Polar group or heterocyclic bridged phthalazinone structure polymer and preparation method thereof

Abstract

The present invention provides a polymer with a polar group or a heterocyclic-bridged phthalazinone structure and a preparation method thereof, which relates to the technical field of synthesis of polymer materials. The polymer with a polar group or a heterocyclic-bridged phthalazinone structure mainly has more excellent heat resistance and good solubility by introducing a polar group or a heterocyclic-bridged phthalazinone structure. Its glass transition temperature can reach up to 405 °C and it 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 regulate the heat resistance and solubility of such polymers by adjusting the structure and proportion of the structural unit with a polar group or a heterocyclic-bridged phthalazinone structure and other structural units, so that it can meet the needs of more different application scenarios. The present invention also provides a preparation method of the above polymer.

Description

Technical Field

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

[0002] Polyaryl ethers are a kind of high-temperature resistant engineering plastics with excellent heat resistance and mechanical properties. They can be used to prepare resin-based composites, high-temperature resistant separation membranes, functional membranes, enameled wires, cables, wear-resistant materials, biomedical materials, etc., and are widely used in the fields of aerospace, ocean engineering, energy, electronics, petrochemical industry, biomedicine, etc. There are many types of polyaryl ether resins, and different polyaryl ethers have different heat resistance characteristics. For example, the glass transition temperature ( T g ) of commercial polyether ether ketone (PEEK, semi-crystalline polymer) is 143 °C, and that of polyphenylene sulfone (PPSU, amorphous polymer) is T g 288 °C. However, with the continuous development of the above fields, higher requirements are put forward for the heat resistance of polyaryl ethers, and good solubility and the ability to be processed and formed in various ways are needed. Our research group has reported a series of polyaryl ether ketones containing a phthalazinone biphenyl structure ( T g = 263 °C), polyaryl ether sulfones ( T g = 305 °C), polyaryl ether nitrile ketones ( T g = 268 - 289 °C, Wang Mingjing, Ph.D. thesis of Dalian University of Technology, 2007; Chinese invention patent ZL03111540.3) resins, which have both excellent heat resistance and good solubility. A.S. Hay et al. (Macromolecules, 1997, 30(8), 2254) reported polyaryl ether ketones with a diphenyl ether or diphenyl sulfide structure and a bisphthalazinone structure ( T g : 301 °C and 281 °C) and polyaryl ether sulfones ( T g : 295 °C and 279 °C), and based on dianhydride-synthesized bisphenol-like monomers, prepared polyaryl sulfones with a bisphthalazinone structure ( T g : 221 °C, 310 °C, 344 °C), polyaryl ketones ( T g : 195 °C, 286 °C) and polyaryl nitriles ( T g: (200 °C, 301 °C). However, due to the high cost and price of dianhydride compounds, the synthesis cost of monomers and their polymers is significantly high. Moreover, since there are no flexible ether bond groups in the molecular main chain and some monomers with a rigid phthalazinone structure are very rigid, the polymers have poor solubility, are difficult to synthesize, and have a low molecular weight. For example, for monomers with a phthalazinone structure synthesized based on sulfone-containing dianhydride, the resulting polyarylsulfone (main chain without ether bonds) has poor solubility and an intrinsic viscosity of only 0.11 dL / g, indicating a very low molecular weight of the polymer. Zhang Shouhai et al. disclosed a copolymerized polyarylethersulfone with a phthalazinone structure and its preparation method (Chinese Patent, Publication No. CN113461943A) and a copolymerized polyarylethernitrile with a phthalazinone structure and its preparation method (Chinese Patent, Publication No. CN116675849A), and the glass transition temperature of the examples can reach 373 °C.

[0003] In summary, although introducing rigid heteroaromatic ring structures into the molecular chain of polyarylethers can improve the heat resistance of the polymer, it is necessary to consider both the heat resistance and solubility of the polymer. Therefore, it is necessary to obtain polymers with both excellent heat resistance and good solubility through molecular structure design and synthesis.

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

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

[0006] To achieve the above purpose, the following technical solutions are adopted:

[0007] The first purpose of the present invention is to provide a polymer with a polar group or heterocyclic-bridged phthalazinone structure, and its structural formula is shown in Formula (1) or Formula (2):

[0008] (1);

[0009] (2);

[0010] In Formula (1) and Formula (2), The structure of is one or more of the following structures:

[0011] ; ;

[0012] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0013] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0014] , 2, 2 - position, 2, 3 - position or 3, 3 - position;

[0015] , 2, 2 - position, 2, 3 - position or 3, 3 - position;

[0016] , 2, 2 - position, 2, 3 - position or 3, 3 - position;

[0017] In formula (1) and formula (2), the structure of —Ar2— is one or more of the following structures:

[0018] ; ; ; ; , R is selected from hydrogen, phenyl, alkyl or alkoxy, where the alkyl or alkoxy is a straight - chain or branched - chain alkyl or alkoxy containing 1 to 20 carbon atoms;

[0019] In formula (1), the structure of —Ar3— is one or more of the following structures:

[0020] , 1, 2 - position, 1, 3 - position or 1, 4 - position;

[0021] , 2, 2′ - position or 4, 4′ - position;

[0022] , 1, 4 - position, 1, 5 - position, 1, 6 - position, 2, 6 - position or 2, 7 - position;

[0023] , 3, 3′ - position or 4, 4′ - position;

[0024] , 3, 3′ - position or 4, 4′ - position;

[0025] , 3, 3′ - position or 4, 4′ - position;

[0026] , 3, 3′ - position or 4, 4′ - position;

[0027] , 3, 3′ - position or 4, 4′ - position;

