Polar group or heterocyclic ring bridged bis (phthalazinone) structure polymer and preparation method thereof

Abstract

The invention provides a polar group or heterocyclic ring bridged bis (phthalazinone) structure polymer and a preparation method thereof, and relates to the technical field of high polymer material synthesis. According to the polar group or heterocyclic ring bridged bis (phthalazinone) structure polymer, the polar group or heterocyclic ring bridged bis (phthalazinone) structure is introduced, so that the polymer has more excellent heat resistance and good solubility, the glass-transition temperature of the polymer can be up to 405 DEG C, and the polymer can be dissolved in N-methyl pyrrolidone, 1, 1, 2, 3, 4-tetramethyl-3-pyrrolidone, 1, 1, 2, 3-tetramethyl-3-pyrrolidone, 1, 1, 2, 3, 3-tetramethyl-3-pyrrolidone and 1, 1, 2, 3, 3-tetramethyl-3-pyrrolidone. A polar aprotic organic solvent such as 1, 1, 2, 2-tetrachloroethane; besides, the heat resistance and solubility of the polymer can be regulated and controlled by regulating the structures and proportions of the polar group or heterocyclic bridged bis (phthalazinone) structural unit and other structural units, so that the polymer can meet the requirements of more different application scenes. The invention also provides a preparation method of the polymer.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material synthesis, and relates to a polar group or heterocyclic bridged phthalazinone structure polymer and a preparation method thereof. Background Art

[0002] Polyarylether is a type of high temperature resistant engineering plastics with excellent heat resistance and mechanical properties. It can be used to prepare resin-based composite materials, high temperature resistant separation membranes, functional membranes, enameled wires, cables, wear-resistant materials, biomedical materials, etc. It is widely used in aerospace, marine engineering, energy, electronics, petrochemicals, biomedicine and other fields. There are many types of polyarylether resins, and different polyarylethers have different heat resistance properties. For example, the glass transition temperature of commercial polyetheretherketone (PEEK, a semi-crystalline polymer) is ( T g ) is 143°C, polyphenylene sulfone (PPSU, amorphous polymer) T g 288℃. However, with the continuous development of the above fields, higher requirements are put forward for the heat resistance of polyarylether, and it is required to have good solubility and be processed in various ways. Our research group reported a series of polyaryletherketones containing diazonium phthalide biphenyl structures ( T g =263℃)、polyarylethersulfone( T g =305℃)、polyarylethernitrileketone( T g =268~289℃, Wang Mingjing, PhD thesis of Dalian University of Technology, 2007; Chinese invention patent ZL03111540.3) resin, which has both excellent heat resistance and good solubility. AS Hay et al. (Macromolecules, 1997, 30(8), 2254) reported poly(aryletherketone) containing diphenyl ether or diphenyl sulfide structure T g : 301℃ and 281℃) and polyarylethersulfone ( T g : 295℃ and 279℃), and prepared polyarylsulfones with bis(phthalazinone) structures based on bisphenol-like monomers synthesized from dianhydrides. T g :221℃、310℃、344℃)、polyaryl ketone( T g : 195℃, 286℃) and polyaromatic nitrile ( T g: 200℃, 301℃), but due to the high cost and price of dianhydride compounds, the synthesis cost of monomers and polymers is significantly high, and because there is no flexible ether bond group in the main chain of the molecule, and some diphenylamine structure monomers are very rigid, the solubility of the polymer is poor, the synthesis is difficult, and the molecular weight is not high. For example, the diphenylamine structure monomer synthesized based on sulfone-containing dianhydride, the polymerization to obtain polyaryl sulfone (main chain does not contain ether bonds) has poor solubility and an intrinsic viscosity of only 0.11dL / g, indicating that the molecular weight of the polymer is very low. Zhang Shouhai et al. disclosed a diphenylamine structure-containing copolyaryl ether sulfone and its preparation method (Chinese patent, publication number CN113461943A) and a diphenylamine structure-containing copolyaryl ether nitrile and its preparation method (Chinese patent, publication number CN116675849A), and the glass transition temperature of the embodiment can reach 373℃.

[0003] In summary, although the heat resistance of the polymer can be improved by introducing a rigid aromatic heterocyclic structure into the polyarylether molecular chain, the heat resistance and solubility of the polymer need to be considered. Therefore, it is necessary to obtain a polymer with both excellent heat resistance and good solubility through molecular structure design and synthesis.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The object of the present invention is to provide a polar group or heterocyclic bridged phthalazinone structure polymer and a preparation method and application thereof, so as to solve the above technical problems.

[0006] In order to achieve the above purpose, the following technical solutions are adopted: The first object of the present invention is to provide a polar group or heterocyclic bridged phthalazinone structure polymer, the structural formula of which is shown in formula (1) or formula (2): (1); (2); In formula (1) and formula (2), The structure is one or more of the following structures: ; ; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; In formula (1) and formula (2), the structure of —Ar2— is one or more of the following structures: ; ; ; ; , R is selected from hydrogen, phenyl, alkyl or alkoxy, wherein the alkyl or alkoxy is a straight chain or branched alkyl or alkoxy containing 1 to 20 carbon atoms; In formula (1), the structure of —Ar3— is one or more of the following structures: , 1, 2 digits, 1, 3 digits or 1, 4 digits; , 2, 2′ position or 4, 4′ position; , 1, 4 digits, 1, 5 digits, 1, 6 digits, 2, 6 digits or 2, 7 digits; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group, or an alkoxy group, and the structures of R1, R2, R3, and R4 are the same or different, wherein the alkyl group or the alkoxy group is a straight chain or branched alkyl group or alkoxy group containing at least one carbon atom; ; ; ; ; ; ; ; ; ; ; ; ; ; ; in, One or more of the following structures: ; ; ; ; ; ; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; for , One or more of the .

