High temperature resistant polymers comprising carbazole groups and bis- phthalazinone structures, methods of making and uses thereof

Abstract

The present application belongs to the technical field of polymer material synthesis, and particularly relates to a high-temperature-resistant polymer containing a carbazole group and a bisphthalazinone structure, a preparation method and use thereof. The present application introduces a carbazole group and a bisphthalazinone structure into a polyarylene ether or a polyarylene ether-like molecular main chain from the design of a molecular structure, which can impart strong rigidity to the polymer main chain, adjust and improve the heat resistance and mechanical properties thereof, break the symmetry of the molecular chain by virtue of the twisted and non-planar structure characteristics of the bisphthalazinone structure, and realize the solubility. The present application also realizes the purpose of adjusting and controlling the heat resistance and solubility of the polymer by regulating the proportion of the structural unit containing the carbazole group and the bisphthalazinone structure and other structural units. The present application solves the problem of insufficient high-temperature resistance of the existing electromagnetic wire paint, and meets the application needs of the heat resistance grade of the electromagnetic wire paint.

Description

Technical Field

[0001] This invention belongs to the field of polymer material synthesis technology, and specifically relates to high-temperature resistant polymers containing carbazole groups and bis(diazanaphthone) structures, their preparation methods, and applications. Background Technology

[0002] Magnet wire is an insulated wire used to manufacture coils or windings in electrical products. It is widely used in motors, electrical appliances, instruments, transformers, electronic components, new energy vehicles, wind power generation, and other fields. With the rapid development of new energy electric vehicles and the technological upgrades of high-end equipment such as aerospace and industrial variable frequency motors, higher requirements are placed on the high-temperature resistance of magnet wire windings. The increase in motor efficiency and power density has led to a continuous rise in winding operating temperatures. The insulating varnish of magnet wire needs to meet the requirements of heat resistance stability at temperatures above 350°C, while also possessing good solubility and mechanical toughness.

[0003] Polyaryl ethers or polyaryl ether-like materials are a class of high-temperature engineering plastics with excellent heat resistance and mechanical properties. They can be used to prepare resin-based composite materials, high-temperature separation membranes, functional membranes, enameled wires, cables, wear-resistant materials, biomedical materials, etc., and are widely used in aerospace, marine engineering, energy, electronics, petrochemicals, biomedicine, and other fields. The glass transition temperature T0 of commercially available polyaryl ethers is... g It can reach temperatures between approximately 143 and approximately 225°C, which does not meet the above-mentioned high-temperature resistance requirements.

[0004] A series of polyaryl ethers containing diazanaphthone structures have been reported in the prior art. The twisted, non-coplanar structural features of the diazanaphthone structure break the symmetry of the molecular chain, thus endowing polyaryl ether resins with excellent solubility and high-temperature resistance, including polyaryl ether ketone resins (T...). g (approximately 263°C), polyarylethersulfone resin (T) g (approximately 305°C), polyarylethernitrile ketone resin (T) g (Approximately 268 to approximately 289°C), see: Wang Mingjing's doctoral dissertation at Dalian University of Technology, 2007; Chinese invention patent application CN1513897A, etc. Ashay et al. (Macromolecules, 1997, 30(8), 2254) also reported polyaryletherketones (T) containing diphenyl ether or diphenyl sulfide structures and bis(diazanaphthone) structures. g (approximately 301°C and approximately 281°C) and polyarylethersulfone (T g (approximately 295°C and approximately 279°C), and based on bisphenol-like monomers synthesized from dianhydrides, polysulfones with a bis(diazanaphthone) structure were prepared (T). g (approximately 221°C, approximately 310°C, and approximately 344°C), polyaryl ketone (T g(approximately 195°C and approximately 286°C) and polyarylonitrile (T g (Approximately 200°C and approximately 301°C). However, no technology currently exists that combines low cost with excellent heat resistance (T). g The polyarylene ether or polyarylene-like ether has a temperature of not less than about 369°C, preferably not less than about 400°C, more preferably not less than about 420°C, and good solubility.

[0005] Therefore, from the perspective of molecular design, it is necessary to develop a material that combines high temperature resistance (T... g A novel electromagnetic wire coating with a temperature not lower than about 369°C, preferably not lower than about 400°C, and more preferably not lower than about 420°C, which is soluble and has excellent mechanical toughness, is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] Purpose of the invention In view of the problems existing in the prior art described in the background section above, the object of the present invention is to provide a high-temperature resistant polymer comprising a carbazole group and a bis(diazanaphthone) structure, a method for preparing the polymer thereof, and its uses.

[0007] Technical solution To achieve the above objectives, the present invention adopts the following technical solution: Option 1: A high-temperature resistant polymer comprising a carbazole group and a bis(diazanaphthone) structure, wherein the polymer contains structural units of formula (I) in the main chain: (I) in, n represents the molar percentage of the structural units of formula (I) contained in the main chain of each polymer molecule, and n is in the range of about 10 to about 90 mol%, preferably not less than about 30 mol%, more preferably not less than about 50 mol%, particularly preferably not less than about 70 mol%; Ar1, each time it appears, independently and identically or differently from each other, represents a structural part represented by one or more of the following structural formulas: ; ; ; ; ; and ; In the above structural formula representing Ar1, there is a " The single bond of the '' group is attached to the nitrogen atom of the five-membered ring of the carbazole group contained in structural formula (I). Ar2, each time it appears, independently and identically or differently from each other, represents a structural part represented by one or more of the following structural formulas: ; ; ; ;and , In the above structural formula representing Ar2, R represents a substituent on the benzene ring to which it is attached, and the substituent, each time it appears, independently and identically or differently from each other, represents a phenyl group, an alkyl group containing 1 to 20 carbon atoms, or an alkoxy group containing 1 to 20 carbon atoms; 'a' represents the number of substituents R on the benzene ring, a = 0 or 1; and With " One of the two single bonds is attached to the nitrogen atom of the six-membered ring of the diazanaphthone structure linked to Ar2 in formula (I), and the single bond with " The other of the two single bonds in the "" bond connects to another structural unit in the main chain of the polymer molecule. In the above structural formulas representing monomers, polymers, and groups, the chemical bond extending from the outside of the benzene ring and extending into the interior of the benzene ring means that the group or structure connected to the benzene ring by the bond is not fixedly connected to a specific carbon atom of the benzene ring, but is connected to any unoccupied optional position in the benzene ring.

[0008] Option 2: The polymer according to Option 1 above, wherein the main chain of the polymer further comprises structural units of formula (II): (II) In the structural unit of equation (II) above, p represents the molar percentage of the structural units of formula (II) contained in the main chain of each polymer molecule, and p is in the range of about 10 to about 90 mol%, preferably not more than about 70 mol%, more preferably not more than about 50 mol%, particularly preferably not more than about 30 mol%; Ar2 has the same meaning as Ar2 given in equation (I) above, except that in the structural formula representing Ar2, it contains " One of the two single bonds is attached to the Ar3 group in the structural formula (II), and the group with the " The other of the two single bonds of the "" is attached to another structural unit in the main chain of the polymer molecule; Ar3, each time it appears, independently and identically or differently from each other, represents a structural part represented by one or more of the following structural formulas: ; ; ; ; ; ; ; ; ; In the above structural formula representing Ar3, R' represents a substituent on the benzene ring to which it is attached, and the substituent, each time it appears, is independently and identically or differently selected from one or more of a halogen group, a phenoxy group, an alkyl group containing 1 to 20 carbon atoms, and an alkoxy group containing 1 to 20 carbon atoms; m represents the number of substituents R' on the benzene ring containing substituent R', m = 0, 1, 2, 3 or 4; and With " One of the two single bonds of “” is attached to the Ar2 group in the structural formula (II), and the group with “” The other of the two single bonds is attached to another structural unit in the main chain of the polymer molecule.

