structure of the polyarylether sulphone amide at least contains a repeating unit as shown in formula I: # imgabs0 #, wherein X, Y and Z are respectively and independently selected from substituted or unsubstituted aromatic rings, aromatic heterocyclic rings or heterocyclic rings; n is an integer between 0 and 4; a > = 1, c > = 1, and a + c = b. According to the polyarylether sulphone amide, the structure is optimized and modified, multiple key groups are introduced into the structure, and through the synergistic effect of the groups, the polyarylether sulphone amide has excellent comprehensive performance; meanwhile, the preparation method of the polyarylether sulphone amide provided by the invention is simple to operate, and the monomer is easy to obtain, so that industrialization of the polyarylether sulphone amide is easy to realize.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyamides, and in particular relates to polyarylethersulfoneamide and a preparation method and application thereof. Background Art

[0002] Aromatic polyamide (aramid) is a specialty organic polymer obtained through polycondensation using aromatics as raw materials. It exhibits excellent heat resistance and insulation properties, stable chemical properties, and excellent resistance to weak acids, weak bases, and most organic solvents. Consequently, it is widely used in the textile, machinery, electrical, chemical, automotive, daily chemical, pharmaceutical, and construction industries. Aramid can be primarily divided into meta-aramid and para-aramid based on its chemical structure, with the main varieties being poly(p-phenylene terephthalamide) and poly(m-phenylene isophthalamide) fibers.

[0003] In order to give aromatic polyamides excellent properties, the existing technology often uses block copolymerization or blending methods to modify their structure, while retaining their original excellent properties, so that their solubility, light resistance, thermal properties or toughness are improved. The most typical case is HM-50, which is a copolymer of 3,4'-diaminodiphenyl ether, p-phenylenediamine and terephthaloyl chloride. In addition, the existing technology also reports the synthesis of aromatic polyamides by ternary co-condensation of p-phenylenediamine, terephthaloyl chloride and a third monomer, 4,4'-di(p-aminophenoxy)diphenyl sulfone, in an NMP / CaCl2 solvent system. By introducing semi-flexible segments into its rigid chain structure, its toughness, fatigue resistance and solubility are improved, while maintaining excellent tensile strength, modulus and thermal properties.

[0004] However, in actual application, aramid materials have the following performance defects: ① The aramid material structure contains a large number of rigid benzene rings, and the polymer molecular structure is highly regular, resulting in low toughness of the aramid material; ② The film-forming properties of para-aramid and meta-aramid materials are poor, especially high molecular weight para-aramid is difficult to process into a film. During the film making process, the film is prone to breakage and has low transparency; ③ The aramid material has poor adhesion to the metal interface. The above performance defects limit the application of aramid materials. Summary of the Invention

[0005] In view of this, the primary purpose of the present invention is to provide a polyarylethersulfoneamide, which utilizes the synergistic effect of the functional groups contained in the monomer structure to improve material properties, has a simple preparation process, and has high catalytic activity.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention first provides a poly(arylene ether sulfone amide), wherein the poly(arylene ether sulfone amide) structure contains at least a repeating unit represented by formula I:

[0008]

[0009] Wherein, X, Y, and Z are independently substituted or unsubstituted aromatic rings, aromatic heterocycles, or heterocycles; n is an integer between 0 and 4; a≥1, c≥1, and a+c=b.

[0010] The polyarylethersulfoneamide in the present invention increases its toughness, solubility and adhesion by introducing monomers containing ether bonds into its structure; in addition, its transparency is increased by introducing sulfone groups, that is, the synergistic effect of sulfone groups, ether bonds and amide bonds is utilized to improve the overall performance of the material.

[0011] In a further embodiment, the polyarylethersulfoneamide of the present invention is obtained by copolymerizing a first monomer, a second monomer and a third monomer, wherein:

[0012] The first monomer is at least one of an aromatic dibasic acid chloride, an aromatic heterocyclic dibasic acid chloride, and a heterocyclic dibasic acid chloride;

[0013] The second monomer is a diamine containing an alkyl ether group, and its general structural formula is shown in Formula II:

[0014]

[0015] Wherein, n is an integer between 0 and 4;

[0016] The third monomer is an aromatic, aromatic heterocyclic or heterocyclic diamine containing a sulfone group, or a mixture thereof with other diamines.