[0028] , R1, R2, R3, R4 are each independently selected from hydrogen, halogen substituents, phenyl, phenoxy, alkyl or alkoxy, and the structures of R1, R2, R3 and R4 are the same or different, where the alkyl or alkoxy is a straight - chain or branched - chain alkyl or alkoxy containing at least 1 carbon atom;

[0029] ; ; ;

[0030] ; ; ; ; ; ; ; ; ; ; ;

[0031] Among them, is one or more of the following structures:

[0032] ; ; ; ; ; ;

[0033] , 2, 2-bit, 2, 3-bit or 3, 3-bit;

[0034] , 2, 2-bit, 2, 3-bit or 3, 3-bit;

[0035] , 2, 2-bit, 2, 3-bit or 3, 3-bit;

[0036] , 2, 2-bit, 2, 3-bit or 3, 3-bit;

[0037] , 2, 2-bit, 2, 3-bit or 3, 3-bit;

[0038] is 、 one or more of.

[0039] The second object of the present invention is to provide a method for preparing a polymer with a polar group or a heterocyclic bridged bisphthalazinone structure, comprising the following steps:

[0040] Using a bisphenol monomer containing a polar group or a heterocyclic bridged phthalazinone structure, an aromatic dihalide monomer, and optionally other bisphenol or bisphenol-like monomers as polycondensation monomers, mixing with a solvent, an azeotropic water-carrying agent, and a catalyst, carrying out a stepwise polymerization reaction under an inert gas atmosphere, sedimenting the reaction solution obtained after the polymerization reaction in a precipitant, and washing, filtering, and drying the precipitated solid product to obtain a polymer with a polar group or a heterocyclic bridged phthalazinone structure.

[0041] Further, on the basis of the above technical solution of the present invention, the bisphenol monomer containing a polar group or a heterocyclic bridged phthalazinone structure has the following molecular structure:

[0042]

[0043] Among them, the structure of —Ar1— is one or more of the following structures:

[0044] ; ;

[0045] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0046] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0047] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0048] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0049] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0050] And / or, the structure of the aromatic dihalide monomer is one or more of the following structures:

[0051] ; ; ; ; , R is selected from hydrogen, phenyl, alkyl, or alkoxy, where the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing 1 to 20 carbon atoms; X is F or Cl;

[0052] And / or, the structure of the other bisphenol monomer or bisphenol-like monomer is one or more of the following structures:

[0053] , at the 1, 2-position, 1, 3-position, or 1, 4-position;

[0054] at the 2, 2'-position or 4, 4'-position;

[0055] at the 1, 4-position, 1, 5-position, 1, 6-position, 2, 6-position or 2, 7-position;

[0056] at the 3, 3'-position or 4, 4'-position;

[0057] at the 3, 3'-position or 4, 4'-position;

[0058] at the 3, 3'-position or 4, 4'-position;

[0059] at the 3, 3'-position or 4, 4'-position;

[0060] at the 3, 3'-position or 4, 4'-position;

[0061] R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, phenyl, phenoxy, alkyl, or alkoxy, and the structures of R1, R2, R3, and R4 are the same or different, where the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing at least 1 carbon atom;

[0062] ; ; ;

[0063] ; ; ; ; ; ; ; ; ; ; ;

[0064] wherein, ―X1― is one or more of the following structures:

[0065] ; ; ; ; ; ;

[0066] at the 2, 2-position, 2, 3-position or 3, 3-position;

[0067] , 2, 2-position, 2, 3-position or 3, 3-position;

[0068] , 2, 2-position, 2, 3-position or 3, 3-position;

[0069] , 2, 2-position, 2, 3-position or 3, 3-position;

[0070] , 2, 2-position, 2, 3-position or 3, 3-position;

[0071] is 、 one or more of the following.

[0072] Compared with the prior art, the technical solution of the present invention has at least the following technical effects:

[0073] (1) The present invention provides a polar group or heterocyclic bridged bisphthalazinone structure polymer with both excellent heat resistance and good solubility. By introducing a polar group or heterocyclic bridged bisphthalazinone structure, the polymer has more excellent heat resistance and good solubility. Its glass transition temperature ( T g ) can reach up to 405 °C and it 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 regulate the heat resistance and solubility of such polymers by adjusting the structure and proportion of the polar group or heterocyclic bridged bisphthalazinone structure unit and other structure units, so that it can meet the needs of more different application scenarios.

[0074] (2) The present invention also provides a preparation method of the above-mentioned polar group or heterocyclic bridged bisphthalazinone structure polymer. By using nucleophilic substitution stepwise polymerization reaction, the stable preparation of the polymer can be realized.

[0075] (3) The present invention also provides the application of the above-mentioned polar group or heterocyclic bridged bisphthalazinone structure polymer. Due to the advantages of the above-mentioned polar group or heterocyclic bridged bisphthalazinone structure polymer, it can be widely used in technical fields such as the preparation of high-temperature resistant resin matrix composites, coatings, adhesives, functional films, copper clad laminates, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 is the infrared spectrum (a) and proton nuclear magnetic resonance spectrum (b) of the polymer prepared in Example 1 of the present invention;

[0077] Figure 2 is the infrared spectrum (a) and proton nuclear magnetic resonance spectrum (b) of the polymer prepared in Example 2 of the present invention;

[0078] Figure 3 The infrared spectrum (a) and proton nuclear magnetic resonance spectrum (b) of the polymer prepared in Example 3 of the present invention;

[0079] Figure 4 The infrared spectrum (a) and proton nuclear magnetic resonance spectrum (b) of the polymer prepared in Example 4 of the present invention;