[0009] Option 3: The polymer according to Option 2 above, wherein Ar3, each time it appears, independently and identically or differently represents a structural part represented by one or more of the following structural formulas: The two oxygen atoms on the benzene ring are located at positions 1,2, 1,3, or 1,4. The two oxygen atoms on the benzene ring are located at the 2,2' or 4,4' positions; The two oxygen atoms on the benzene ring are located at positions 1,4, 1,5, 1,6, 2,6, or 2,7. The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions.

[0010] Scheme 4: The polymer according to any one of Schemes 1 to 3 above, wherein the structural unit of formula (I) comprises structural units of formula (I-1) and / or (I-2): (I-1) (I-2).

[0011] Option 5: A polymer according to any one of Options 1 to 4 above, wherein Ar1, each time it appears, independently and identically or differently represents a structural part represented by one or more of the following structural formulas: ; ; ; ; ; ; ; ;and .

[0012] Option 6: A polymer according to any one of Options 1 to 5 above, wherein Ar2, each time it appears, independently and identically or differently represents a structural part represented by one or more of the following structural formulas: ; ; ; ;and .

[0013] Option 7: The polymer according to any one of Options 1 to 6 above, wherein the polymer has one or more of the following properties: The polymer has a molecular weight of not less than about 9,000 g / mol, preferably in the range of about 40,000 to about 60,000 g / mol; The glass transition temperature T of the polymer g The temperature is not lower than about 369°C, preferably not lower than about 400°C, more preferably not lower than about 420°C, and most preferably not lower than about 430°C; The polymer has a solubility of not less than about 0.1 g / mL in any one of polar aprotic organic solvents selected from sulfolane, N-methylpyrrolidone, N,N-dimethylacetamide, and 1,1,2,2-tetrachloroethane. The tensile strength of the polymer is not less than about 89.5 MPa, preferably not less than about 97.5 MPa, and more preferably not less than about 102.3 MPa; The polymer has a tensile modulus of not less than about 3.03 GPa, preferably not less than about 3.55 GPa, and more preferably not less than about 4.0 GPa; and The elongation at break of the polymer is in the range of about 3.7% to about 6.6%.

[0014] Scheme 8: A method for preparing a polymer according to any one of Schemes 1 to 7 above, wherein the preparation method comprises: mixing a bisphenol-like monomer of formula (III), an aromatic dihalogen monomer of formula (IV), and optionally a bisphenol or bisphenol-like monomer of formula (V) with a solvent, an azeotropic dehydrating agent, and a catalyst, thereby subjecting the resulting reaction system to a stepwise polymerization reaction under a protective gas atmosphere, and settling the reaction mixture obtained after the polymerization reaction is completed in a settling agent to obtain the polymer as the settling material, wherein the ratio of the total molar number of the bisphenol-like monomer of formula (III) and optionally the bisphenol or bisphenol-like monomer of formula (V) to the molar number of the aromatic dihalogen monomer of formula (IV) is in the range of about (0.9-1.1):(0.9-1.1), preferably about 1:1. (III) X-Ar2-X (IV) H-Ar3-H (V) In the above equations (III), (IV) and (V) Ar1 has the same meaning as Ar1 given in equation (I) above, except that in the structural formula representing Ar1, it contains " The single bond of “” is attached to the nitrogen atom of the five-membered ring of the carbazole group contained in the structural formula (III); Ar2 has the same meaning as Ar2 given in equation (I) above, except that it includes " One of the two single bonds of “” is attached to a group X in structural formula (IV), and the “” The other of the two single bonds of the "" is attached to another group X in the structural formula (IV); X represents a halogen, such as F, Cl, Br, or I; Ar3 has the same meaning as Ar3 given in equation (II) above, except that it includes " One of the two single bonds is connected to an H in the (V) structural formula, and the bond with " The other of the two single bonds is connected to the other H in the structure (V).

[0015] Option 9: The preparation method according to Option 8 above, wherein the solvent includes a polar organic solvent, preferably one or more of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, hexamethylphosphoric triamine or sulfolane.

[0016] Option 10: The preparation method according to Option 8 or 9 above, wherein the azeotropic aqueous agent includes one or more of aromatic hydrocarbons and halogenated aromatic hydrocarbons, preferably including one or more of benzene, toluene, xylene and halogenated benzene.

[0017] Scheme 11: The preparation method according to any one of Schemes 8 to 10 above, wherein the catalyst comprises a carbonate and / or bicarbonate and optionally a fluoride catalyst, wherein the carbonate and / or bicarbonate preferably comprises an alkali metal carbonate and / or an alkali metal bicarbonate and / or an alkaline earth metal carbonate and / or an alkaline earth metal bicarbonate; and the fluoride catalyst preferably comprises an alkali metal fluoride.

[0018] Scheme 12: The preparation method according to any one of Schemes 8 to 11 above, wherein the volume of the azeotropic water-carrying agent is about 0.1 to about 20 times the volume of the solvent used in the polymerization reaction.

[0019] Scheme 13: The preparation method according to any one of Schemes 8 to 12 above, wherein the molar amount of the catalyst is about 1 to about 10 times the total molar amount of bisphenol monomers and bisphenol-like monomers contained in the reaction mixture.

[0020] Scheme 14: The preparation method according to any one of Schemes 8 to 13 above, wherein the mass of the solvent is about 0.2 to about 50 times the total mass of the bisphenol monomer, bisphenol-like monomer and aromatic dihalogen monomer contained in the reaction mixture.

[0021] Scheme 15: The preparation method according to any one of Schemes 8 to 14 above, wherein the protective gas includes one or more of nitrogen, helium, argon, neon, krypton, xenon, radon and carbon dioxide.

[0022] Option 16: The preparation method according to any one of Options 8 to 15 above, wherein the step-growth polymerization reaction comprises carrying out a step-growth reaction in the reaction system within the range of about 110 to about 280°C, preferably comprising first carrying out an azeotropic dehydration reaction in the reaction system at a temperature of about 110 to about 150°C, wherein water in the reaction system is carried out of the reaction system by an azeotropic dehydrating agent until the water content in the reaction system is reduced to below the detection limit, then the azeotropic dehydrating agent is distilled off until the content of the azeotropic dehydrating agent in the reaction system is reduced to below the detection limit, and then the reaction is carried out in the temperature range of about 150 to about 280°C until the viscosity no longer increases.

[0023] Scheme 17: The preparation method according to any one of Schemes 8 to 16 above, wherein the settling agent comprises one or more of water, alcohol, tetrahydrofuran and acetone.

[0024] Scheme 18: The use of the polymer as described in any one of Schemes 1 to 7 above, or the polymer prepared by any one of Schemes 8 to 17 above, for preparing high-temperature resistant electromagnetic wire paint.

[0025] Technical effect Starting from molecular structure design, this invention introduces carbazole groups and bis(diazanaphthone) structures into the main chain of polyarylene ethers or polyarylene ether-like molecules. On the one hand, this can endow the polymer main chain with strong rigidity, improving its heat resistance and mechanical properties; on the other hand, by utilizing the twisted and non-coplanar structural features of the bis(diazanaphthone) structure, the symmetry of the molecular chain is broken, achieving solubility.