[0017] In a further embodiment, the first monomer is at least one of isophthaloyl chloride, terephthaloyl chloride, naphthalene dicarboxylic acid chloride, 1,3,5-benzene trimethylene glycol chloride, 4,4'-diphenyl ether dicarboxylic acid chloride, imidazole dicarboxylic acid chloride, furan dicarboxylic acid chloride, and pyridine dicarboxylic acid chloride.

[0018] In a further embodiment, the second monomer is any one of the following compounds A to C:

[0019]

[0020] In a further embodiment, the sulfone-containing aromatic, aromatic heterocyclic or heterocyclic diamine is at least one of 4,4-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3-diaminodiphenyl sulfone and 3,6-thioanthracene diamine;

[0021] And / or, the other diamine is at least one of m-phenylenediamine, p-phenylenediamine, pyridinediamine, naphthalenediamine, butanediamine, and pentamethylenediamine.

[0022] In a further embodiment, the molar ratio of the first monomer, the second monomer and the third monomer is n1:(n2+n3)=(0.95-1.05):1.

[0023] The present invention further provides a method for preparing the aforementioned polyarylethersulfoneamide, comprising the following steps:

[0024] Under the protection of an inert atmosphere, an organic solvent, a second monomer, and a third monomer are sequentially added to the reaction vessel and stirred; then a catalyst is added and stirring is continued;

[0025] The temperature is adjusted to 0-10° C., the first monomer is added to the system, and the reaction is completed to obtain polyarylethersulfoneamide.

[0026] In a further embodiment, the organic solvent is at least one of DMF, DMAC, NMP, THF, and dichloromethane;

[0027] And / or, the mass of the organic solvent is 3 to 10 times the mass of the total diamine.

[0028] In a further embodiment, the catalyst is at least one of tungsten sulfate, tungsten hexachloride, and zirconium sulfate;

[0029] And / or, the content of the catalyst is 0.5%-5% by mass of the total diamine.

[0030] A further solution, after the reaction is completed, further comprises the following steps:

[0031] A poor solvent for polyarylethersulfoneamide is added to the solution after the reaction is completed, and the mixture is stirred, filtered, and dried.

[0032] In a further embodiment, the poor solvent is at least one of methanol, ethanol, isopropanol, acetonitrile, and n-butanol;

[0033] And / or, the mass of the poor solvent is 1 to 3 times the mass of the organic solvent.

[0034] The present invention further provides the use of the polyarylethersulfoneamide as described above or the polyarylethersulfoneamide prepared by the above preparation method in the preparation of special membrane materials, high temperature resistant materials, composite materials, engineering plastics, and new energy materials.

[0035] Beneficial effects of the present invention:

[0036] The polyarylethersulfoneamide in the present invention has excellent comprehensive properties by optimizing and modifying its structure and introducing multiple key groups into the structure. The synergistic effect between the groups is achieved:

[0037] (1) The polyarylethersulfoneamide in the present invention has rigid benzene rings and alternating amide bonds, so the material maintains high strength, high modulus, and strong heat resistance;

[0038] (2) In the present invention, by copolymerizing a diamine containing an alkyl ether structure, on the one hand, the copolymerization appropriately reduces the regularity of the material molecular structure, and on the other hand, the alkyl ether itself has extremely strong flexibility. The diamine containing an alkyl ether structure can improve the flexibility of the polymer, and the ether bond forms a hydrogen bond with the metal surface, thereby increasing the adhesion;

[0039] (3) In the present invention, by introducing a sulfone-containing aromatic diamine, on the one hand, the conjugated effect of the sulfone structure further improves the heat resistance of the material. On the other hand, due to the high polarity of the sulfone structure, when the sulfone group combines with the metal, charge transfer occurs to form a strong coordination effect, thereby increasing the interfacial bonding force between the material and the metal.

[0040] (4) In addition, the strong electron-withdrawing property of the sulfone group can effectively prevent the formation of charge transfer complexes in the polymer molecular structure, thereby weakening the absorption of visible light and thus exhibiting higher transparency.