[0007] The second object of the present invention is to provide a method for preparing a polar group or heterocyclic bridged phthalazinone structure polymer, comprising the following steps: A bisphenol monomer containing a polar group or heterocyclic bridging bisphthalazinone structure and an aromatic dihalogen monomer, as well as other optional bisphenols or bisphenol-like monomers are used as polycondensation monomers, mixed with a solvent, an azeotropic water-carrying agent and a catalyst, and a stepwise polymerization reaction is carried out under a protective gas atmosphere. The reaction solution obtained after the polymerization reaction is precipitated in a precipitant, and the precipitated solid product is washed, filtered and dried to obtain a polar group or heterocyclic bridging bisphthalazinone structure polymer.

[0008] Further, on the basis of the above technical solution of the present invention, the bisphenol monomer containing polar groups or heterocyclic bridged phthalazinone structures has the following molecular structure: Wherein, the structure of —Ar1— is one or more of the following structures: ; ; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; And / or, the structure of the aromatic dihalogen monomer is one or more of the following structures: ; ; ; ; , R is selected from hydrogen, phenyl, alkyl or alkoxy, wherein the alkyl or alkoxy is a straight chain or branched alkyl or alkoxy containing 1 to 20 carbon atoms; X is F or Cl; And / or, the structure of the other bisphenol monomer or bisphenol-like monomer is one or more of the following structures: , 1, 2 digits, 1, 3 digits or 1, 4 digits; , 2, 2′ position or 4, 4′ position; , 1, 4 digits, 1, 5 digits, 1, 6 digits, 2, 6 digits or 2, 7 digits; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group, or an alkoxy group, and the structures of R1, R2, R3, and R4 are the same or different, wherein the alkyl group or the alkoxy group is a straight chain or branched alkyl group or alkoxy group containing at least one carbon atom; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Wherein, "X1" is one or more of the following structures: ; ; ; ; ; ; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; for , One or more of the .

[0009] Compared with the prior art, the technical solution of the present invention has at least the following technical effects: (1) The present invention provides a polar group or heterocyclic bridged phthalazinone structure polymer having both excellent heat resistance and good solubility. The polymer has better heat resistance and good solubility by introducing a polar group or heterocyclic bridged phthalazinone structure. The glass transition temperature ( T g ) can reach up to 405°C and can be dissolved in polar aprotic organic solvents such as N-methylpyrrolidone and 1,1,2,2-tetrachloroethane; in addition, the present invention can also adjust the heat resistance and solubility of this type of polymer by adjusting the structure and ratio of the polar group-containing or heterocyclic-bridged phthalazinone structural unit and other structural units, so that it can meet the needs of more different application scenarios.

[0010] (2) The present invention also provides a method for preparing the above-mentioned polar group or heterocyclic bridged phthalazinone structure polymer, which adopts nucleophilic substitution stepwise polymerization reaction to achieve stable preparation of the polymer.

[0011] (3) The present invention also provides the application of the above-mentioned polar group or heterocyclic bridged phthalazinone structure polymer. In view of the advantages of the above-mentioned polar group or heterocyclic bridged phthalazinone structure polymer, it can be widely used in the preparation of high temperature resistant resin-based composite materials, coatings, adhesives, functional films, copper clad laminates and other technical fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 The infrared spectrum (a) and nuclear magnetic resonance hydrogen spectrum (b) of the polymer prepared in Example 1 of the present invention; Figure 2 The infrared spectrum (a) and nuclear magnetic resonance hydrogen spectrum (b) of the polymer prepared in Example 2 of the present invention; Figure 3 The infrared spectrum (a) and nuclear magnetic resonance hydrogen spectrum (b) of the polymer prepared in Example 3 of the present invention; Figure 4 The infrared spectrum (a) and nuclear magnetic resonance hydrogen spectrum (b) of the polymer prepared in Example 4 of the present invention; Figure 5 The infrared spectrum (a) and nuclear magnetic hydrogen spectrum (b) of the polymer prepared in Example 5 of the present invention; Figure 6 The infrared spectrum (a) and nuclear magnetic resonance hydrogen spectrum (b) of the polymer prepared in Example 6 of the present invention; Figure 7 The infrared spectrum (a) and nuclear magnetic resonance hydrogen spectrum (b) of the polymer prepared in Example 7 of the present invention; Figure 8 The infrared spectrum (a) and nuclear magnetic resonance hydrogen spectrum (b) of the polymer prepared in Example 8 of the present invention; Fig. 9 The infrared spectrum (a) and nuclear magnetic hydrogen spectrum (b) of the polymer prepared in comparative example 1 of the present invention are shown. DETAILED DESCRIPTION

[0013] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention. The process parameters of the following embodiments that do not specify specific conditions are usually based on conventional conditions.

[0014] The endpoints and any values ​​of the ranges disclosed in the present 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. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, 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 the present invention. In addition, "A and / or B" in the present invention means that it can include only A, only B, or both A and B.

[0015] According to a first aspect of the present invention, a polar group or heterocyclic bridged phthalazinone structure polymer is provided, that is, the polymer contains a phthalazinone structure, and the phthalazinone structure contains a polar group bridged structure or a heterocyclic bridged structure, and the polymer structure is shown in formula (1) or formula (2): (1); (2); In formula (1) and formula (2), the structure of —Ar1— is one or a combination of the following structures: ; ; , 2, 2, 2, 3 or 3, 3; wherein, 2, 2, 2, 3 or 3, 3 is the connection site with diazinone, which is the isomer produced by the reaction of dithiophene compound, and there are 3 structures, which can also be separated and polymerized separately, or directly polymerized. The following structures all belong to this situation, and will not be described in detail later; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; The structure adopts a bridged structure containing a polar group or a ladder-shaped heterocycle, which is beneficial to further improve the heat resistance of the polar group or heterocycle-bridged phthalazinone structure polymer.