[0080] Figure 5 The infrared spectrum (a) and proton nuclear magnetic resonance spectrum (b) of the polymer prepared in Example 5 of the present invention;

[0081] Figure 6 The infrared spectrum (a) and proton nuclear magnetic resonance spectrum (b) of the polymer prepared in Example 6 of the present invention;

[0082] Figure 7 The infrared spectrum (a) and proton nuclear magnetic resonance spectrum (b) of the polymer prepared in Example 7 of the present invention;

[0083] Figure 8 The infrared spectrum (a) and proton nuclear magnetic resonance spectrum (b) of the polymer prepared in Example 8 of the present invention;

[0084] Figure 9 The infrared spectrum (a) and proton nuclear magnetic resonance spectrum (b) of the polymer prepared in Comparative Example 1 of the present invention. Detailed implementation manners

[0085] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention. The process parameters without specific conditions noted in the following embodiments are usually in accordance with conventional conditions.

[0086] In the present invention, the endpoints and any values within the disclosed ranges are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in the present invention. In addition, "A and / or B" in the present invention means that it can include only A, can also include only B, or can include both A and B simultaneously.

[0087] According to the first aspect of the present invention, there is provided a polymer with a polar group or a heterocyclic-bridged bisphthalazinone structure, that is, the polymer contains a bisphthalazinone structure, and the bisphthalazinone structure contains a polar-group bridging structure or a heterocyclic-bridging structure. The structural formula of the polymer is shown in Formula (1) or Formula (2):

[0088] (1);

[0089] (2);

[0090] In Formula (1) and Formula (2), the structure of —Ar1— is a combination of one or more of the following structures:

[0091] ; ;

[0092] , at the 2, 2-position, 2, 3-position or 3, 3-position; among them, the 2, 2-position, 2, 3-position or 3, 3-position is the connection site with phthalazinone, which are isomers generated by the reaction of thiophene compounds and there are 3 structures. These three structures can also be separated, polymerized separately, or directly polymerized. The following structures are all in this situation and will not be elaborated later;

[0093] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0094] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0095] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0096] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0097] The structure of uses a bridging structure containing a polar group or a ladder-shaped heterocycle, which is beneficial to further improving the heat resistance of the polymer with a polar group or a heterocyclic-bridged bisphthalazinone structure.

[0098] In Formula (1) and Formula (2), The structure of is generated by the reaction of the corresponding aromatic dihalide monomer and is determined by the structure of the selected aromatic dihalide monomer. The structure of is a combination of one or more of the following structures:

[0099] ; ; ; ; wherein R is selected from hydrogen, phenyl, alkyl or alkoxy, and the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing 1 to 20 carbon atoms;

[0100] In formula (1), The structure of is produced by the reaction of the corresponding bisphenol or bisphenol-like monomer and is determined by the structure of the selected bisphenol or bisphenol-like monomer. The structure of is one or more of the following structures:

[0101] , at the 1,2-, 1,3- or 1,4-position; wherein the 1,2-, 1,3- and 1,4-positions are the positions where oxygen is connected to the benzene ring, mainly depending 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 the 1,2-, 1,3- or 1,4-position. The subsequent structures are similar and will not be elaborated further;

[0102] , at the 2,2'- or 4,4'-position;

[0103] , at the 1,4-, 1,5-, 1,6-, 2,6- or 2,7-position;

[0104] , at the 3,3'- or 4,4'-position;

[0105] , at the 3,3'- or 4,4'-position;

[0106] , at the 3,3'- or 4,4'-position;

[0107] , at the 3,3'- or 4,4'-position;

[0108] , at the 3,3'- or 4,4'-position;

[0109] , R1, R2, R3 and R4 are each independently selected from hydrogen, halogen substituents, phenyl, phenoxy, alkyl or alkoxy, and the structures of R1, R2, R3 and R4 are the same or different, wherein the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing at least 1 carbon atom;

[0110] ; ; ;

[0111] ; ; ; ; ; ; ; ; ; ; ;

[0112] Among them, ―X1― is one or more of the following structures:

[0113] ; ; ; ; ; ;

[0114] , 2, 2-position, 2, 3-position or 3, 3-position;

[0115] , 2, 2-position, 2, 3-position or 3, 3-position;

[0116] , 2, 2-position, 2, 3-position or 3, 3-position;

[0117] , 2, 2-position, 2, 3-position or 3, 3-position;

[0118] , 2, 2-position, 2, 3-position or 3, 3-position;

[0119] is 、 one or more of.

[0120] It should be noted that in the structural formulas (1) and (2) of the polymer containing a polar group or a heterocyclic bridged phthalazinone structure in the present invention, only the repeating unit structures contained are shown, and the molecular weight or degree of polymerization is not limited. As a linear polymer, different applications (such as different uses of resin matrix composites, coatings, adhesives, functional films, etc.) have different requirements for the molecular weight of the polymer, and the molecular weight of the polymer containing a phthalazinone structure can be adjusted according to the molar ratio of the polymerization monomers.

[0121] The present invention provides a polymer containing a polar group or a heterocyclic bridged phthalazinone structure, which has both excellent heat resistance and good solubility. By introducing a polar group or a heterocyclic bridged phthalazinone structure, the polymer has more excellent heat resistance and good solubility, and its glass transition temperature ( T gIt 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 bisphenol or bisphenol-like monomers, the heat resistance and solubility of the polymer containing polar groups or heterocyclic bridged phthalazinone structures can be flexibly regulated. When increasing the content of flexible groups in the molecular chain or decreasing the content of aromatic heterocyclic structures and polar groups, the heat resistance of the polymer containing polar groups or heterocyclic bridged phthalazinone structures can be reduced, but its solubility in polar aprotic organic solvents such as N,N-dimethylacetamide (DMAc) and chloroform can be increased. That is, by adjusting the structure and ratio of the phthalazinone structure unit and other structure units, the heat resistance and solubility of this type of polymer can be regulated, enabling it to meet the needs of more different application scenarios.