[0026] Specifically, the polymer of the present invention has the following advantages: (1) The polymer of the present invention has both excellent heat resistance and good solubility. The main reason is that by introducing carbazole group and bis(diazanaphthone) structure, the polymer has better heat resistance and good solubility, and its glass transition temperature T g It can reach about 369°C, preferably about 400°C, more preferably about 420°C, and most preferably about 430°C, and is soluble in polar aprotic organic solvents such as N-methylpyrrolidone and 1,1,2,2-tetrachloroethane.

[0027] (2) The preparation method of the above-mentioned polymer containing carbazole group and bis(diazanaphthone) structure of the present invention adopts nucleophilic substitution stepwise polymerization reaction, which can achieve stable preparation of polymer; (3) The present invention can also regulate and improve the mechanical properties, heat resistance and solubility of the polymer by adjusting the structure and ratio of the structural units containing carbazole group and bis(diazanaphthone) structure and other structural units, so that it can meet the needs of more different application scenarios.

[0028] (4) The polymers of the present invention containing carbazole groups and bis(diazanaphthone) structures, given the advantages described above, can be widely used in the technical fields of electromagnetic wire coatings. The present invention solves the problem of insufficient high-temperature resistance of existing electromagnetic wire coatings and meets the application requirements for the heat resistance level of electromagnetic wire coatings. Attached Figure Description

[0029] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the specific embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0030] Figure 1 The infrared spectrum of the polyarylene ether nitrile containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure prepared in Examples E1-2 of this invention; Figure 2 The infrared spectrum of the polyarylene ether nitrile containing an N-m-dicyanophenylcarbazole group and a bis(diazanaphthone) structure prepared in Example E3 of this invention; Figure 3 The infrared spectrum of the polyarylene ether nitrile containing an N-p-cyanooxyphenylcarbazole group and a bis(diazanaphthone) structure prepared in Example E4 of this invention; Figure 4 Infrared spectra of polyarylene sulfononitriles containing bis(diazanaphthone) structures prepared for comparative examples CE1 to CE4.

[0031] Figure 5 The nuclear magnetic resonance spectra of polyarylene ether nitrile containing N-p-cyanophenylcarbazole groups and bis(diazanaphthone) structures prepared in Examples E1-1, E1-2 and E1-3 of this invention.

[0032] In the infrared spectrum above, the horizontal axis represents wavenumber, and the vertical axis represents transmittance.

[0033] In the above NMR spectrum, the horizontal axis represents the chemical shift. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Those skilled in the art should understand that the embodiments described are merely for the purpose of aiding understanding of this invention and should not be considered as specific limitations on this invention. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. Process parameters in the following embodiments that are not specifically specified are generally performed under conventional conditions.

[0035] The endpoints and any values ​​of the ranges disclosed in this invention 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. The term "about" as used in this invention means that the number it modifies may fluctuate within ±20%, ±15%, ±10%, ±5%, or ±2% of that number. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and the individual point values ​​contained within them, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0036] According to a first aspect of the present invention, the present invention provides a high-temperature resistant polymer comprising a carbazole group and a bis(diazanaphthone) structure.

[0037] According to the first aspect of the present invention, the high-temperature resistant polymer contains structural units of formula (I) in the main chain: (I).

[0038] In the context of this invention, in structural formulas representing monomers, polymers, and groups, a chemical bond extending from the outside of the benzene ring and extending into the interior of the benzene ring means that the group or structure connected to the benzene ring by the bond is not fixedly connected to a specific carbon atom of the benzene ring, but is connected to any unoccupied optional position in the benzene ring.

[0039] More preferably, the high-temperature resistant polymer according to the first aspect of the present invention includes structural units of formula (I) in the main chain comprising structural units of formula (I-1) and / or (I-2): (I-1) (I-2).

[0040] In the structural unit of formula (I) above, n represents the molar percentage of structural units of formula (I) contained in the main chain of each polymer molecule, wherein n is in the range of about 10 mol% to about 90 mol%, preferably at least about 20 mol%, about 30 mol%, about 40 mol%, about 50 mol%, about 60 mol%, about 70 mol%, or about 80 mol%. Here, the molar percentage of structural units of formula (I) should not exceed about 90 mol%, otherwise it may lead to problems such as difficulty in processing and molding the product and increased brittleness; in addition, the molar percentage of structural units of formula (I) should not be less than about 10 mol%, otherwise it may lead to problems such as insufficient heat resistance and decreased mechanical properties of the product.

[0041] In the structural unit of the above formula (I), Ar1, each time it appears, independently and identically or differently represents a structural part represented by one or more of the following structural formulas: , , , , , and , More preferably, Ar1 in the structural unit of the above formula (I), each time it appears, independently and identically or differently represents a structural part represented by one or more of the following structural formulas: ; ; ; ; ; ; ; ;and ; In the above structural formula representing Ar1, there is a " The single bond of '' is attached to the nitrogen atom of the five-membered ring of the carbazole group contained in the structural formula (I).

[0042] In the structural unit of the above formula (I), Ar2, each time it appears, independently and identically or differently represents a structural part represented by one or more of the following structural formulas: ; ; ; ;and , More preferably, Ar2 in the structural unit of the above formula (I), each time it appears, independently and identically or differently represents a structural part represented by one or more of the following structural formulas: ; ; ; ;and .

[0043] In the above structural formula representing Ar2, R represents a substituent on the benzene ring to which it is attached, and each time the substituent appears, it independently and identically or differently represents a phenyl group, an alkyl group containing 1 to 20 carbon atoms, or an alkoxy group containing 1 to 20 carbon atoms.

[0044] In the above structural formula representing Ar2, a represents the number of substituents R on the benzene ring with substituent R, a = 0 or 1.

[0045] In the above structural formula representing Ar2, the part containing " One of the two single bonds is attached to the nitrogen atom of the six-membered ring of the diazanaphthone structure linked to Ar2 in formula (I), and the single bond with " The other of the two single bonds is attached to another structural unit in the main chain of the polymer molecule.

[0046] In some further preferred embodiments of the high-temperature resistant polymer according to the first aspect of the invention, in addition to the structural units of formula (I), the polymer backbone preferably also includes structural units of formula (II): (II) In the structural unit of formula (II) above, p represents the molar percentage of structural units of formula (II) contained in the main chain of each polymer molecule, wherein p is in the range of about 10 mol% to about 90 mol%, preferably not exceeding about 20 mol%, about 30 mol%, about 40 mol%, about 50 mol%, about 60 mol%, about 70 mol%, or about 80 mol%. Here, the molar percentage of structural units of formula (II) should not exceed about 90 mol%, otherwise it may lead to problems such as insufficient heat resistance and decreased mechanical properties of the product; in addition, the molar percentage of structural units of formula (II) should not be less than about 10 mol%, otherwise it may lead to problems such as difficulty in processing and molding the product and increased brittleness.

[0047] In some specific embodiments of the present invention, the molar percentage ratios n and p can be adjusted according to the type of comonomer and the target performance.

[0048] In some particularly preferred embodiments of the high-temperature resistant polymer according to the first aspect of the invention, the polymer is composed only of structural units of formula (I) and formula (II), except for the end-capping groups.

[0049] The high-temperature resistant polymer according to the first aspect of the present invention can be a random copolymer, a block copolymer, or an alternating copolymer.