[0016] In formula (1) and formula (2), The structure is produced by the reaction of the corresponding aromatic dihalogen monomer and is determined by the structure of the selected aromatic dihalogen monomer. The structure is one or a combination of the following structures: ; ; ; ; , R is selected from hydrogen, phenyl, alkyl or alkoxy, wherein the alkyl or alkoxy is a straight chain or branched alkyl or alkoxy containing 1 to 20 carbon atoms; In formula (1), The structure of is produced by the reaction of the corresponding bisphenol or bisphenol-like monomers, and is determined by the structure of the selected bisphenol or bisphenol-like monomers. The structure is one or more of the following structures: , 1, 2, 1, 3 or 1, 4; wherein 1, 2, 1, 3, 1, 4 are the connection positions of oxygen on the benzene ring, which mainly depends on the structure of the bisphenol monomer used, and can be one or more of the three bisphenol monomers of hydroquinone, resorcinol or catechol, respectively producing 1, 2, 1, 3 or 1, 4, and the subsequent structures are similar and will not be repeated; , 2, 2′ position or 4, 4′ position; , 1, 4 digits, 1, 5 digits, 1, 6 digits, 2, 6 digits or 2, 7 digits; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group, or an alkoxy group, and the structures of R1, R2, R3, and R4 are the same or different, wherein the alkyl group or the alkoxy group is a straight chain or branched alkyl group or alkoxy group containing at least one carbon atom; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Wherein, "X1" is one or more of the following structures: ; ; ; ; ; ; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; for , One or more of the .

[0017] It should be noted that the polar group or heterocyclic bridged phthalazinone structure polymer structural formula (1) and formula (2) of the present invention only show the repeating unit structure contained therein, and do not limit the molecular weight or degree of polymerization. As a linear polymer, different applications (such as resin-based composite materials, coatings, adhesives, functional films and other different uses) have different requirements for the molecular weight of the polymer. The molecular weight of the phthalazinone structure polymer can be regulated according to the molar ratio of the polymerized monomers.

[0018] The present invention provides a polar group- or heterocyclic-bridged phthalazinone structure polymer having both excellent heat resistance and good solubility. The polymer has better heat resistance and good solubility by introducing a polar group- or heterocyclic-bridged phthalazinone structure. The glass transition temperature ( T g ) can reach up to 405°C, and can be dissolved in polar aprotic organic solvents such as N-methylpyrrolidone (NMP) and 1,1,2,2-tetrachloroethane; at the same time, by adding other bisphenols or bisphenol-like monomers, the heat resistance and solubility of the synthesized polar group or heterocyclic bridged phthalazinone structure polymer can be flexibly adjusted. When the content of flexible groups in the molecular chain is increased or the content of aromatic heterocyclic structure and polar groups is reduced, the heat resistance of the polar group or heterocyclic bridged phthalazinone structure polymer can be reduced, but its solubility in polar aprotic organic solvents such as N,N-dimethylacetamide (DMAc) and chloroform can be improved. That is, by adjusting the structure and ratio of the phthalazinone structural unit and other structural units, the heat resistance and solubility of this type of polymer can be adjusted, so that it can meet the needs of more different application scenarios.

[0019] As an optional implementation of the technical solution of the present invention, in formula (1) and formula (2), the structure of —Ar1— is one or more of the following structures: ; ; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; And / or, in formula (1) and formula (2), the structure of —Ar2— is one or more of the following structures: ; ; ; And / or, in formula (1), the structure of —Ar3— is one or more of the following structures: ; ; , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group or an alkoxy group, and the structures of R1, R2, R3 and R4 are the same or different, wherein the alkyl group or the alkoxy group is a straight chain or branched alkyl group or alkoxy group containing at least 1 carbon atom.

[0020] As an optional implementation of the technical solution of the present invention, the glass transition temperature of the polar group or heterocyclic bridged phthalazinone structure polymer can reach up to 405°C.

[0021] As an optional implementation of the technical solution of the present invention, the polar group or heterocyclic bridged phthalazinone structure polymer is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane.

[0022] According to a second aspect of the present invention, there is also provided a method for preparing the above-mentioned polar group or heterocyclic bridged phthalazinone structure polymer, comprising the following steps: A bisphenol monomer containing a polar group or heterocyclic bridging bisphthalazinone structure and an aromatic dihalogen monomer, as well as other optional bisphenols or bisphenol-like monomers are used as polycondensation monomers, mixed with a solvent, an azeotropic water-carrying agent and a catalyst, and a stepwise polymerization reaction is carried out under a protective gas atmosphere. The reaction solution obtained after the polymerization reaction is precipitated in a precipitant, and the precipitated solid product is washed, filtered and dried to obtain a polar group or heterocyclic bridging bisphthalazinone structure polymer.

[0023] It should be noted that "optionally other bisphenols or bisphenol-like monomers" means that other bisphenols or bisphenol-like monomers may or may not be added. When other bisphenols or bisphenol-like monomers are added, they can be polymerized with polar group or heterocyclic bridging bisphthalazinone structure-like bisphenol monomers and aromatic dihalogen monomers to generate a polymer having a structure as shown in formula (1). When other bisphenols or bisphenol-like monomers are not added and only polar group or heterocyclic bridging bisphthalazinone structure-like bisphenol monomers and aromatic dihalogen monomers are used as condensation monomers, a polymer having a structure as shown in formula (2) can be polymerized.

[0024] The method for preparing a polar group or heterocyclic bridged phthalazinone structure polymer provided by the invention adopts a nucleophilic substitution stepwise polymerization reaction, and can realize the stable preparation of the polymer.