[0041] At the same time, the present invention also provides a preparation method of polyarylethersulfoneamide, which is simple to operate and the monomers are easily available, so that the polyarylethersulfoneamide can be easily industrialized.

[0042] The polyarylethersulfoneamide has excellent comprehensive properties and can therefore be used in the preparation of special membrane materials, high-temperature resistant materials, composite materials, engineering plastics, new energy materials, etc., and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is the NMR characterization result of compound A in Example 1.

[0044] Figure 2 This is the nuclear magnetic resonance characterization result of the poly(arylethersulfoneamide) in Example 1.

[0045] Figure 3-Figure 6 The appearances of the film materials prepared in Example 1, Example 2, Example 5 and Comparative Example 1 are shown in order. DETAILED DESCRIPTION

[0046] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and are not to be construed as limiting the present invention.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0048] The first aspect of the present invention provides a polyarylethersulfoneamide, the structure of which contains at least a repeating unit as shown in Formula I:

[0049]

[0050] Wherein, X, Y, and Z are independently substituted or unsubstituted aromatic rings, aromatic heterocycles, or heterocycles; n is an integer between 0 and 4; a≥1, c≥1, and a+c=b.

[0051] The polyarylethersulfoneamide is obtained by copolymerizing a first monomer, a second monomer and a third monomer. By copolymerizing monomers containing different key groups and utilizing the synergistic effect of the key groups, a polyarylethersulfoneamide with excellent comprehensive properties is obtained.

[0052] The first monomer is at least one of an aromatic dicarboxylic acid chloride, an aromatic heterocyclic dicarboxylic acid chloride, and a heterocyclic dicarboxylic acid chloride. Specific examples include at least one of isophthaloyl chloride, terephthaloyl chloride, naphthalene dicarboxylic acid chloride, 1,3,5-benzenetricarboxylic acid chloride, 4,4'-diphenyl ether dicarboxylic acid chloride, imidazole dicarboxylic acid chloride, furan dicarboxylic acid chloride, and pyridine dicarboxylic acid chloride, but are not limited thereto.

[0053] The second monomer is a diamine containing an alkyl ether group, and its general structural formula is shown in Formula II:

[0054]

[0055] Here, n is an integer between 0 and 4.

[0056] In some specific embodiments of the present invention, the second monomer is any one of the following compounds A to C:

[0057]

[0058] The second monomer described herein can be prepared by itself or obtained from the market.

[0059] The third monomer may be a sulfone-containing aromatic, aromatic heterocyclic or heterocyclic diamine, or a mixture of a sulfone-containing aromatic, aromatic heterocyclic or heterocyclic diamine and other diamines.

[0060] Wherein, the sulfone-containing aromatic, aromatic heterocyclic or heterocyclic diamine is at least one of 4,4-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3-diaminodiphenyl sulfone and 3,6-thioanthracene diamine.

[0061] The other diamines are aromatic, aromatic heterocyclic, heterocyclic or aliphatic diamines without sulfone groups. Specific examples include at least one of m-phenylenediamine, p-phenylenediamine, pyridinediamine, naphthalenediamine, butanediamine and pentamethylenediamine, but are not limited thereto.

[0062] Furthermore, the specific amounts of the first monomer, the second monomer and the third monomer can be adjusted according to actual needs. In some specific embodiments of the present invention, the molar ratio of the first monomer n1, the second monomer n2 and the third monomer n2 is n1:(n2+n3)=(0.95~1.05):1, preferably, n1:(n2+n3)=1:1.

[0063] The second aspect of the present invention provides a method for preparing the polyarylethersulfoneamide according to the first aspect of the present invention, comprising the following steps:

[0064] Under the protection of an inert atmosphere, an organic solvent, a second monomer, and a third monomer are sequentially added to the reaction vessel and stirred; then a catalyst is added and stirring is continued;

[0065] The temperature is adjusted to 0-10° C., the first monomer is added to the system, and the reaction is completed to obtain polyarylethersulfoneamide.

[0066] The inert atmosphere refers to the reaction being carried out in an oxygen-isolated environment by introducing an inert atmosphere. The inert atmosphere used can be one of the rare gases or nitrogen, without any particular limitation.