[0050] In the structural unit of equation (II) above, the meaning of Ar2 is similar to that of Ar2 given in equation (I) above, except that the structural formula representing Ar2 includes " One of the two single bonds is attached to the Ar3 group in the structural formula (II), and the group with the " The other of the two single bonds of the "" is attached to another structural unit in the main chain of the polymer molecule; In the structural unit of the above formula (II), Ar3, each time it appears, independently and identically or differently represents a structural part represented by one or more of the following structural formulas: ; ; ; ; ; ; ; ; ; In some further preferred embodiments, Ar3 in the structural unit of formula (II) above, each time appearing, independently and identically or differently represents a structural part represented by one or more of the following structural formulas: The two oxygen atoms on the benzene ring are located at positions 1,2, 1,3, or 1,4. The two oxygen atoms on the benzene ring are located at the 2,2' or 4,4' positions; The two oxygen atoms on the benzene ring are located at positions 1,4, 1,5, 1,6, 2,6, or 2,7. The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions.

[0051] In the above structural formula representing Ar3, R' represents a substituent on the benzene ring to which it is attached, and the substituent, each time it appears, is independently and identically or differently selected from one or more of halogen groups, phenoxy groups, alkyl groups containing 1 to 20 carbon atoms, and alkoxy groups containing 1 to 20 carbon atoms.

[0052] In the above structural formula representing Ar3, m represents the number of substituents R' on the benzene ring with substituent R', where m = 0, 1, 2, 3 or 4.

[0053] In the structural formula representing Ar3 above, the part containing " One of the two single bonds of “” is attached to the Ar2 group in the structural formula (II), and the group with “” The other of the two single bonds is attached to another structural unit in the main chain of the polymer molecule.

[0054] The high-temperature resistant polymer according to the first aspect of the present invention preferably has one or more of the following properties: The polymer has a molecular weight of not less than about 9000 g / mol, preferably in the range of 40000 to 60000 g / mol; The glass transition temperature T of the polymer g The temperature is not lower than about 369°C, preferably not lower than about 400°C, more preferably not lower than about 420°C, and most preferably not lower than about 430°C; The polymer has a solubility of not less than about 0.1 g / mL in any one of polar aprotic organic solvents selected from sulfolane, N-methylpyrrolidone, N,N-dimethylacetamide, and 1,1,2,2-tetrachloroethane. The tensile strength of the polymer is not less than about 89.5 MPa, preferably not less than about 97.5 MPa, and more preferably not less than about 102.3 MPa; The polymer has a tensile modulus of not less than about 3.03 GPa, preferably not less than about 3.55 GPa, and more preferably not less than about 4.0 GPa; and The elongation at break of the polymer is in the range of about 3.7% to about 6.6%, for example, about 4.5% or about 5.5%.

[0055] According to a second aspect of the present invention, the present invention provides a method for preparing the high-temperature resistant polymer described in the first aspect of the present invention.

[0056] The preparation method according to the second aspect of the present invention includes mixing a bisphenol-like monomer of formula (III), an aromatic dihalogen monomer of formula (IV), and optionally a bisphenol or bisphenol-like monomer of formula (V) with a solvent, an azeotropic dehydrating agent, and a catalyst, so that the formed reaction system undergoes a stepwise polymerization reaction under a protective gas atmosphere, and the reaction mixture obtained after the polymerization reaction is completed is precipitated in a precipitant to obtain the polymer as the precipitate, wherein the total molar number of the bisphenol-like monomer of formula (III) and the optional bisphenol or bisphenol-like monomer of formula (V) is substantially the same as the molar number of the aromatic dihalogen monomer of formula (IV), that is, the ratio of the two is in the range of about (0.9-1.1):(0.9-1.1), preferably about 1:1. (III) X-Ar2-X (IV) H-Ar3-H (V) In equations (III), (IV), and (V) above, Ar1 has the same meaning as Ar1 given in equation (I) above, except that in the structural formula representing Ar1, it contains " The single bond of “” is attached to the nitrogen atom of the five-membered ring of the carbazole group contained in the structural formula (III); Ar2 has the same meaning as Ar2 given in equation (I) above, except that in the structural formula representing Ar2, it contains " One of the two single bonds of “” is attached to a group X in structural formula (IV), and the “” The other of the two single bonds of the "" is attached to another group X in the structural formula (IV); X represents a halogen, such as F, Cl, Br, or I; Ar3 has the same meaning as Ar3 given in equation (II) above, except that in the structural formula representing Ar3, it contains " One of the two single bonds is connected to an H in the (V) structural formula, and the bond with " The other of the two single bonds is connected to the other H in the structure (V).

[0057] In some preferred embodiments of the preparation method according to the second aspect of the present invention, the volume of the azeotropic dehydrating agent is about 0.1 to about 20 times the volume of the solvent used in the polymerization reaction, for example, about 5 times, about 10 times, or about 15 times. Here, the volume of the azeotropic dehydrating agent should not be too large, for example, it should not exceed about 20 times the volume of the solvent used in the polymerization reaction, otherwise it may lead to problems such as a decrease in the polymerization rate and an increase in side reactions; in addition, the volume of the azeotropic dehydrating agent should not be too small, for example, it should not be less than about 0.1 times the volume of the solvent used in the polymerization reaction, otherwise it may lead to problems such as incomplete dehydration and difficulty in increasing molecular weight.

[0058] In some preferred embodiments of the preparation method according to the second aspect of the present invention, the molar amount of the catalyst is about 1 to about 10 times the total molar amount of the bisphenol monomer and bisphenol-like monomers contained in the reaction mixture, for example, about 2 times, about 3 times, about 4 times, about 5 times, about 6 times, about 7 times, about 8 times, or about 9 times. Here, the amount of catalyst should not be excessive, for example, it should not exceed about 10 times the total molar amount of the bisphenol monomer and bisphenol-like monomers, otherwise it may lead to problems such as uncontrollable reaction, increased side reactions, and increased costs; in addition, the amount of catalyst should not be too small, for example, it should not be less than about 1 times the total molar amount of the bisphenol monomer and bisphenol-like monomers, otherwise the reaction may not proceed smoothly.

[0059] In some preferred embodiments of the preparation method according to the second aspect of the present invention, the mass of the solvent is about 0.2 to about 50 times the total mass of the bisphenol monomer, bisphenol-like monomer, and aromatic dihalogen monomer contained in the reaction mixture, for example, about 5 times, about 10 times, about 15 times, about 20 times, about 25 times, about 30 times, about 35 times, about 40 times, or about 45 times. Here, the amount of solvent should not be excessive, for example, it should not exceed about 50 times the total mass of the bisphenol monomer, bisphenol-like monomer, and aromatic dihalogen monomer, otherwise it may lead to problems such as a slow reaction rate, difficulty in increasing molecular weight, and increased post-processing costs; in addition, the amount of solvent should not be too small, for example, it should not be less than about 0.2 times the total mass of the bisphenol monomer, bisphenol-like monomer, and aromatic dihalogen monomer, otherwise it may lead to problems such as difficulty in monomer dissolution and cross-linking during polymerization.

[0060] In some preferred embodiments of the preparation method according to the second aspect of the present invention, the protective gas includes one or more of nitrogen, helium, argon, neon, krypton, xenon, radon and carbon dioxide.

[0061] In some preferred embodiments of the preparation method according to the second aspect of the invention, the step-growth polymerization reaction includes subjecting the reaction system to a step-growth reaction in the range of about 110 to about 280°C, preferably including first subjecting the reaction system to an azeotropic dehydration reaction at a temperature of about 110 to about 150°C (e.g., at a temperature of about 120°C, about 130°C, or about 140°C), wherein water in the reaction system is carried out of the reaction system by an azeotropic dehydrating agent until the water content in the reaction system is reduced to below the detection limit, then the azeotropic dehydrating agent is distilled off until the content of the azeotropic dehydrating agent in the reaction system is reduced to below the detection limit, and then the reaction is carried out in the range of about 150 to about 280°C (e.g., at a temperature of about 175°C, about 200°C, about 225°C, about 250°C, or about about 275°C) until the viscosity no longer increases (indicating the end of the polymerization reaction).