[0025] As an optional implementation of the technical solution of the present invention, the bisphenol monomer containing a polar group or a heterocyclic bridged phthalazinone structure has the following molecular structure: in, The structure is one or more of the following structures: ; ; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits, or 3, 3 digits.

[0026] As an optional implementation of the technical solution of the present invention, the structure of the aromatic dihalogen monomer is one or more of the following structures: ; ; ; ; , R is selected from hydrogen, phenyl, alkyl or alkoxy, wherein the alkyl or alkoxy is a straight chain or branched alkyl or alkoxy containing 1 to 20 carbon atoms; X is a halogen, including F or Cl.

[0027] As an optional implementation of the technical solution of the present invention, the structure of other bisphenol monomers or bisphenol-like monomers is one or more of the following structures: , 1, 2 digits, 1, 3 digits or 1, 4 digits; , 2, 2′ position or 4, 4′ position; , 1, 4 digits, 1, 5 digits, 1, 6 digits, 2, 6 digits or 2, 7 digits; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group, or an alkoxy group, and the structures of R1, R2, R3, and R4 are the same or different, wherein the alkyl group or the alkoxy group is a straight chain or branched alkyl group or alkoxy group containing at least one carbon atom; ; ; ; ; ; ; ; ; ; ; ; ; ; ; in, One or more of the following structures: ; ; ; ; ; ; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; for , One or more of the .

[0028] As an optional implementation of the technical solution of the present invention, the solvent includes one or a mixture of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide or cyclopentane sulfone.

[0029] As an optional implementation of the technical solution of the present invention, the azeotropic water-carrying agent includes one or a mixture of benzene, halogenated benzene or alkylbenzene.

[0030] As an optional embodiment of the technical solution of the present invention, the catalyst includes a carbonate catalyst or a bicarbonate catalyst. Carbonate catalysts include alkali metal carbonates and / or alkaline earth metal carbonates, and bicarbonate catalysts include alkali metal bicarbonates and / or alkaline earth metal bicarbonates. For example, alkali metal carbonates include but are not limited to sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, etc., alkaline earth metal carbonates include but are not limited to magnesium carbonate, calcium carbonate, etc., alkali metal bicarbonates include but are not limited to sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, etc., and alkaline earth metal bicarbonates include but are not limited to magnesium bicarbonate, calcium bicarbonate, etc.

[0031] As a preferred embodiment of the technical solution of the present invention, the catalyst also includes a fluoride catalyst. The fluoride catalyst includes an alkali metal fluoride. The alkali metal fluoride includes but is not limited to potassium fluoride, rubidium fluoride, cesium fluoride, etc. When an aromatic dichloro monomer is added to the polymerization system, the alkali metal fluoride can increase its polymerization reaction activity.

[0032] As an optional implementation scheme of the technical solution of the present invention, the volume usage of the azeotropic water-carrying agent is 0.1-20 times (for example, 0.1 times, 1 times, 2 times, 4 times, 5 times, 6 times, 8 times, 10 times, 12 times, 15 times, 16 times, 18 times or 20 times, etc.) of the volume usage of the solvent in the polymerization reaction.

[0033] As an optional implementation of the technical solution of the present invention, the molar amount of the catalyst is 1-10 times (for example, 1 times, 2 times, 4 times, 5 times, 6 times, 8 times, 10 times, etc.) the total molar amount of the bisphenol monomer and the bisphenol-like monomer in the reaction feed.

[0034] As an optional implementation scheme of the technical solution of the present invention, the mass of the solvent is 0.2-50 times (for example, 1 times, 5 times, 10 times, 15 times, 20 times, 25 times, 30 times, 35 times, 40 times, 45 times or 50 times, etc.) the total mass of the bisphenol monomer, bisphenol-like monomer and aromatic dihalogen monomer in the reaction feed.

[0035] As an optional implementation of the technical solution of the present invention, the protective gas includes one or a mixture of nitrogen, helium, argon, neon, krypton, xenon, radon or carbon dioxide.

[0036] As an optional implementation scheme of the technical scheme of the present invention, the temperature of the polymerization reaction is 110-280°C (for example, 110°C, 120°C, 140°C, 150°C, 160°C, 180°C, 190°C, 200°C, 220°C, 240°C, 250°C, 260°C or 280°C, etc.); preferably, during the polymerization reaction, the reaction is first carried out at 110-150°C for azeotropic dehydration until water is completely taken out of the reaction system by the azeotropic water-carrying agent, and then the azeotropic water-carrying agent is evaporated. After the azeotropic water-carrying agent is evaporated, the reaction is carried out at 150-280°C until the polymerization reaction is completed.

[0037] As an optional implementation of the technical solution of the present invention, the sedimentation agent includes one or a mixture of water, alcohol, tetrahydrofuran or acetone.

[0038] According to the third aspect of the present invention, there is also provided a polar group or heterocyclic bridged phthalazinone structure polymer or the use of the polar group or heterocyclic bridged phthalazinone structure polymer prepared by the above preparation method.

[0039] In view of the advantages of the polar group or heterocyclic bridged phthalazinone structure polymer provided by the present invention, it can be used to prepare high temperature resistant resin-based composite materials, coatings, insulating paints, adhesives, films, functional films, copper clad laminates, separation membranes, etc., and has broad application prospects.

[0040] The present invention is further described in detail below in conjunction with specific examples and comparative examples. It should be noted that the test methods in the following examples, unless otherwise specified, are conventional methods and can be performed according to the techniques or conditions described in the literature in the art or according to the product instructions.