[0067] In a further embodiment, the organic solvent can be any common organic solvent in the art. Specific examples include, but are not limited to, at least one of N,N-dimethylformamide (DMF), dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), and dichloromethane. The specific amount used can be adjusted based on actual conditions. In some specific embodiments of the present invention, the mass of the organic solvent is 3 to 10 times the mass of the total diamine.

[0068] A further solution is to increase the polymerization efficiency of the reaction by adding a catalyst to the reaction, thereby obtaining polyarylethersulfoneamide with excellent performance. In some specific embodiments of the present invention, the catalyst is at least one of tungsten sulfate, tungsten hexachloride, and zirconium sulfate, and the content of the catalyst is 0.5%-5% of the total mass of the diamine.

[0069] A further solution, after the reaction is completed, further comprises the following steps:

[0070] A poor solvent for polyarylethersulfoneamide is added to the solution after the reaction is completed, and the mixture is stirred, filtered, and dried.

[0071] The poor solvent described herein refers to a poorly soluble solvent for poly(arylethersulfoneamide), and poly(arylethersulfoneamide) is precipitated by adding the poor solvent for poly(arylethersulfoneamide). In some specific embodiments of the present invention, the poor solvent is at least one of methanol, ethanol, isopropanol, acetonitrile, and n-butanol, but is not limited thereto. The specific amount used can be selected according to the amount of the organic solvent. In some specific embodiments of the present invention, preferably, the mass of the poor solvent is 1 to 3 times the mass of the organic solvent.

[0072] The third aspect of the present invention provides the use of the polyarylethersulfoneamide as described in the first aspect of the present invention or the polyarylethersulfoneamide prepared by the preparation method described in the second aspect of the present invention in the preparation of special membrane materials, high temperature resistant materials, composite materials, engineering plastics, and new energy materials.

[0073] The present invention is described below by means of specific examples. It should be noted that the following specific examples are for illustrative purposes only and do not limit the scope of the present invention in any way. In addition, unless otherwise specified, methods without specific conditions or steps are conventional methods, and the reagents and materials used are all commercially available.

[0074] Example 1

[0075] This embodiment provides a method for preparing polyarylethersulfoneamide, and the specific steps are as follows:

[0076] S1. Preparation of Compound A

[0077] Dichloroethyl ether (0.1 mol), p-nitrophenol (0.2 mol), and potassium carbonate (0.2 mol) were added to DMF (100 mL), and the mixture was reacted at 125° C. for 5 hours. The mixture was filtered and the solvent was dried to obtain a nitro intermediate. The nitro intermediate was dissolved in ethanol (100 mL), and palladium carbon (1 g) was added. The mixture was heated to 45° C. under a 0.2 MPa hydrogen atmosphere and reacted for 12 hours. The reaction was stopped, filtered and dried, and column chromatography was performed to obtain compound A with the following structure:

[0078]

[0079] The NMR characterization results are shown in Figure 1 : 1 H NMR (400MHz, DMSO) δ6.65(m,1H),6.49(m,1H),4.59(s,1H),3.94(m,1H),3.72(m,1H).

[0080] S2. Preparation of polyarylethersulfoneamide

[0081] Under nitrogen protection, DMAC (200 g), 4,4-diaminodiphenyl sulfone (24.8 g, 0.1 mol), compound A (28.8 g, 0.1 mol), and tungsten sulfate (0.5 g) were added to the reactor, stirred, and a cooling bath was turned on to reduce the internal temperature to 0°C. Then, isophthaloyl chloride (40.6 g, 0.2 mol) was added thereto and reacted for 1 h to obtain a polyarylethersulfoneamide slurry; methanol (600 g) was added thereto, stirred for 1 h, filtered, and dried to obtain polyarylethersulfoneamide.

[0082] The nuclear magnetic resonance results of the polyarylethersulfoneamide in this embodiment are: 1 HNMR(400MHz,)δ11.04(m,1H),10.51(d,J=5.8Hz,1H),8.71(m,1H),8.08(m,4H) ,7.91(m,2H),7.73(m,2H),7.61(m,1H),6.91(m,2H),4.07(s,2H),3.77(s,2H).

[0083] Example 2-3

[0084] This example adopts the same implementation as Example 1, with the only difference being that the second monomer is replaced by equimolar amounts of Compound B and Compound C, respectively. Other steps and conditions are the same as in Example 1.