[0062] In some preferred embodiments of the preparation method according to the second aspect of the invention, the settling agent comprises one or more of water, alcohol, tetrahydrofuran, and acetone.

[0063] According to a third aspect of the present invention, the present invention provides the use of the high-temperature resistant polymer described in the first aspect of the present invention or the high-temperature resistant polymer prepared according to the preparation method described in the second aspect of the present invention for preparing high-temperature resistant electromagnetic wire paint.

[0064] The present invention will now be described in further detail with reference to specific embodiments and comparative examples.

[0065] Unless otherwise stated, all chemicals used in the following examples are commercially available analytical grade chemicals.

[0066] The following monomers are used in the following embodiments: Bisphenol monomers containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure. Bisphenol-like monomers containing an N-p-ethynylphenylcarbazole group and a bis(diazanaphthone) structure. Bisphenol monomers containing an N-m-dicyanophenylcarbazole group and a bis(diazanaphthone) structure. Bisphenol monomers containing an N-p-cyanooxyphenylcarbazole group and a bis(diazanaphthone) structure. It was prepared according to the method disclosed by Ashay et al. (Macromolecules, 1997, 30(8), 2254): including first preparing the corresponding intermediate acid by Friedel-Crafts reaction, and then cyclizing the intermediate acid with hydrazine hydrate to obtain the corresponding product.

[0067] The 4-(4-hydroxyphenyl)-2,3-diazanaphth-1-one (DHPZ) used in the following examples was prepared according to the method disclosed in Chinese Patent CN109813A.

[0068] The bis(diazanaphthone) monomers used in the following comparative examples were prepared according to the method disclosed by Ashay et al. (Macromolecules, 1997, 30(8), 2254).

[0069] Example 1-1 (E1-1) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 3 mol of a bisphenol-like monomer containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure, approximately 7 mol of 4-(4-hydroxyphenyl)-2,3-diazanaphth-1-one (DHPZ) monomer, approximately 16 mol of anhydrous sodium carbonate, approximately 20 mol of potassium fluoride, approximately 10 mol of 2,6-difluorobenzonitrile, approximately 8 L of xylene, and approximately 15 L of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 150°C under an argon atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 220°C, with stirring continued for approximately 16 hours to form a polyarylene ether nitrile containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure.

[0070] After the reaction was completed, the reaction mixture was sprayed and precipitated in hot water to obtain a white solid. This solid was then washed with water and dried to obtain a polyarylene ether nitrile containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure. Its molecular weight and T... g The data is shown in the attached table.

[0071] Tests showed that the polyarylene ether nitrile resin containing N-p-cyanophenylcarbazole groups and bis(diazanaphthyl)one structures obtained in Example 1 is soluble in polar aprotic organic solvents such as N-methylpyrrolidone (NMP) and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0072] Examples 1-2 (E1-2) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 5 mol of a bisphenol-like monomer containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure, approximately 5 mol of 4-(4-hydroxyphenyl)-2,3-diazanaphth-1-one (DHPZ) monomer, approximately 16 mol of anhydrous sodium carbonate, approximately 20 mol of potassium fluoride, approximately 10 mol of 2,6-difluorobenzonitrile, approximately 8 L of xylene, and approximately 15 L of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 150°C under an argon atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 220°C, with stirring continued for approximately 16 hours to form a polyarylene ether nitrile containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure.

[0073] After the reaction was completed, the reaction mixture was sprayed and precipitated in hot water to obtain a white solid. This solid was then washed with water and dried to obtain a polyarylene ether nitrile containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure. Its infrared spectrum is shown below. Figure 1 As shown, its molecular weight and T g The data is shown in the attached table.

[0074] Tests showed that the polyarylene ether nitrile resin containing N-p-cyanophenylcarbazole groups and bis(diazanaphthone) structures obtained in Example 1 is soluble in polar aprotic organic solvents such as N-methylpyrrolidone (NMP) and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0075] Examples 1-3 (E1-3) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 7 mol of a bisphenol-like monomer containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure, approximately 3 mol of 4-(4-hydroxyphenyl)-2,3-diazanaphth-1-one (DHPZ) monomer, approximately 16 mol of anhydrous sodium carbonate, approximately 20 mol of potassium fluoride, approximately 10 mol of 2,6-difluorobenzonitrile, approximately 8 L of xylene, and approximately 15 L of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 150°C under an argon atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 220°C, with stirring continued for approximately 16 hours to form a polyarylene ether nitrile containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure.

[0076] After the reaction was completed, the reaction mixture was sprayed and precipitated in hot water to obtain a white solid. This solid was then washed with water and dried to obtain a polyarylene ether nitrile containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure. Its molecular weight and T... g The data is shown in the attached table.

[0077] Tests showed that the polyarylene ether nitrile resin containing N-p-cyanophenylcarbazole groups and bis(diazanaphthone) structures obtained in Example 1 is soluble in polar aprotic organic solvents such as N-methylpyrrolidone (NMP) and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0078] The proton NMR spectra of the polymers obtained in Examples E1-1, E1-2, and E1-3 above are shown in the appendix. Figure 5 As can be seen from the infrared spectrum and the proton nuclear magnetic resonance spectrum, the desired polymer was successfully synthesized in the embodiments of the present invention.

[0079] Example 2 (E2) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 0.005 mol of a bisphenol-like monomer containing an N-p-ethynylphenylcarbazole group and a bis(diazanthone) structure, approximately 0.005 mol of DHPZ monomer, approximately 0.03 mol of anhydrous sodium carbonate, approximately 0.01 mol of 2,6-difluorobenzonitrile, approximately 8 mL of xylene, and approximately 15 mL of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 120°C under a nitrogen atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 220°C, with stirring continued for approximately 10 hours to form a polyarylene ether nitrile containing an N-p-ethynylphenylcarbazole group and a bis(diazanthone) structure.

[0080] After the reaction was completed, the reaction mixture was poured into acetone to obtain a white strip-shaped solid, which was then washed with water and dried to obtain a polyarylene ether nitrile containing an N-p-ethynylphenylcarbazole group and a bis(diazanaphthone) structure.

[0081] Tests showed that the polyarylene ether nitrile resin containing N-p-ethynylphenylcarbazole groups and bis(diazanaphthone) structures obtained in Example 2 is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0082] Example 3 (E3) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 0.005 mol of a bisphenol-like monomer containing N-m-dicyanophenylcarbazole groups and a bis(diazanthone) structure, approximately 0.005 mol of DHPZ monomer, approximately 0.03 mol of anhydrous potassium carbonate, approximately 0.01 mol of 2,6-difluorobenzonitrile, approximately 8 mL of xylene, and approximately 15 mL of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 120°C under a nitrogen atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 200°C, with stirring continued for approximately 10 hours to form a polyarylene ether nitrile containing N-m-dicyanophenylcarbazole groups and a bis(diazanthone) structure.

[0083] After the reaction was complete, the reaction mixture was poured into boiling water to obtain a white, strip-shaped solid. This solid was then washed with water and dried to obtain a polyarylene ether nitrile containing an N-m-dicyanophenylcarbazole group and a bis(diazanaphthone) structure. Its infrared spectrum is shown below. Figure 2 As shown.