[0122] As an optional implementation manner 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:

[0123] ; ;

[0124] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0125] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0126] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0127] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0128] And / or, in formula (1) and formula (2), the structure of —Ar2— is one or more of the following structures:

[0129] ; ; ;

[0130] And / or, in formula (1), the structure of —Ar3— is one or more of the following structures:

[0131] ; ; , R1, R2, R3, and R4 are each independently selected from hydrogen, halogen substituents, phenyl, phenoxy, alkyl, or alkoxy, and the structures of R1, R2, R3, and R4 are the same or different, where the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing at least 1 carbon atom.

[0132] As an alternative embodiment of the technical solution of the present invention, the glass transition temperature of the polymer with a polar group or a heterocyclic-bridged phthalazinone structure can reach up to 405 °C.

[0133] As an alternative embodiment of the technical solution of the present invention, the polymer with a polar group or a heterocyclic-bridged phthalazinone structure is soluble in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane.

[0134] According to the second aspect of the present invention, there is also provided a method for preparing the above-mentioned polymer with a polar group or a heterocyclic-bridged phthalazinone structure, comprising the following steps:

[0135] Using a bisphenol monomer containing a polar group or a heterocyclic-bridged phthalazinone structure, an aromatic dihalide monomer, and optionally other bisphenol or bisphenol-like monomers as polycondensation monomers, mixing them with a solvent, an azeotropic water-carrying agent, and a catalyst, and carrying out a stepwise polymerization reaction under a protective gas atmosphere. The reaction solution obtained after the polymerization reaction is sedimented in a precipitant, and the precipitated solid product is washed, filtered, and dried to obtain a polymer with a polar group or a heterocyclic-bridged phthalazinone structure.

[0136] It should be noted that "optionally other bisphenol or bisphenol-like monomers" means that other bisphenol or bisphenol-like monomers can be added or not. When other bisphenol or bisphenol-like monomers are added, they can polymerize with the bisphenol monomer containing a polar group or a heterocyclic-bridged phthalazinone structure and the aromatic dihalide monomer to form a polymer with the structure shown in formula (1). When other bisphenol or bisphenol-like monomers are not added and only the bisphenol monomer containing a polar group or a heterocyclic-bridged phthalazinone structure and the aromatic dihalide monomer are used as polycondensation monomers, a polymer with the structure shown in formula (2) can be polymerized.

[0137] The method for preparing the polymer with a polar group or a heterocyclic-bridged phthalazinone structure provided by the present invention adopts a nucleophilic substitution stepwise polymerization reaction, which can achieve the stable preparation of the polymer.

[0138] As an alternative embodiment 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:

[0139]

[0140] Among them, The structure of is one or more of the following structures:

[0141] ; ;

[0142] , 2, 2-position, 2, 3-position or 3, 3-position;

[0143] , 2, 2-position, 2, 3-position or 3, 3-position;

[0144] , 2, 2-position, 2, 3-position or 3, 3-position;

[0145] , 2, 2-position, 2, 3-position or 3, 3-position;

[0146] , 2, 2-position, 2, 3-position or 3, 3-position.

[0147] As an optional implementation mode of the technical solution of the present invention, the structure of the aromatic dihalo monomer is one or several of the following structures:

[0148] ; ; ; ; , 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.

[0149] As an optional implementation mode of the technical solution of the present invention, the structure of other bisphenol monomers or bisphenol-like monomers is one or several of the following structures:

[0150] , 1, 2-position, 1, 3-position or 1, 4-position;

[0151] , 2, 2'-position or 4, 4'-position;

[0152] , 1, 4-position, 1, 5-position, 1, 6-position, 2, 6-position or 2, 7-position;

[0153] , 3, 3'-position or 4, 4'-position;

[0154] , 3, 3'-position or 4, 4'-position;

[0155] , 3, 3'-position or 4, 4'-position;

[0156] , 3, 3'-position or 4, 4'-position;

[0157] , 3, 3'-position or 4, 4'-position;

[0158] , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, phenyl, phenoxy, alkyl, or alkoxy, and the structures of R1, R2, R3, and R4 are the same or different, where the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing at least 1 carbon atom;

[0159] ; ; ;

[0160] ; ; ; ; ; ; ; ; ; ; ;

[0161] Wherein, is one or more of the following structures:

[0162] ; ; ; ; ; ;

[0163] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0164] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0165] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0166] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0167] , at the 2, 2-position, 2, 3-position, or 3, 3-position;

[0168] is 、 one or more of.

[0169] As an optional embodiment of the technical solution of the present invention, the solvent includes one or a mixture of several of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide or sulfolane.

[0170] As an optional embodiment of the technical solution of the present invention, the azeotropic water-carrying agent includes one or a mixture of several of benzene, halogenated benzene or alkylbenzene.

[0171] As an optional embodiment of the technical solution of the present invention, the catalyst includes a carbonate catalyst or a bicarbonate catalyst. The carbonate catalyst includes an alkali metal carbonate and / or an alkaline earth metal carbonate, and the bicarbonate catalyst includes an alkali metal bicarbonate and / or an alkaline earth metal bicarbonate. For example, the alkali metal carbonate includes but is not limited to sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, etc., the alkaline earth metal carbonate includes but is not limited to magnesium carbonate, calcium carbonate, etc., the alkali metal bicarbonate includes but is not limited to sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, etc., and the alkaline earth metal bicarbonate includes but is not limited to magnesium bicarbonate, calcium bicarbonate, etc.