[0085] Wherein, the preparation process of compound B is as follows:

[0086] 1,2-bis(2-chloroethoxy)ethane (0.1 mol), p-nitrophenol (0.2 mol), and potassium carbonate (0.2 mol) were added to DMF (100 mL), and the mixture was reacted at 125° C. for 5 hours. The mixture was filtered and the solvent was dried to obtain a nitro-containing intermediate. The nitro-containing intermediate was dissolved in ethanol (100 mL), and palladium carbon (1 g) was added. The mixture was heated to 45° C. under a 0.2 MPa hydrogen atmosphere and reacted for 12 hours. The reaction was stopped, filtered and dried, and column chromatography was performed to obtain compound B with the following structure:

[0087]

[0088] The preparation process of compound C is as follows:

[0089] To DMF (100 mL) were added dichloroethyl ether (0.1 mol), p-nitrophenol (0.1 mol), m-nitrophenol (0.1 mol), and potassium carbonate (0.2 mol), and the mixture was reacted at 125° C. for 5 hours. The mixture was filtered and the solvent was dried to obtain a nitro intermediate. The nitro intermediate was dissolved in ethanol (100 mL), and palladium carbon (1 g) was added. The mixture was heated to 45° C. under a 0.2 MPa hydrogen atmosphere and reacted for 12 hours. The reaction was stopped, filtered and dried, and column chromatography was performed to obtain compound C having the structure shown below:

[0090]

[0091] Example 4

[0092] This example adopts the same implementation as Example 1, with the only difference being that the first monomer is replaced with an equal molar amount of terephthaloyl chloride, and the other steps and conditions are the same as Example 1.

[0093] Example 5

[0094] This example adopts the same implementation as Example 1, with the only difference being that the third monomer is replaced with an equimolar amount of 3,3-diaminodiphenyl sulfone, and the other steps and conditions are the same as Example 1.

[0095] Example 6

[0096] This example adopts the same implementation as Example 1, with the only difference being that the first monomer is replaced with an equimolar amount of 4,4'-diphenyl ether dicarbonyl chloride, and the other steps and conditions are the same as those in Example 1.

[0097] Example 7

[0098] This example adopts the same implementation as Example 1, except that the third monomer is replaced by an equimolar mixture of 4,4-diaminodiphenyl sulfone and pentamethylenediamine (0.05 mol each). Other steps and conditions are the same as Example 1.

[0099] Comparative Example 1

[0100] This comparative example adopts the same implementation as Example 1, with the only difference being that the second monomer and the third monomer are both replaced with equimolar amounts of m-phenylenediamine, and the other steps and conditions are the same as Example 1.

[0101] Comparative Example 2

[0102] This comparative example adopts the same implementation as Example 1, except that the catalyst tungsten sulfate is not added, and the other steps and conditions are the same as Example 1.

[0103] Comparative Example 3

[0104] This comparative example adopts the same implementation as Example 1, with the only difference being that the third monomer 4,4-diaminodiphenyl sulfone is replaced by an equal mole of the second monomer compound A. The other steps and conditions are the same as those in Example 1.

[0105] Comparative Example 4

[0106] This comparative example adopts the same implementation as Example 1, with the only difference being that the second monomer compound A is replaced with an equal molar amount of 4,4-diaminodiphenyl sulfone, and the other steps and conditions are the same as Example 1.

[0107] Table 1 Monomer composition of poly(arylethersulfoneamide) in Examples 1-7 and Comparative Examples 1-4

[0108] First monomer Second monomer The third unit Example 1 Isophthaloyl chloride Compound A 4,4-Diaminodiphenyl sulfone Example 2 Isophthaloyl chloride Compound B 4,4-Diaminodiphenyl sulfone Example 3 Isophthaloyl chloride Compound C 4,4-Diaminodiphenyl sulfone Example 4 Terephthaloyl chloride Compound A 4,4-Diaminodiphenyl sulfone Example 5 Isophthaloyl chloride Compound A 3,3-Diaminodiphenyl sulfone Example 6 4,4'-Diphenyl ether dicarbonyl chloride Compound A 4,4-Diaminodiphenyl sulfone Example 7 Isophthaloyl chloride Compound A 0.05 mol 4,4-diaminodiphenyl sulfone and 0.05 mol pentamethylenediamine mixture Comparative Example 1 Isophthaloyl chloride m-phenylenediamine m-phenylenediamine <![CDATA[Comparative Example 2 a > Isophthaloyl chloride Compound A 4,4-Diaminodiphenyl sulfone Comparative Example 3 Isophthaloyl chloride Compound A Compound A Comparative Example 4 Isophthaloyl chloride 4,4-Diaminodiphenyl sulfone 4,4-Diaminodiphenyl sulfone