[0041] Example 1 This embodiment provides a polar group or heterocyclic bridged phthalazinone structure polymer (containing an oxobenzophenone heterocyclic bridged phthalazinone structure polyarylether nitrile sulfone), the structural formula of which is shown below: The preparation method of the polymer containing the dioxofluorene heterocyclic bridged phthalazinone structure in this embodiment comprises the following steps: In a polymerization reactor equipped with mechanical stirring, reflux condensing device, water separator and air guide pipe, 5 mol of bisphenol monomer containing oxofluorene heterocyclic bridged phthalazinone structure, 5 mol of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one (abbreviated as: DHPZ) monomer, 16 mol of anhydrous sodium carbonate, 20 mol of potassium fluoride, 6 mol of 2,6-dichlorobenzonitrile, 4 mol of 4,4′-dichlorodiphenyl sulfone, 8 L of xylene and 15 L of sulfolane were added, and the mixture was reacted at 150° C. for 2 hours under argon atmosphere, and xylene was carried out to carry out water removal, and then xylene was evaporated, and the temperature was raised to 220° C. and stirred for reaction for 16 hours. The specific reaction formula is as follows: After the reaction is completed, the reaction solution is sprayed and precipitated in hot water to obtain a white solid, which is then washed with water and dried to obtain a polar group or heterocyclic bridged phthalazinone structure polymer (containing an oxofluorene heterocyclic bridged phthalazinone structure polyarylether nitrile sulfone), whose infrared spectrum and nuclear magnetic hydrogen spectrum are as follows: Figure 1 As shown in (a) and (b).

[0042] After testing, the polyarylethernitrilesulfone resin containing dioxofluorene heterocyclic bridged bis(phthalazinone) structure in this embodiment T g The polymer can reach 358°C and is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., 0.1 g of the polymer can be dissolved in 1 mL of the solvent).

[0043] Example 2 This embodiment provides a polar group or heterocyclic bridged phthalazinone structure polymer (containing a dithiophene heterocyclic bridged phthalazinone structure polyarylethersulfoneketone), the structural formula of which is shown below: The method for preparing the polar group or heterocyclic bridged phthalazinone structure polymer of this embodiment comprises the following steps: In a dry 50 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, a water separator and a gas guide tube, 0.008 mol of a dithiophene heterocyclic bridged phthalazinone structure-type bisphenol monomer, 0.002 mol of a DHPZ monomer, 0.016 mol of anhydrous potassium carbonate, 0.02 mol of 4,4′-difluorobenzophenone, 0.008 mol of 4,4′-dichlorodiphenyl sulfone, 8 mL of toluene and 10 mL of sulfolane were added, and the mixture was reacted at 140° C. for 4 hours under a nitrogen atmosphere, and toluene was removed by water removal, and toluene was evaporated. The temperature was raised to 200° C. and the reaction was continued with stirring for 10 hours. The specific reaction formula is shown below: After the reaction, the reaction solution was poured into acetone to obtain a white strip solid. After washing with water and drying, a polar group or heterocyclic bridged phthalazinone structure polymer (containing a dithiophene heterocyclic bridged phthalazinone structure polyaryl ether sulfone ketone) was obtained. Its infrared spectrum and nuclear magnetic hydrogen spectrum are shown as follows: Figure 2 As shown in (a) and (b).

[0044] The glass transition temperature of the polyarylethersulfoneketone resin containing the dithiophene heterocyclic bridged phthalazinone structure in this embodiment is T g The polymer can reach 376°C and is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., 0.1 g of the polymer can be dissolved in 1 mL of the solvent).

[0045] Example 3 This embodiment provides a polar group or heterocyclic bridged phthalazinone structure polymer (containing an oxobenzophenone heterocyclic bridged phthalazinone structure polyarylethernitrile), the structural formula of which is as follows: The method for preparing the polar group or heterocyclic bridged phthalazinone structure polymer of this embodiment comprises the following steps: In a polymerization reaction kettle equipped with mechanical stirring, reflux condensing device, water separator and air guide pipe, 9 mol of bisphenol monomer containing oxofluorene heterocyclic bridged phthalazinone structure, 1 mol of DHPZ monomer, 16 mol of anhydrous potassium carbonate, 10 mol of 2,6-difluorobenzonitrile, 4 L of xylene and 12 L of sulfolane were added, and the mixture was reacted at 150° C. for 4 hours under nitrogen atmosphere, and xylene was carried out to carry out water removal, and xylene was evaporated, and the temperature was raised to 220° C. and stirred for reaction for 15 hours. The specific reaction formula is as follows: After the reaction is completed, the reaction solution is sprayed and precipitated into boiling water to obtain a white powder solid. After washing with water and drying, a polar group or heterocyclic bridged phthalazinone structure polymer (containing an oxobenzophenone heterocyclic bridged phthalazinone structure polyarylether nitrile) is obtained. Its infrared spectrum and nuclear magnetic hydrogen spectrum are as follows: Figure 3 As shown in (a) and (b).

[0046] The glass transition temperature of the poly(arylethernitrile) resin containing the dioxofluorene heterocyclic bridged bis(phthalazinone) structure in this embodiment is T g =394℃, soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e. 0.1g of the above polymer can be dissolved in 1mL of the above solvent).