[0172] As a preferred embodiment of the technical solution of the present invention, the catalyst further 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.

[0173] As an optional embodiment of the technical solution of the present invention, the volume dosage of the azeotropic water-carrying agent is 0.1-20 times (such as 0.1 times, 1 time, 2 times, 4 times, 5 times, 6 times, 8 times, 10 times, 12 times, 15 times, 16 times, 18 times or 20 times, etc.) the volume dosage of the solvent in the polymerization reaction.

[0174] As an optional embodiment of the technical solution of the present invention, the molar amount of the catalyst is 1-10 times (such as 1 time, 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 feedstock.

[0175] As an optional embodiment of the technical solution of the present invention, the mass of the solvent is 0.2-50 times (such as 1 time, 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, the bisphenol-like monomer and the aromatic dihalide monomer in the reaction feedstock.

[0176] As an alternative embodiment of the technical solution of the present invention, the protective gas includes one or a mixture of several of nitrogen, helium, argon, neon, krypton, xenon, radon or carbon dioxide.

[0177] As an alternative embodiment of the technical solution 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, azeotropic dehydration is first carried out at 110-150 °C until the water is completely carried out of the reaction system by the azeotropic water-carrying agent, and then the azeotropic water-carrying agent is distilled off. After the azeotropic water-carrying agent is distilled off, the reaction is carried out at 150-280 °C until the polymerization reaction ends.

[0178] As an alternative embodiment of the technical solution of the present invention, the precipitating agent includes one or a mixture of several of water, alcohol, tetrahydrofuran or acetone.

[0179] According to the third aspect of the present invention, there is also provided the use of a polar group or heterocyclic bridged bisphthalazinone structure polymer or a polar group or heterocyclic bridged bisphthalazinone structure polymer prepared by the above preparation method.

[0180] In view of the advantages of the polar group or heterocyclic bridged bisphthalazinone structure polymer provided by the present invention, it can be used to prepare high-temperature resistant resin matrix composites, coatings, insulating paints, adhesives, adhesive films, functional films, copper clad laminates, separation membranes, etc., and has broad application prospects.

[0181] The present invention will be further described in detail below with specific examples and comparative examples. It should be noted that in the test methods in the following examples, unless otherwise specified, they are all conventional methods, and can be carried out according to the techniques or conditions described in the literature in the field or according to the product instructions.

[0182] Example 1

[0183] This example provides a polar group or heterocyclic bridged bisphthalazinone structure polymer (oxofluorene heterocyclic bridged bisphthalazinone structure polyarylether nitrile sulfone), and the structural formula is as follows:

[0184]

[0185] The preparation method of the polymer with an oxofluorene heterocyclic bridged bisphthalazinone structure in this example includes the following steps:

[0186] In a polymerization reactor equipped with mechanical stirring, reflux condenser, water separator and gas conduit, 5 mol of a bisphenol monomer containing an oxygenated fluorene heterocyclic bridged phthalazinone structure, 5 mol of 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one (abbreviation: 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. Under an argon atmosphere, the reaction was carried out at 150 °C for 2 hours to remove water with xylene, then the xylene was distilled off, and the temperature was raised to 220 °C and stirring was continued for 16 hours. The specific reaction formula is as follows:

[0187]

[0188] After the reaction was completed, the reaction solution was sprayed and settled in hot water to obtain a white solid, which was then washed with water and dried to obtain a polymer with polar groups or a heterocyclic bridged phthalazinone structure (oxygenated fluorene heterocyclic bridged phthalazinone structure polyarylether nitrile sulfone). Its infrared spectrum and proton nuclear magnetic resonance spectrum are respectively as shown in Figure 1 in (a) and (b).

[0189] After testing, the T g of the polyarylether nitrile sulfone resin with an oxygenated fluorene heterocyclic bridged phthalazinone structure in this example reached 358 °C and it could be dissolved in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (that is, 0.1 g of the above polymer could be dissolved in 1 mL of the above solvent).

[0190] Example 2

[0191] This example provides a polymer with polar groups or a heterocyclic bridged phthalazinone structure (sulfur-containing fluorene heterocyclic bridged phthalazinone structure polyarylether sulfone ketone), and its structural formula is as follows:

[0192]

[0193] The preparation method of the polymer with polar groups or a heterocyclic bridged phthalazinone structure in this example includes the following steps:

[0194] In a dry 50 mL three-necked flask equipped with mechanical stirring, reflux condenser, water separator and gas conduit, 0.008 mol of a bisphenol monomer containing a sulfur-containing fluorene heterocyclic bridged phthalazinone structure, 0.002 mol of 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. Under a nitrogen atmosphere, the reaction was carried out at 140 °C for 4 hours to remove water with toluene, and the toluene was distilled off. The temperature was raised to 200 °C and stirring was continued for 10 hours. The specific reaction formula is as follows:

[0195]

[0196] After the reaction is completed, the reaction solution is poured into acetone to obtain a white strip solid. After washing with water and drying, a polymer with a polar group or a heterocyclic bridged phthalazinone structure (a poly(arylene ether sulfone ketone) containing a sulfur-fluorene heterocyclic bridged phthalazinone structure) is obtained. Its infrared spectrum and proton nuclear magnetic resonance spectrum are respectively as shown in Figure 2 Figures (a) and (b) below.

[0197] It is detected that the glass transition temperature of the poly(arylene ether sulfone ketone) resin containing a sulfur-fluorene heterocyclic bridged phthalazinone structure in this example T g reaches 376 °C and can be dissolved in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (that is, 0.1 g of the above polymer can be dissolved in 1 mL of the above solvent).