[0109] Note: a in Table 1 indicates that no catalyst was added in this comparative example.

[0110] Performance Testing

[0111] 1. Take a sample and test its inherent viscosity.

[0112] 2. Take the polyarylethersulfoneamide slurry in the examples and comparative examples, use a laboratory small coating machine to cast the sample into a film, and test the film haze, tensile strength, elongation at break and film appearance.

[0113] 3. Take the prepared polyarylethersulfoneamide slurry, apply it on the surface of copper foil, roll it, dry it at 100°C, cool it to room temperature, and test the peel strength between the film and the copper foil.

[0114] Among them, ① Mechanical testing method refers to GB13022-1991.

[0115] ② The inherent viscosity test refers to the following method: DMAC is added to the Ubbelohde viscometer, and the outflow time of the pure solvent is measured, which is recorded as t1; 1 gram of polymer is placed in a 100 mL volumetric flask, and 50 mL of DMAC solvent solution with a concentration of c is added. The solution is added to the Ubbelohde viscometer. The time it takes for the polymer to flow through the two scale lines of the viscometer is the outflow time of the solution, which is recorded as t0; the inherent viscosity {η} = In(t0 / t1) / c.

[0116] ③The haze test method refers to the national standard GB / T 2410-2008.

[0117] The test results are shown in Table 2.

[0118] Table 2

[0119]

[0120] Analysis of Examples 1 to 7 shows that an increase in the monomer ether bond content and the degree of polymerization will improve the toughness and adhesion of the polymer. The higher the monomer ether bond content and the greater the concentrated viscosity, the stronger the adhesion and toughness of the material.

[0121] Analysis of the examples and comparative example 1 shows that the toughness, metal adhesion and transparency of the polymer of the present invention are significantly higher than those of traditional aramid materials.

[0122] Analysis of Example 1 and Comparative Example 2 shows that adding a catalyst can significantly improve the polymerization efficiency of the reaction.

[0123] Analysis of Example 1 and Comparative Example 3 shows that the addition of sulfone-containing diamine can enhance the light transmittance, adhesion and heat resistance of the material.

[0124] Analysis of Example 1 and Comparative Example 4 shows that if the diamine containing alkyl ether is not added, the adhesion and toughness of the polymer will be reduced.

[0125] pass Figure 3-Figure 6 It can be seen from the comparison that the polyarylethersulfoneamide film in the present application has excellent transparency, and the transparency of the polyarylethersulfoneamide film in the present application is better than that of the traditional aramid material and the material in the comparative example.

[0126] Other parallel implementation plans

[0127] In this paper, other parallel implementation schemes were carried out by changing different monomers, etc. The specific monomers and catalyst types are shown in the table below. The other steps and experimental conditions are the same as those in Example 1.

[0128] First monomer Second monomer The third unit catalyst Example 8 Naphthalene dicarboxylic acid chloride Compound A 3,6-Thioanthracene diamine Tungsten hexachloride Example 9 Imidazole dicarbonyl chloride Compound B 4,4-Diaminodiphenylsulfone+naphthalene diamine Tungsten sulfate Example 10 1,3,5-Benzenetricarboxylic acid chloride Compound C 3,4-Diaminodiphenyl sulfone Zirconium sulfate Example 11 Pyridinedicarbonyl chloride Compound A 4,4-Diaminodiphenyl sulfone Tungsten sulfate Example 12 Isophthaloyl chloride Compound A 3,3-Diaminodiphenyl sulfone + p-phenylenediamine Tungsten sulfate

[0129] Using the performance tests described above in this article, the results show that the polyarylethersulfoneamides prepared in Examples 8-12 can all achieve the technical effects of the present invention, and also have the advantages of high strength, high modulus, and strong heat resistance, and have excellent bonding properties and high transparency, and excellent comprehensive performance.