[0047] Example 4 This embodiment provides a polar group or heterocyclic bridged phthalazinone structure polymer (containing dithiophene heterocyclic bridged phthalazinone structure polyaryl sulfone), the structural formula of which is as follows: The preparation method of the polyaryl sulfone resin containing a dithiophene heterocyclic bridged phthalazinone structure in this embodiment comprises the following steps: In a polymerization reactor equipped with mechanical stirring, reflux condensation device, water separator and air duct, 10 mol of bisphenol monomer containing dithiophene heterocyclic bridged phthalazinone structure, 12 mol of anhydrous potassium carbonate, 10 mol of 4,4′-dichlorodiphenyl sulfone, 5 L of xylene and 15 L of cyclopentane sulfone were added, and the reaction was carried out at 145°C for 4 hours under nitrogen atmosphere, and xylene was carried out to carry out water. After the water was completely taken out of the polymerization reaction system, the xylene was evaporated, and the temperature was raised to 200°C and continued to stir for 40 hours. The specific reaction formula is shown below. After the reaction is completed, the reaction solution is precipitated in ethanol to obtain a white powder solid. After washing with water and drying, a polar group or heterocyclic bridged phthalazinone structure polymer (containing dithiophene heterocyclic bridged phthalazinone structure polyaryl sulfone) is obtained, and its infrared spectrum and nuclear magnetic hydrogen spectrum are shown as follows: Figure 4 As shown in (a) and (b).

[0048] After testing, the polymer containing the dithiophene heterocyclic bridged phthalazinone structure in this embodiment T g The polymer can reach 404°C and is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., 0.1 g of the polymer can be dissolved in 1 mL of the solvent).

[0049] Example 5 This embodiment provides a polar group or heterocyclic bridged phthalazinone structure polymer (containing an oxobenzophenone heterocyclic bridged phthalazinone structure polyaromatic nitrile), the structural formula of which is as follows: The method for preparing the polar group or heterocyclic bridged phthalazinone structure polymer of this embodiment comprises the following steps: In a dry 50 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, a water separator and a gas guide tube, 0.010 mol of a bisphenol monomer containing an oxofluorene heterocyclic bridged phthalazinone structure, 0.016 mol of anhydrous potassium carbonate, 0.06 mol of potassium fluoride, 0.010 mol of 2,6-dichlorobenzonitrile, 10 mL of toluene and 15 mL of sulfolane were added, and the mixture was reacted at 140° C. for 6 hours under an argon atmosphere to remove water from the toluene, and then the toluene was evaporated, and the temperature was raised to 200° C. and the stirring reaction was continued for 18 hours. The specific reaction formula is shown below: After the reaction, the reaction solution was precipitated in ethanol to obtain a white strip solid, which was washed with water and dried to obtain a polar group or heterocyclic bridged phthalazinone structure polymer (polyaromatic nitrile containing dibenzofuran bridged phthalazinone structure), whose infrared spectrum and nuclear magnetic hydrogen spectrum were as follows: Figure 5 As shown in (a) and (b).

[0050] The glass transition temperature of the polyaromatic nitrile resin containing the dioxofluorene heterocyclic bridged phthalazinone structure in this embodiment is T g =400℃, soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e. 0.1g of the above polymer can be dissolved in 1mL of the above solvent).

[0051] Example 6 This embodiment provides a polar group or heterocyclic bridged phthalazinone structure polymer (containing dithiophene heterocyclic bridged phthalazinone structure polyaromatic nitrile sulfone), the structural formula of which is as follows: The preparation method of the polymer containing the dithiofluorene heterocycle-bridged phthalazinone structure in this embodiment comprises the following steps: In a polymerization reaction kettle equipped with mechanical stirring, reflux condensing device, water separator and air guide pipe, 10 mol of dithiophene heterocyclic bridged phthalazinone structure bisphenol monomer, 14 mol of anhydrous potassium carbonate, 5 mol of 4,4′-dichlorodiphenyl sulfone, 5 mol of 2,6-dichlorobenzonitrile, 6 L of toluene and 15 L of cyclopentane sulfone were added, and the mixture was reacted at 145° C. for 5 hours under nitrogen atmosphere, and toluene was carried out to carry out water removal, and toluene was evaporated, and the temperature was raised to 200° C. and stirred for 25 hours. The specific reaction formula is shown as follows: After the reaction, the reaction solution was sprayed and precipitated into acetone to obtain a white powder solid. After washing with water and drying, a polar group or heterocyclic bridged phthalazinone structure polymer (containing a dithiophene heterocyclic bridged phthalazinone structure polyaromatic nitrile sulfone) was obtained. Its infrared spectrum and nuclear magnetic hydrogen spectrum are shown as follows: Figure 6 As shown in (a) and (b).

[0052] The glass transition temperature of the polyaromatic nitrile sulfone resin containing the dithiophene heterocyclic bridged bis(phthalazinone) structure of this embodiment is T g =405℃, soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e. 0.1g of the above polymer can be dissolved in 1mL of the above solvent).

[0053] Example 7 This embodiment provides a polar group or heterocyclic bridged phthalazinone structure polymer (containing dithiophene heterocyclic bridged phthalazinone structure polyarylether nitrile), the structural formula of which is as follows: The preparation method of the polyarylether nitrile resin containing a dithiofluorene heterocyclic bridged phthalazinone structure in this embodiment comprises the following steps: In a dry 50 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, a water separator and a gas guide tube, 0.004 mol of a dithiophene heterocyclic bridged phthalazinone structure-based bisphenol monomer, 0.006 mol of 4-(3′-phenyl-4′-hydroxyphenyl)-2,3-phthalazinone-based bisphenol monomer, 0.02 mol of anhydrous potassium carbonate, 0.010 mol of 2,6-dichlorobenzonitrile, 8 mL of toluene and 15 mL of sulfolane were added, and the mixture was reacted at 140° C. for 4 hours under a nitrogen atmosphere, and toluene was removed by water removal, and toluene was evaporated, and the temperature was raised to 195° C. and stirred for 12 hours. The specific reaction formula is shown below; After the reaction is completed, the reaction solution is poured into boiling water to obtain a white strip solid, which is then washed with water and dried to obtain a polar group or heterocyclic bridged phthalazinone structure polymer (containing a dithiophene heterocyclic bridged phthalazinone structure polyarylether nitrile), whose infrared spectrum and nuclear magnetic hydrogen spectrum are as follows: Figure 7 As shown in (a) and (b).