[0084] Tests showed that the polyarylene ether nitrile resin containing N-m-dicyanophenylcarbazole groups and bis(diazanaphthone) structures obtained in Example 3 is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0085] Example 4 (E4) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 0.05 mol of a bisphenol-like monomer containing an N-p-cyanooxyphenylcarbazole group and a bis(diazanthone) structure, approximately 0.05 mol of DHPZ monomer, approximately 0.3 mol of anhydrous sodium carbonate, approximately 0.1 mol of 2,6-difluorobenzonitrile, approximately 80 mL of xylene, and approximately 150 mL of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 110°C under a nitrogen atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 210°C, and the reaction was continued with stirring for approximately 10 hours to form a polyarylene ether nitrile containing an N-p-cyanooxyphenylcarbazole group and a bis(diazanthone) structure.

[0086] After the reaction was completed, the reaction mixture was sprayed and precipitated in ethanol to obtain a white solid. This solid was then washed with water and dried to obtain a polyarylene ether nitrile containing an N-p-cyanooxyphenylcarbazole group and a bis(diazanaphthone) structure. Its infrared spectrum is shown below. Figure 3 As shown.

[0087] Tests showed that the polyarylene ether nitrile resin containing N-p-cyanooxyphenylcarbazole group and bis(diazanaphthone) structure obtained in Example 4 is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0088] Example 5 (E5) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 5 mol of a bisphenol-like monomer containing an N-p-cyanophenylcarbazole group and a bis(diazanthone) structure, approximately 5 mol of DHPZ monomer, approximately 16 mol of anhydrous sodium carbonate, approximately 20 mol of potassium fluoride, approximately 4 mol of 2,6-difluorobenzonitrile, approximately 6 mol of difluorodiphenyl sulfone, approximately 8 L of xylene, and approximately 15 L of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 140°C under an argon atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 200°C, with stirring continued for approximately 16 hours to form a polyarylene ether sulfone containing an N-p-cyanophenylcarbazole group and a bis(diazanthone) structure.

[0089] After the reaction was completed, the reaction mixture was poured into ethanol to obtain a white strip-shaped solid, which was then washed with water and dried to obtain a polyarylene ether sulfone containing an N-p-cyanophenylcarbazole group and a bis(diazanaphthone) structure.

[0090] Tests showed that the polyarylene ether sulfone resin containing N-p-cyanophenylcarbazole groups and bis(diazanaphthone) structures obtained in Example 5 is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0091] Example 6 (E6) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 0.005 mol of a bisphenol-like monomer containing N-m-dicyanophenylcarbazole groups and a bis(diazanthone) structure, approximately 0.005 mol of DHPZ monomer, approximately 0.03 mol of anhydrous sodium carbonate, approximately 0.005 mol of 2,6-difluorobenzonitrile, approximately 0.005 mol of difluorodiphenyl sulfone, approximately 8 mL of xylene, and approximately 15 mL of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 150°C under a nitrogen atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 210°C, and the reaction was continued with stirring for approximately 10 hours to form a polyarylene ether sulfone containing N-m-dicyanophenylcarbazole groups and a bis(diazanthone) structure.

[0092] After the reaction was completed, the reaction mixture was poured into boiling water to obtain a white strip-shaped solid. After washing with water and drying, a polyarylene ether sulfone containing an N-m-dicyanophenylcarbazole group and a bis(diazanaphthone) structure was obtained.

[0093] Tests showed that the polyarylene ether sulfone resin containing N-m-dicyanophenylcarbazole groups and bis(diazanaphthone) structures obtained in Example 6 is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0094] Example 7 (E7) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 0.05 mol of a bisphenol-like monomer containing an N-p-cyanooxyphenylcarbazole group and a bis(diazanaphthone) structure, approximately 0.05 mol of DHPZ monomer, approximately 0.3 mol of anhydrous sodium carbonate, approximately 0.05 mol of 2,6-difluorobenzonitrile, approximately 0.05 mol of difluorodiphenyl sulfone, approximately 80 mL of xylene, and approximately 150 mL of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 110°C under a nitrogen atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 210°C, and the reaction was continued with stirring for approximately 10 hours to form a polyarylene ether sulfone containing an N-p-cyanooxyphenylcarbazole group and a bis(diazanaphthone) structure.

[0095] After the reaction was completed, the reaction mixture was sprayed and precipitated in ethanol to obtain a white strip-shaped solid, which was then washed with water and dried to obtain a polyarylene ether sulfone containing an N-p-cyanooxyphenylcarbazole group and a bis(diazanaphthone) structure.

[0096] Tests showed that the polyarylene ether sulfone resin containing N-p-cyanooxyphenylcarbazole group and bis(diazanaphthone) structure obtained in Example 7 is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0097] Example 8 (E8) In a polymerization reactor equipped with a mechanical stirrer, reflux condenser, water separator, and gas delivery pipe, approximately 0.005 mol of a bisphenol-like monomer containing an N-p-ethynylphenylcarbazole group and a bis(diazanthone) structure, approximately 0.005 mol of DHPZ monomer, approximately 0.03 mol of anhydrous sodium carbonate, approximately 0.005 mol of 2,6-difluorobenzonitrile, approximately 0.005 mol of difluorodiphenyl sulfone, approximately 8 mL of xylene, and approximately 15 mL of sulfolane were added. The reaction mixture was subjected to a xylene-containing aqueous reaction at approximately 120°C under a nitrogen atmosphere for approximately 2 hours. After the reaction system was essentially free of water, the xylene was distilled off, and the temperature was raised to approximately 200°C, with stirring continued for approximately 10 hours to form a polyarylene ether nitrile sulfone containing an N-p-ethynylphenylcarbazole group and a bis(diazanthone) structure.

[0098] After the reaction was completed, the reaction mixture was sprayed into acetone to obtain a white strip-shaped solid. After washing with water and drying, a polyarylene ether nitrile sulfone containing an N-p-ethynylphenylcarbazole group and a bis(diazanaphthone) structure was obtained.

[0099] Tests showed that the polyarylene ether sulfone resin containing N-p-ethynylphenylcarbazole groups and bis(diazanaphthone) structures obtained in Example 8 is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0100] Comparative Example 1 (CE1) In a 1L three-necked flask equipped with a mechanical stirrer, reflux separator, condenser, and nitrogen delivery tube, add approximately 0.2 mol of bis(diazanaphthyl) monomer, approximately 0.3 mol of anhydrous potassium carbonate, approximately 0.16 mol of 4,4'-difluorodiphenyl sulfone, approximately 0.04 mol of 2,6-difluorodiphenyl nitrile, approximately 100 mL of sulfolane as solvent, and approximately 120 mL of... Using toluene as a dehydrating agent, a high-temperature solution stepwise polymerization was carried out under nitrogen protection. The reaction was stirred and refluxed at approximately 140°C for about 3 hours, allowing the bisphenol-like monomer to react with K₂CO₃ to form a salt, carrying out toluene and the generated water. The temperature was then raised to approximately 190°C and reacted for about 8 to 10 hours. After dilution with solvent, the polymer was precipitated in hot water to obtain thin, pale yellow strips. The polymer was placed in boiling water to remove residual inorganic salts and sulfolane solvent. After filtration and drying, a polyarylethene sulfone ketone (PBPENS-8020) with a diphenyl ether bis(diazanaphthyl) ketone structure was obtained, wherein the molar ratio of the dihalogen monomers 2,6-difluorodiphenyl nitrile and 4,4′-difluorodiphenyl sulfone was approximately 20:80. Its infrared spectrum is shown below. Figure 4 As shown.