[0198] Example 3

[0199] This example provides a polymer with a polar group or a heterocyclic bridged phthalazinone structure (a poly(arylene ether nitrile) containing an oxygen-fluorene heterocyclic bridged phthalazinone structure), and its structural formula is as follows:

[0200]

[0201] The preparation method of the polymer with a polar group or a heterocyclic bridged phthalazinone structure in this example includes the following steps:

[0202] In a polymerization reaction kettle equipped with a mechanical stirrer, a reflux condenser, a water separator and a gas guide tube, 9 mol of a bisphenol monomer containing an oxygen-fluorene 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 are added. Under a nitrogen atmosphere, the reaction is carried out at 150 °C for 4 hours to carry out water-carrying with xylene and distill out xylene. Then the temperature is raised to 220 °C and stirring reaction is continued for 15 hours. The specific reaction formula is as follows:

[0203]

[0204] After the reaction is completed, the reaction solution is sprayed and settled into boiling water to obtain a white powder solid. After washing with water and drying, a polymer with a polar group or a heterocyclic bridged phthalazinone structure (a poly(arylene ether nitrile) containing an oxygen-fluorene heterocyclic bridged phthalazinone structure) is obtained. Its infrared spectrum and proton nuclear magnetic resonance spectrum are respectively as shown in Figure 3 Figures (a) and (b) below.

[0205] It is detected that the glass transition temperature of the poly(arylene ether nitrile) resin containing an oxygen-fluorene heterocyclic bridged phthalazinone structure in this exampleT g = 394 °C, and it can be dissolved in polar aprotic organic solvents such as NMP and 1,1,2,2 - tetrachloroethane (that is, 0.1 g of the above polymer can be dissolved in 1 mL of the above solvent).

[0206] Example 4

[0207] This example provides a polymer with a polar group or heterocyclic - bridged bisphthalazinone structure (a polysulfone containing a sulfur - fluorene heterocyclic - bridged bisphthalazinone structure), and its structural formula is as follows:

[0208]

[0209] The preparation method of the polysulfone resin with a sulfur - fluorene heterocyclic - bridged bisphthalazinone structure in this example includes the following steps:

[0210] Into a polymerization reactor equipped with a mechanical stirrer, a reflux condenser, a water separator and a gas guide tube, add 10 mol of a bisphenol monomer with a sulfur - fluorene heterocyclic - bridged bisphthalazinone structure, 12 mol of anhydrous potassium carbonate, 10 mol of 4,4′ - dichlorodiphenyl sulfone, 5 L of xylene and 15 L of sulfolane. Under a nitrogen atmosphere, react at 145 °C for 4 hours to carry out water - carrying with xylene. After the water is completely removed from the polymerization reaction system, distill out the xylene and raise the temperature to 200 °C and continue stirring for 40 hours. The specific reaction formula is as follows. After the reaction is completed, precipitate the reaction solution in ethanol to obtain a white powder solid. After washing with water and drying, a polymer with a polar group or heterocyclic - bridged bisphthalazinone structure (a polysulfone containing a sulfur - fluorene heterocyclic - bridged bisphthalazinone structure) is obtained, and its infrared spectrum and proton nuclear magnetic resonance spectrum are respectively as Figure 4 shown in (a) and (b) below.

[0211]

[0212] After testing, the T g of the polymer with a sulfur - fluorene heterocyclic - bridged bisphthalazinone structure in this example reaches 404 °C, and it can be dissolved in polar aprotic organic solvents such as NMP and 1,1,2,2 - tetrachloroethane (that is, 0.1 g of the above polymer can be dissolved in 1 mL of the above solvent).

[0213] Example 5

[0214] This example provides a polymer with a polar group or heterocyclic - bridged bisphthalazinone structure (a polyarylonitrile containing an oxygen - fluorene heterocyclic - bridged bisphthalazinone structure), and its structural formula is as follows:

[0215]

[0216] The preparation method of the polymer with polar group or heterocyclic bridged bisphthalazinone structure in this example includes the following steps:

[0217] In a dry 50 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, a water separator and a gas pipe, add 0.010 mol of oxygen-containing fluorene heterocyclic bridged bisphthalazinone structure bisphenol monomer, 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. Under an argon atmosphere, react at 140 °C for 6 hours to carry out water-carrying with toluene, then distill off toluene, and raise the temperature to 200 °C and continue stirring and reacting for 18 hours. The specific reaction formula is as follows:

[0218]

[0219] After the reaction is completed, precipitate the reaction solution in ethanol to obtain a white strip solid. After washing with water and drying, a polymer with polar group or heterocyclic bridged bisphthalazinone structure (polyarylonitrile with oxygen-containing fluorene bridged bisphthalazinone structure) is obtained. Its infrared spectrum and proton nuclear magnetic resonance spectrum are respectively as Figure 5 shown in (a) and (b) below.

[0220] After testing, the glass transition temperature of the polyarylonitrile resin with oxygen-containing fluorene heterocyclic bridged bisphthalazinone structure in this example T g = 400 °C, and it can be dissolved in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (that is, 0.1 g of the above polymer can be dissolved in 1 mL of the above solvent).