[0054] After testing, the glass transition temperature of the poly(arylether nitrile) containing the dithiophene heterocyclic bridged bis(phthalazinone) structure in this embodiment is T g =334°C, soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (i.e., 0.1 g of the above polymer can be dissolved in 1 mL of the above solvent).

[0055] Example 8 This embodiment provides a polar group or heterocyclic bridged phthalazinone structure polymer (sulfone-containing polar group bridged phthalazinone structure polyarylethersulfoneketone), the structural formula of which is as follows: The preparation method of the polymer containing a sulfone polar group-bridged phthalazinone structure in this embodiment comprises the following steps: In a dry 50 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, a water separator and a gas guide tube, 0.010 mol of a bis(phthalazinone) structure-type bisphenol monomer containing a sulfone polar group, 0.014 mol of anhydrous potassium carbonate, 0.002 mol of 4,4′-difluorobenzophenone, 0.008 mol of 4,4′-difluorodiphenyl sulfone, 5 mL of toluene and 8 mL of sulfolane were added, and the mixture was reacted at 140° C. for 4 hours under a nitrogen atmosphere, and toluene was removed by water removal, and toluene was evaporated. The temperature was raised to 190° C. and stirring was continued for 12 hours. The specific reaction formula is shown below: After the reaction, the reaction solution was precipitated in ethanol to obtain a white solid, which was washed with water and dried to obtain a polyarylethersulfoneketone resin containing a sulfone polar group-bridged phthalazinone structure. Its infrared spectrum and nuclear magnetic hydrogen spectrum are as follows: Figure 8 As shown in (a) and (b).

[0056] After testing, the glass transition temperature of the poly(aryl ether sulfone ketone) containing a sulfone polar group-bridged bis(phthalazinone) structure in this embodiment is T g =367℃, soluble in polar aprotic organic solvents such as NMP, DMAc, pyridine, 1,1,2,2-tetrachloroethane, etc. (i.e. 0.1g of the above polymer can be dissolved in 1mL of the above solvent).

[0057] Comparative Example 1 This comparative example provides a polymer with a phthalazinone structure (diphenyl ether phthalazinone structure polyarylethersulfoneketone), the structural formula of which is shown below: The preparation method of the polymer with a phthalazinone structure in this comparative example comprises the following steps: Under nitrogen protection, in a 100mL three-necked flask equipped with mechanical stirring, liquid seal, nitrogen gas guide tube and water separator, 0.010mol of diphenyl ether phthalazinone bisphenol monomer, 0.014mol of anhydrous potassium carbonate, 0.002mol of 4,4′-difluorobenzophenone and 0.008mol of 4,4′-difluorodiphenyl sulfone were accurately added, 5mL of toluene was added as a water-carrying agent, 8mL of cyclopentane was added as a solvent, the mixture was stirred and the temperature was evenly raised to 140°C, and after reflux for 3h, the toluene and the generated water were completely evaporated, the reaction temperature was raised to 190°C, and the reaction was carried out for about 8h (the reaction formula is as follows), and the reaction product was precipitated in hot water, and the product was in the form of white filaments. The inorganic salt and residual sulfolane solvent in the product were removed by boiling water, and after filtration and drying, the polymer was dissolved in chloroform, filtered and precipitated in ethanol solvent to obtain a white flocculent polymer, and after filtration, a diphenyl ether diphthalazinone structure polyaryl ether sulfone ketone was obtained, and its infrared spectrum and nuclear magnetic hydrogen spectrum were as follows: Fig. 9As shown in (a) and (b).

[0058] After testing, the glass transition temperature of the polyarylethersulfoneketone resin of the comparative example is T g The temperature of the polymer is 324 °C and it is soluble in chloroform, tetrachloroethane and NMP (i.e., 0.1 g of the polymer can be dissolved in 1 mL of the solvent).

[0059] The structure of the polyaryl ether sulfone ketone resin with a phthalazinone structure in this comparative example is compared with the structure of the polyaryl ether containing a polar group or heterocyclic bridging phthalazinone structure provided in Example 8, and it does not contain the sulfone-containing polar group bridging structure in the structure of Example 8, while the other copolymer compositions are the same. From the heat resistance and solubility data of Example 8 and Comparative Example 1, the polar group or heterocyclic bridging phthalazinone structure polymer in Example 8 has a higher glass transition temperature and is still soluble in polar aprotic organic solvents, which is mainly due to the introduction of the polar group or heterocyclic bridging phthalazinone structure.

[0060] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention are within the scope of protection of the pending claims of the present invention.

Claims

1. A polar group or heterocyclic bridged phthalazinone structure polymer, characterized in that: Its structural formula is shown in formula (1) or formula (2): （1）； （2）； In formula (1) and formula (2), The structure is one or more of the following structures: ； ； , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; In formula (1) and formula (2), The structure is one or more of the following structures: ; ; ; ; , R is selected from hydrogen, phenyl, alkyl or alkoxy, wherein the alkyl or alkoxy is a straight chain or branched alkyl or alkoxy containing 1 to 20 carbon atoms; In formula (1), the structure of —Ar3— is one or more of the following structures: , 1, 2 digits, 1, 3 digits or 1, 4 digits; , 2, 2′ position or 4, 4′ position; , 1, 4 digits, 1, 5 digits, 1, 6 digits, 2, 6 digits or 2, 7 digits; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group, or an alkoxy group, and the structures of R1, R2, R3, and R4 are the same or different, wherein the alkyl group or the alkoxy group is a straight chain or branched alkyl group or alkoxy group containing at least one carbon atom; ； ； ； ； ； ； ； ； ； ； ； ； ； ； in, One or more of the following structures: ； ； ； ； ； ； , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; for , One or more of the .