[0101] Tests showed that the diphenyl ether bis(diazanaphthone)-structured polyarylether sulfone ketone resin obtained in Comparative Example 1 is soluble in chloroform, tetrachloroethane, and NMP organic solvents (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0102] Comparative Examples 2 to 4 (CE2 to CE4) Polyarylene ether sulfone ketones PBPENS-4060, PBPENS-5050, and PBPENS-6040 with diphenyl ether bis(diazanaphthyl) ketone structures were synthesized using a process similar to that of Comparative Example 1. The difference lay in controlling the molar ratio of the dihalogen monomer 2,6-difluorodiphenyl nitrile and 4,4′-difluorodiphenyl sulfone to be 40:60, 50:50, and 60:40, respectively, to obtain the polyarylene ether sulfone ketones PBPENS-4060, PBPENS-5050, and PBPENS-6040 of Comparative Examples 2 to 4, respectively. Their infrared spectra are shown below. Figure 4 As shown.

[0103] Tests showed that the diphenyl ether bis(diazanaphthone)-structured polyarylether sulfone ketone resins obtained in Comparative Examples 2 to 4 are soluble in chloroform, tetrachloroethane, and NMP organic solvents (i.e., at least about 0.1 g of the polymer is soluble in about 1 mL of the above solvents).

[0104] The molecular weight and T of the polymers obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were measured. g Equal performance, among which Molecular weight was determined by gel permeation chromatography (GPC) using N-methylpyrrolidone (NMP) as the mobile phase. The test temperature was approximately 80°C, and the flow rate of the mobile phase was approximately 1.0 mL / min. The relative molecular weight and its distribution of the sample were determined. T g The measurements included the study of the dynamic mechanical and thermal properties of the polymers using a dynamic thermomechanical analyzer (DMA, METTLER DMA861e, Switzerland). The thin films were measured in a stretching mode, with the stretching measurements performed at a frequency of approximately 1 Hz, a tensile stress of approximately 15 N, and a heating rate of approximately 5 °C / min. The resin sheets were measured in a single cantilever mode with an amplitude of approximately 1 Hz and a heating rate of approximately 5 °C / min.

[0105] The structures and properties of the obtained polymers are summarized in Table 1 below: In addition, the mechanical properties of the polymers obtained in the above examples and comparative examples were measured using methods commonly used in the art (specific test conditions: using an AnInstron-5869 machine, a load of approximately 100 N, a strain rate of approximately 2 mm / min, an effective tensile length of approximately 20 mm, and a width of approximately 6 mm). The results are shown in Table 2 below. Table 2: Mechanical properties of polymers from the examples and comparative examples As can be seen from the mechanical property test results of E1-1, E1-2, and E1-3 in Table 2 above, with the continuous increase of the proportion of structure (I), the rotational steric hindrance within the polymer backbone gradually increases, resulting in a slight increase in the tensile strength of the material. Simultaneously, the tensile modulus steadily increases, while the elongation at break shows a continuous downward trend. This trend indicates that structure (I) enhances the rigidity of the molecular chain and intermolecular interactions, thereby improving the mechanical strength and stiffness of the material while restricting the chain segment mobility, leading to a decrease in plasticity and an increase in brittleness.

[0106] Comparing the three groups of samples—E2 (ethynyl-modified), E3 (dicyano-modified), and E4 (cyanate-modified)—it can be found that the polarity of the side groups significantly modulates the mechanical properties of polyarylethers. The dicyano group exhibits the strongest dipole interaction, greatly restricting molecular chain movement; therefore, E3 possesses the highest tensile strength and modulus, with an elongation at break of only about 4.5%. The ethynyl group has the weakest polarity, allowing for greater freedom of chain segment movement, resulting in E2 maintaining the highest elongation at break and optimal toughness. The polarity of the cyanate group is intermediate, thus E4 has a moderate elongation at break. After introducing a rigid diphenyl sulfone structure into the main chain, the polymers E5, E6, E7, and E8 maintain consistent structural property characteristics. This result further verifies the regulatory effect of side group polarity on mechanical properties.

[0107] For the random copolymer systems from CE1 to CE4, as the proportion of sulfone-based rigid monomers increases, the tensile strength and tensile modulus of the material increase, while the elongation at break decreases. The increase in rigid monomer components raises the rotational barrier within the molecular chain, achieving a simultaneous increase in polymer strength and modulus, while sacrificing some elongation capacity. The mechanical properties exhibit a continuous and monotonic evolution trend with changes in copolymer composition.

[0108] Overall experimental results show that by adjusting the ratio of comonomers and the polarity of side groups, the rigidity of molecular chains and intermolecular forces can be precisely adjusted, thereby achieving systematic control of the tensile strength, modulus and elongation at break of high-temperature resistant polyarylethers.

[0109] The performance data of Examples E1-1, E1-2, and E1-3 above (see Table 1) also show that as the content of structure (I) increases, the internal rotation barrier of the polymer backbone increases, making it more difficult for the molecular chain to transition from a frozen state to a mobile state when heated. Higher temperatures are required to impart sufficient energy to the chain segments to overcome the energy barrier, thus manifesting as T g The temperature rises continuously. Therefore, it can be seen that by controlling the structure and ratio of structural units containing carbazole groups and bis(diazanaphthone) structures with other structural units, the heat resistance and solubility of the polymer of this invention can be adjusted, thus increasing the polymer's Tg. g It can reach temperatures of approximately 400°C or even 420°C, thus meeting the needs of a wider range of applications.

[0110] Compared to the polyarylene ether sulfononitrile polymers containing substituted carbazole groups and bis(diazanaphthone) structures obtained in Examples E6 to E8 of the present invention, the structure of the polyarylene ether polymer containing substituted carbazole groups and bis(diazanaphthone) structures in Comparative Example CE3 is different. The polymer in Comparative Example CE3 does not contain the carbazole structure found in the polymers of Examples E6 to E8, while the other copolymer monomer units are similar. Based on the heat resistance and solubility data of Examples E6 to E8 and Comparative Example CE3, the polymers of Examples E6 to E8 have higher glass transition temperatures T0. g It is still soluble in polar aprotic organic solvents.

[0111] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions claimed by the present invention.

Claims

1. A high-temperature resistant polymer comprising a carbazole group and a bis(diazanaphthone) structure, characterized in that, The polymer contains structural units of formula (I) in its main chain: （I） in, n represents the molar percentage of the structural units of formula (I) contained in the main chain of each polymer molecule, 90% ≥ n ≥ 10%, preferably not less than 30%, more preferably not less than 50%, and particularly preferably not less than 70%; Ar1, each time it appears, independently and identically or differently from each other, represents a structural part represented by one or more of the following structural formulas: ； ； ； ； ； and ; In the above structural formula representing Ar1, the part containing " The single bond of the '' group is attached to the nitrogen atom of the five-membered ring of the carbazole group contained in structural formula (I). Ar2, each time it appears, independently and identically or differently from each other, represents a structural part represented by one or more of the following structural formulas: ； ； ； ;and , In the above structural formula representing Ar2, R represents a substituent on the benzene ring to which it is attached, and the substituent, each time it appears, independently and identically or differently from each other, represents a phenyl group, an alkyl group containing 1 to 20 carbon atoms, or an alkoxy group containing 1 to 20 carbon atoms; 'a' represents the number of substituents R on the benzene ring, a = 0 or 1; and With " One of the two single bonds is attached to the nitrogen atom of the six-membered ring of the diazanaphthone structure linked to Ar2 in formula (I), and the single bond with " The other of the two single bonds in the "" bond connects to another structural unit in the main chain of the polymer molecule. In the above structural formulas representing monomers, polymers, and groups, the chemical bond extending from the outside of the benzene ring and extending into the interior of the benzene ring means that the group or structure connected to the benzene ring by the bond is not fixedly connected to a specific carbon atom of the benzene ring, but is connected to any unoccupied optional position in the benzene ring.