[0221] Example 6

[0222] This example provides a polymer with polar group or heterocyclic bridged bisphthalazinone structure (polyarylonitrile sulfone with sulfur-containing fluorene heterocyclic bridged bisphthalazinone structure), and its structural formula is as follows:

[0223]

[0224] The preparation method of the polymer with sulfur-containing fluorene heterocyclic bridged bisphthalazinone structure in this example includes the following steps:

[0225] In a polymerization reactor equipped with a mechanical stirrer, a reflux condensation device, a water separator and a gas pipe, add 10 mol of sulfur-containing fluorene heterocyclic bridged bisphthalazinone 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 sulfolane. Under a nitrogen atmosphere, react at 145 °C for 5 hours to carry out water-carrying with toluene, and distill off toluene. Raise the temperature to 200 °C and continue stirring and reacting for 25 hours. The specific reaction formula is as follows:

[0226]

[0227] After the reaction is completed, the reaction solution is sprayed and settled into acetone to obtain a white powder solid. After washing with water and drying, a polymer with a polar group or a heterocyclic bridged phthalazinone structure (a poly(aryl nitrile sulfone) containing a sulfur-fluorene heterocyclic bridged phthalazinone structure) is obtained. Its infrared spectrum and proton nuclear magnetic resonance spectrum are respectively as shown in Figure 6 (a) and (b) below.

[0228] It is detected that the glass transition temperature of the poly(aryl nitrile sulfone) resin containing a sulfur-fluorene heterocyclic bridged phthalazinone structure in this example T g = 405 °C, and it can be dissolved in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (that is, 0.1 g of the above polymer can be dissolved in 1 mL of the above solvent).

[0229] Example 7

[0230] This example provides a polymer with a polar group or a heterocyclic bridged phthalazinone structure (a poly(aryl ether nitrile) containing a sulfur-fluorene heterocyclic bridged phthalazinone structure), and its structural formula is as follows:

[0231]

[0232] The preparation method of the poly(aryl ether nitrile) resin containing a sulfur-fluorene heterocyclic bridged phthalazinone structure in this example includes the following steps:

[0233] 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 bisphenol monomer containing a sulfur-fluorene heterocyclic bridged phthalazinone structure, 0.006 mol of a bisphenol monomer of 4-(3'-phenyl-4'-hydroxyphenyl)-2,3-phthalazinone, 0.02 mol of anhydrous potassium carbonate, 0.010 mol of 2,6-dichlorobenzonitrile, 8 mL of toluene and 15 mL of sulfolane are added. Under a nitrogen atmosphere, the reaction is carried out at 140 °C for 4 hours to remove water with toluene, and toluene is distilled off. Then the temperature is raised to 195 °C and stirring reaction is continued for 12 hours. The specific reaction formula is as follows;

[0234] After the reaction is completed, the reaction solution is poured into boiling water to obtain a white strip solid, and then after washing with water and drying, a polymer with a polar group or a heterocyclic bridged phthalazinone structure (a poly(aryl ether nitrile) containing a sulfur-fluorene heterocyclic bridged phthalazinone structure) is obtained. Its infrared spectrum and proton nuclear magnetic resonance spectrum are respectively as shown in Figure 7 (a) and (b) below.

[0235]

[0236] After testing, the glass transition temperature of the polyarylether nitrile with a sulfur-containing fluorene heterocyclic bridged bisphthalazinone structure in this example T g = 334 °C, and it can be dissolved in polar aprotic organic solvents such as NMP and 1,1,2,2-tetrachloroethane (that is, 0.1 g of the above polymer can be dissolved in 1 mL of the above solvent).

[0237] Example 8

[0238] This example provides a polymer with a polar group or a heterocyclic bridged bisphthalazinone structure (a polyarylether sulfone ketone with a sulfone-based polar group bridged bisphthalazinone structure), and its structural formula is as follows:

[0239]

[0240] The preparation method of the polymer with a sulfone-based polar group bridged bisphthalazinone structure in this example includes the following steps:

[0241] In a dry 50 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, a water separator and a gas pipe, add 0.010 mol of a bisphenol monomer with a sulfone-based polar group bisphthalazinone structure, 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. Under a nitrogen atmosphere, react at 140 °C for 4 hours to carry out water removal with toluene and distill out toluene. Then raise the temperature to 190 °C and continue stirring for 12 hours. The specific reaction formula is as follows:

[0242]

[0243] After the reaction is completed, precipitate the reaction solution in ethanol to obtain a white solid. After washing with water and drying, a polyarylether sulfone ketone resin with a sulfone-based polar group bridged bisphthalazinone structure is obtained, and its infrared spectrum and 1H NMR spectrum are respectively as Figure 8 shown in (a) and (b) below.

[0244] After testing, the glass transition temperature of the polyarylether sulfone ketone with a sulfone-based polar group bridged bisphthalazinone structure in this example T g = 367 °C, and it can be dissolved in polar aprotic organic solvents such as NMP, DMAc, pyridine and 1,1,2,2-tetrachloroethane (that is, 0.1 g of the above polymer can be dissolved in 1 mL of the above solvent).

[0245] Comparative Example 1

[0246] This comparative example provides a polymer with a bisphthalazinone structure (a polyarylether sulfone ketone with a diphenyl ether bisphthalazinone structure), and its structural formula is as follows:

[0247]

[0248] The preparation method of the polyarylethersulfoneketone with a phthalazinone structure in this comparative example includes the following steps:

[0249] Under the protection of nitrogen, accurately add 0.010 mol of diphenyl ether phthalazinone-based bisphenol monomer, 0.014 mol of anhydrous potassium carbonate, 0.002 mol of 4,4′-difluorobenzophenone, and 0.008 mol of 4,4′-difluorodiphenyl sulfone into a 100 mL three-necked flask equipped with mechanical stirring, liquid seal, nitrogen gas inlet pipe, and water separator. Add 5 mL of toluene as a water-carrying agent and 8 mL of sulfolane as a solvent. Stir and evenly heat up to 140 °C. After refluxing for 3 h, distill out all the toluene and the generated water. Raise the reaction temperature to 190 °C and react for about 8 h (the reaction formula is as follows). Deposit the reaction product in hot water, and the product is in the form of white filaments. Remove the inorganic salts and residual sulfolane solvent in the product by boiling water. After filtration and drying, dissolve the polymer in chloroform, filter, and then deposit it in ethanol solvent to obtain a white flocculent polymer. After filtration, polyarylethersulfoneketone with a diphenyl ether phthalazinone structure is obtained, and its infrared spectrum and 1H NMR spectrum are respectively as Figure 9 shown in (a) and (b) below.