2. The polar group or heterocyclic bridged phthalazinone structure polymer according to claim 1, characterized in that: In formula (1) and formula (2), the structure of —Ar1— is one or more of the following structures: ； ； , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; And / or, in formula (1) and formula (2), the structure of —Ar2— is one or more of the following structures: ； ； ； And / or, in formula (1), the structure of —Ar3— is one or more of the following structures: ； ； , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group or an alkoxy group, and the structures of R1, R2, R3 and R4 are the same or different, wherein the alkyl group or the alkoxy group is a straight chain or branched alkyl group or alkoxy group containing at least 1 carbon atom.

3. The polar group or heterocyclic bridged phthalazinone structure polymer according to claim 1 or 2, characterized in that: The glass transition temperature of the polar group or heterocyclic bridged phthalazinone structure polymer is up to 405°C; And / or, the polar group or heterocyclic bridged phthalazinone structure polymer is soluble in a polar aprotic organic solvent, and the polar aprotic organic solvent includes at least one of N-methylpyrrolidone, dimethylacetamide, pyridine or 1,1,2,2-tetrachloroethane.

4. The method for preparing the polar group or heterocyclic bridged phthalazinone structure polymer according to any one of claims 1 to 3, characterized in that: The following steps are involved: A bisphenol monomer containing a polar group or heterocyclic bridging bisphthalazinone structure and an aromatic dihalogen monomer, as well as other optional bisphenols or bisphenol-like monomers are used as polycondensation monomers, mixed with a solvent, an azeotropic water-carrying agent and a catalyst, and a stepwise polymerization reaction is carried out under a protective gas atmosphere. The reaction solution obtained after the polymerization reaction is precipitated in a precipitant, and the precipitated solid product is washed, filtered and dried to obtain a polar group or heterocyclic bridging bisphthalazinone structure polymer.

5. The method for preparing the polar group or heterocyclic bridged phthalazinone structure polymer according to claim 4, characterized in that: The polar group- or heterocyclic-bridged phthalazinone-type bisphenol monomer has the following molecular structure: Wherein, the structure of —Ar1— is one or more of the following structures: ； ； , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; And / or, the structure of the aromatic dihalogen monomer is one or more of the following structures: ; ; ; ; , R is selected from hydrogen, phenyl, alkyl or alkoxy, wherein the alkyl or alkoxy is a straight chain or branched alkyl or alkoxy containing 1 to 20 carbon atoms; X is F or Cl; And / or, the structure of the other bisphenol monomer or bisphenol-like monomer is one or more of the following structures: , 1, 2 digits, 1, 3 digits or 1, 4 digits; , 2, 2′ position or 4, 4′ position; , 1, 4 digits, 1, 5 digits, 1, 6 digits, 2, 6 digits or 2, 7 digits; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , 3, 3′ position or 4, 4′ position; , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group, or an alkoxy group, and the structures of R1, R2, R3, and R4 are the same or different, wherein the alkyl group or the alkoxy group is a straight chain or branched alkyl group or alkoxy group containing at least one carbon atom; ； ； ； ； ； ； ； ； ； ； ； ； ； ； in One or more of the following structures: ； ； ； ； ； ； , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; , 2, 2 digits, 2, 3 digits or 3, 3 digits; for , One or more of the .

6. The method for preparing the polar group or heterocyclic bridged phthalazinone structure polymer according to claim 4 or 5, characterized in that: The solvent includes one or a mixture of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide or cyclopentane; And / or, the azeotropic water-carrying agent comprises one or a mixture of benzene, halogenated benzene or alkylbenzene; And / or, the catalyst comprises a carbonate catalyst or a bicarbonate catalyst, the carbonate catalyst comprises an alkali metal carbonate and / or an alkaline earth metal carbonate, and the bicarbonate catalyst comprises an alkali metal bicarbonate and / or an alkaline earth metal bicarbonate.

7. The method for preparing a polar group or heterocyclic bridged phthalazinone structure polymer according to claim 6, characterized in that: The volume usage of the azeotropic water-carrying agent is 0.1-20 times the volume usage of the solvent in the polymerization reaction; And / or, the molar amount of the catalyst is 1-10 times the total molar amount of the bisphenol monomer and the bisphenol-like monomer in the reaction feed; And / or, the mass amount of the solvent is 0.2-50 times the total mass of the bisphenol monomer, bisphenol-like monomer and aromatic dihalogen monomer in the reaction feed; And / or, the catalyst further comprises a fluoride catalyst, and the fluoride catalyst comprises an alkali metal fluoride.

8. The method for preparing the polar group or heterocyclic bridged phthalazinone structure polymer according to claim 4 or 5, characterized in that: The protective gas includes one or a mixture of nitrogen, helium, argon, neon, krypton, xenon, radon or carbon dioxide; And / or, the polymerization reaction temperature is 110-280°C.

9. The method for preparing a polar group or heterocyclic bridged phthalazinone structure polymer according to claim 8, characterized in that: During the polymerization reaction, the reaction is first carried out at 110-150°C for azeotropic dehydration until the water is completely taken out of the reaction system by the azeotropic water-carrying agent, and then the azeotropic water-carrying agent is evaporated. After the azeotropic water-carrying agent is evaporated, the reaction is continued at 150-280°C until the polymerization reaction is completed; And / or, the precipitant includes one or a mixture of water, alcohol, tetrahydrofuran or acetone.

10. Use of the polar group or heterocyclic bridged phthalazinone structure polymer according to any one of claims 1 to 3 or the polar group or heterocyclic bridged phthalazinone structure polymer prepared by the preparation method according to any one of claims 4 to 9 in the preparation of high temperature resistant resin-based composite materials, coatings, adhesives, functional films or copper clad laminates.

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