2. The polymer according to claim 1, characterized in that, The polymer backbone also contains structural units of formula (II): (II) In the structural unit of equation (II) above, p represents the molar percentage of the structural units of formula (II) contained in the main chain of each polymer molecule, 90% ≥ p ≥ 10%, preferably not higher than 30%, more preferably not higher than 50%, and particularly preferably not higher than 70%; Ar2 has the same meaning as given in claim 1, except that in the structural formula representing Ar2, it contains " One of the two single bonds is attached to the Ar3 group in the structural formula (II), and the group with " The other of the two single bonds of the "" is attached to another structural unit in the main chain of the polymer molecule; Ar3, each time it appears, independently and identically or differently from each other, represents a structural part represented by one or more of the following structural formulas: ； ； ； ； ； ； ； ； ； In the above structural formula representing Ar3, R' represents a substituent on the benzene ring to which it is attached, and the substituent, each time it appears, is independently and identically or differently selected from one or more of a halogen group, a phenoxy group, an alkyl group containing 1 to 20 carbon atoms, and an alkoxy group containing 1 to 20 carbon atoms; m represents the number of substituents R' on the benzene ring containing the substituent R', m = 0, 1, 2, 3 or 4; and With " One of the two single bonds is attached to the Ar2 group in the structural formula (II), and the group with " The other of the two single bonds is attached to another structural unit in the main chain of the polymer molecule.

3. The polymer according to claim 2, characterized in that, Each time Ar3 appears, it independently and identically or differently represents a structural part represented by one or more of the following structural formulas: The two oxygen atoms on the benzene ring are located at positions 1,2, 1,3, or 1,4. The two oxygen atoms on the benzene ring are located at the 2,2' or 4,4' positions; The two oxygen atoms on the benzene ring are located at positions 1,4, 1,5, 1,6, 2,6, or 2,7. The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions; The two oxygen atoms on the benzene ring are located at the 3,3' or 4,4' positions.

4. The polymer according to claim 1, characterized in that, The structural unit of formula (I) includes structural units of formula (I-1) and / or (I-2): （I-1） （I-2）。 5. The polymer according to any one of claims 1 to 4, characterized in that, Each time Ar1 appears, it independently and identically or differently represents a structural part represented by one or more of the following structural formulas: ； ； ； ； ； ； ； ;and ; and / or Each time Ar2 appears, it independently and identically or differently represents a structural part represented by one or more of the following structural formulas: ； ； ; ;and 。 6. The polymer according to any one of claims 1 to 4, characterized in that, The polymer has one or more of the following properties: The polymer has a molecular weight of not less than 9000 g / mol, preferably in the range of 40000 to 60000 g / mol; The glass transition temperature T of the polymer g The temperature should be no less than 369°C, preferably no less than 400°C, more preferably no less than 420°C, and most preferably no less than 430°C. The polymer has a solubility of not less than 0.1 g / mL in any one of the polar aprotic organic solvents selected from sulfolane, N-methylpyrrolidone, N,N-dimethylacetamide, and 1,1,2,2-tetrachloroethane. The tensile strength of the polymer is not less than 89.5 MPa, preferably not less than 97.5 MPa, and more preferably not less than 102.3 MPa; The polymer has a tensile modulus of not less than 3.03 GPa, preferably not less than 3.55 GPa, and more preferably not less than 4.0 GPa; and The elongation at break of the polymer is in the range of 3.7% to 6.6%.

7. A method for preparing the polymer according to any one of claims 1 to 6, characterized in that, The preparation method includes: The bisphenol-like monomer of formula (III), the aromatic dihalogen monomer of formula (IV), and optionally the bisphenol or bisphenol-like monomer of formula (V) are mixed with a solvent, an azeotropic dehydrating agent, and a catalyst. The resulting reaction system undergoes a stepwise polymerization reaction under a protective gas atmosphere. After the polymerization reaction is completed, the resulting reaction mixture is precipitated in a settling agent to obtain the polymer as the precipitate. The ratio of the total molar number of the bisphenol-like monomer of formula (III) and optionally the bisphenol or bisphenol-like monomer of formula (V) to the molar number of the aromatic dihalogen monomer of formula (IV) is in the range of (0.9-1.1):(0.9-1.1), preferably 1:

1. (III) X-Ar2-X (IV) H-Ar3-H (V) In the above equations (III), (IV) and (V) Ar1 has the same meaning as given in claim 1, except that in the structural formula representing Ar1, it contains " The single bond of “” is attached to the nitrogen atom of the five-membered ring of the carbazole group contained in the structural formula (III); Ar2 has the same meaning as given in claim 1, except that it contains " One of the two single bonds of the symbol is attached to a group X in structural formula (IV), and the symbol carries the symbol " The other of the two single bonds of the "" is attached to another group X in the structural formula (IV); X represents a halogen, such as F, Cl, Br, or I; Ar3 has the same meaning as given in claim 2, except that it contains " One of the two single bonds is connected to an H in the (V) structural formula, and with " The other of the two single bonds is connected to the other H in the structure (V).

8. The preparation method according to claim 7, characterized in that, The solvent comprises a polar organic solvent, preferably containing one or more of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone, hexamethylphosphoric triamine, or sulfolane; and / or The azeotropic aqueous agent comprises one or more of aromatic hydrocarbons and halogenated aromatic hydrocarbons, preferably including one or more of benzene, toluene, xylene, and halogenated benzenes; and / or The catalyst comprises carbonates and / or bicarbonates and optionally fluoride catalysts, wherein the carbonates and / or bicarbonates preferably comprise alkali metal carbonates and / or alkali metal bicarbonates and / or alkaline earth metal carbonates and / or alkaline earth metal bicarbonates; and the fluoride catalyst preferably comprises alkali metal fluorides.

9. The preparation method according to claim 7 or 8, characterized in that, The volumetric amount of the azeotropic dehydrating agent is 0.1 to 20 times the volume of the solvent used in the polymerization reaction; and / or The molar amount of the catalyst is 1 to 10 times the total molar amount of bisphenol monomers and bisphenol-like monomers contained in the reaction mixture; and / or The mass of the solvent is 0.2 to 50 times the total mass of the bisphenol monomer, bisphenol-like monomer, and aromatic dihalogen monomer contained in the reaction mixture; and / or The protective gas includes one or more of nitrogen, helium, argon, neon, krypton, xenon, radon, and carbon dioxide; and / or The step-growth polymerization reaction includes conducting a step-growth reaction in the range of 110 to 280°C, preferably including first conducting an azeotropic dehydration reaction in the reaction system at a temperature of 110 to 150°C, wherein water in the reaction system is carried out of the reaction system by an azeotropic dehydrating agent until the water content in the reaction system is reduced below the detection limit, then distilling off the azeotropic dehydrating agent until the content of the azeotropic dehydrating agent in the reaction system is reduced below the detection limit, and then reacting again in the temperature range of 150 to 280°C until the viscosity no longer increases; and / or The settling agent includes one or more of water, alcohol, tetrahydrofuran, and acetone.

10. Use of the polymer according to any one of claims 1 to 6 or the polymer prepared by any one of claims 7 to 9 for the preparation of high-temperature resistant electromagnetic wire varnish.

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