[0130] In summary, the polyarylethersulfoneamide of this invention maintains its heat resistance and high strength while improving its toughness, film-forming properties, transparency, and metal bonding. Furthermore, the product's preparation process is environmentally friendly, simple to operate, and suitable for industrialization. This enables the localization of high-performance materials, and holds broad market prospects.

[0131] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0132] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A polyarylethersulfoneamide, characterized in that The structure of the polyarylethersulfoneamide contains at least a repeating unit shown in Formula I: Wherein, X, Y, and Z are independently selected from substituted or unsubstituted aromatic rings, aromatic heterocycles, or heterocycles; n is an integer between 0 and 4; a≥1, c≥1, and a+c=b.

2. The polyarylethersulfoneamide according to claim 1, characterized in that It is obtained by copolymerizing a first monomer, a second monomer and a third monomer, wherein: The first monomer is at least one of an aromatic dibasic acid chloride, an aromatic heterocyclic dibasic acid chloride, and a heterocyclic dibasic acid chloride; The second monomer is a diamine containing an alkyl ether group, and its general structural formula is shown in Formula II: Wherein, n is an integer between 0 and 4; The third monomer is an aromatic, aromatic heterocyclic or heterocyclic diamine containing a sulfone group, or a mixture thereof with other diamines.

3. The polyarylethersulfoneamide according to claim 2, characterized in that The first monomer is at least one of isophthaloyl chloride, terephthaloyl chloride, naphthalene dicarboxylic acid chloride, 1,3,5-benzene trimecyl chloride, 4,4'-diphenyl ether dicarboxylic acid chloride, imidazole dicarboxylic acid chloride, furan dicarboxylic acid chloride, and pyridine dicarboxylic acid chloride.

4. The polyarylethersulfoneamide according to claim 2, characterized in that The second monomer is any one of the following compounds A to C:

5. The polyarylethersulfoneamide according to claim 2, characterized in that The sulfone-containing aromatic, aromatic heterocyclic or heterocyclic diamine is at least one of 4,4-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3-diaminodiphenyl sulfone and 3,6-thioanthracene diamine; And / or, the other diamine is at least one of m-phenylenediamine, p-phenylenediamine, pyridinediamine, naphthalenediamine, butanediamine, and pentamethylenediamine.

6. The polyarylethersulfoneamide according to claim 2, characterized in that The molar ratio of the first monomer, the second monomer and the third monomer is n1:(n2+n3)=(0.95-1.05):

1.

7. A method for preparing the polyarylethersulfoneamide according to any one of claims 1 to 6, characterized in that: The following steps are involved: Under the protection of an inert atmosphere, an organic solvent, a second monomer and a third monomer are sequentially added to the reaction container and stirred; then a catalyst is added and stirring is continued; The temperature is adjusted to 0-10° C., the first monomer is added into the system, and the reaction is completed to obtain polyarylethersulfoneamide.

8. The preparation method according to claim 7, characterized in that: The organic solvent is at least one of DMF, DMAC, NMP, THF and dichloromethane; And / or, the mass of the organic solvent is 3 to 10 times the mass of the total diamine; And / or, the catalyst is at least one of tungsten sulfate, tungsten hexachloride, and zirconium sulfate; And / or, the content of the catalyst is 0.5%-5% of the total mass of the diamine.

9. The preparation method according to claim 7, characterized in that: After the reaction is completed, the following steps are further included: Adding a poor solvent of polyarylethersulfoneamide to the solution after the reaction is completed, stirring, filtering and drying; And / or, the poor solvent is at least one of methanol, ethanol, isopropanol, acetonitrile and n-butanol; And / or, the mass of the poor solvent is 1 to 3 times the mass of the organic solvent.

10. Use of the polyarylethersulfoneamide according to any one of claims 1 to 6 or the polyarylethersulfoneamide prepared by the preparation method according to any one of claims 7 to 9 in the preparation of special membrane materials, high temperature resistant materials, composite materials, engineering plastics and new energy materials.

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