[0250]

[0251] After testing, the glass transition temperature of the polyarylethersulfoneketone resin with a phthalazinone structure in this comparative example T g is 324 °C and it can be dissolved in chloroform, tetrachloroethane, and NMP (that is, 0.1 g of the above polymer can be dissolved in 1 mL of the above solvents).

[0252] Compared with the structure of the polyarylether with a polar group or heterocyclic bridged phthalazinone structure provided in Example 8, the polyarylethersulfoneketone resin with a phthalazinone structure in this comparative example does not contain the sulfone group-containing polar group bridged 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 polymer with a polar group or heterocyclic bridged phthalazinone structure in Example 8 has a higher glass transition temperature and can still be dissolved in polar aprotic organic solvents, which is mainly due to the introduction of the polar group or heterocyclic bridged phthalazinone structure.

[0253] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention are within the scope of the claims of the present invention pending approval.

Claims

1. A polymer with a polar group or a heterocyclic bridged phthalazinone structure, characterized in that, Its structural formula is shown in Formula (1) or Formula (2): （1）； （2）； In Formula (1) and Formula (2), The structure of is one or several of the following structures: ； ； , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; In formulas (1) and (2), has a structure that 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-position, 1, 3-position or 1, 4-position; , at the 2, 2'-position or 4, 4'-position; , 1, 4-position, 1, 5-position, 1, 6-position, 2, 6-position or 2, 7-position; , the 3, 3'-position or 4, 4'-position; , the 3, 3'-position or 4, 4'-position; , at the 3, 3'-position or 4, 4'-position; , the 3, 3'-position or 4, 4'-position; , at the 3, 3'-position or 4, 4'-position; , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, phenyl, phenoxy, alkyl, or alkoxy, and the structures of R1, R2, R3, and R4 are the same or different, where the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing at least 1 carbon atom; ； ； ； ； ； ； ； ； ； ； ； ； ； ； Among them, is one or more of the following structures: ； ； ； ； ； ； , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; For , one or more of the following.

2. The polar group or heterocyclic bridge-linked phthalazinone structure polymer according to claim 1, characterized in that 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, phenyl, phenoxy, alkyl, or alkoxy, and the structures of R1, R2, R3, and R4 are the same or different, wherein the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing at least 1 carbon atom.

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

4. A method for preparing a polymer having a polar group or a heterocyclic bridged phthalazinone structure according to any one of claims 1 to 3, characterized in that, It includes the following steps: Using a bisphenol monomer containing a polar group or a heterocyclic bridged bisphthalazinone structure, an aromatic dihalogen monomer, and optionally other bisphenol or bisphenol-like monomers as polycondensation monomers, mixing with a solvent, an azeotropic water-carrying agent and a catalyst, and carrying out a stepwise polymerization reaction under an inert 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 bridged bisphthalazinone structure polymer.

5. The preparation method of the polymer with a polar group or a heterocyclic bridge-linked phthalazinone structure according to claim 4, characterized in that, The bisphenol monomer containing a polar group or a heterocyclic bridged bisphthalazinone structure has the following molecular structure: Among them, the structure of —Ar1— is one or more of the following structures: ； ； , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; 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-position, 1, 3-position or 1, 4-position; , 2, 2'-position or 4, 4'-position; , 1, 4-position, 1, 5-position, 1, 6-position, 2, 6-position or 2, 7-position; , at the 3, 3'- or 4, 4'-position; at the 3, 3'- or 4, 4'-position; , at the 3, 3'- or 4, 4'-position; , at the 3, 3'-position or 4, 4'-position; , at the 3, 3'-position or 4, 4'-position; , R1, R2, R3, and R4 are each independently selected from hydrogen, a halogen substituent, phenyl, phenoxy, alkyl, or alkoxy, and the structures of R1, R2, R3, and R4 are the same or different, wherein the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing at least 1 carbon atom; ； ； ； ； ； ； ； ； ； ； ； ； ； ； Among them is one or more of the following structures: ； ； ； ； ； ； , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; , 2, 2-position, 2, 3-position or 3, 3-position; is and / or one or more of the following.

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

7. The preparation method of the polymer with a polar group or a heterocyclic bridged phthalazinone structure according to claim 6, characterized in that, The volume dosage of the azeotropic water-carrying agent is 0.1-20 times the volume dosage 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 dosage of the solvent is 0.2-50 times the total mass of the bisphenol monomer, the bisphenol-like monomer and the aromatic dihalogen monomer in the reaction feed; And / or, the catalyst further includes a fluoride catalyst, and the fluoride catalyst includes an alkali metal fluoride.

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

9. The preparation method of the polar group or heterocyclic bridge-linked phthalazinone structure polymer according to claim 8, characterized in that, During the polymerization reaction, azeotropic dehydration is first carried out at 110 - 150 °C until the water is completely carried out of the reaction system by the azeotropic entrainer, and then the azeotropic entrainer is distilled off. After the azeotropic entrainer is distilled off, the reaction is carried out at 150 - 280 °C until the polymerization reaction ends; And / or, the precipitating agent comprises one or a mixture of several of water, alcohol, tetrahydrofuran or acetone.

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

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