Bis-phthalazinone structure polymer toughened bismaleimide resin and preparation method and application thereof

Abstract

The invention provides bis (phthalazinone) structure polymer toughened bismaleimide resin as well as a preparation method and application thereof, and relates to the technical field of high polymer material synthesis. The bis (phthalazinone) structure polymer toughened bismaleimide resin is mainly prepared from a bismaleimide monomer, an allyl compound, a bis (phthalazinone) structure polymer, other optional thermoplastic resin toughening agents, an optional co-curing component and an optional curing agent, the bis (phthalazinone) structure polymer has excellent heat resistance and good solubility, the heat resistance of the bis (phthalazinone) structure polymer is matched with that of high-temperature-resistant bismaleimide resin, and the bis (phthalazinone) structure polymer can be used as a toughening agent to remarkably improve the impact toughness of the bismaleimide resin and a composite material thereof and maintain the excellent heat resistance of the bismaleimide resin; therefore, the bismaleimide resin can be suitable for more application scenes.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material synthesis, and relates to a bis(phthalazinone) structured polymer toughened bismaleimide resin and a preparation method and application thereof. Background Art

[0002] Bismaleimide resin (BMI resin for short) is a bifunctional compound with maleimide as the active end group. Due to its good mechanical properties, heat resistance, wave transmission, radiation resistance, low melt viscosity, wide processing window and other advantages, it is used as a resin matrix to prepare continuous fiber reinforced resin-based composite materials and high temperature resistant structural adhesives. It is widely used in aerospace, electronics and electrical fields. Bismaleimide resin undergoes a curing and cross-linking reaction under the effect of heat to form a network structure with a high cross-linking density, resulting in poor impact resistance and stress cracking resistance of the resin matrix and its composite materials. Toughening modification is required in practical applications.

[0003] At present, the main methods for toughening and modifying bismaleimide resins are: synthesizing new bismaleimide resin monomers; introducing diamines or allyl compounds for copolymerization; adding blended liquid rubber, nano components, thermotropic liquid crystals, thermoplastic resins, etc. Liquid rubber and thermotropic liquid crystal polymers have insufficient heat resistance and are difficult to match the heat resistance of bismaleimide resins. Nano components are easy to agglomerate, have poor processing performance and high cost. High-performance thermoplastic resins have both high heat resistance temperatures that match bismaleimide resins and good processing performance. They are an important and effective toughening and modifier for bismaleimide resins.

[0004] The polyarylether thermoplastic resin containing diazinone biphenyl structure is a type of high-performance thermoplastic resin independently developed by Dalian University of Technology. For example, polyaryletherketone containing diazinone biphenyl structure (glass transition temperature T g :263℃)、polyarylethersulfone( T g : 305℃), poly(arylether nitrile ketone) T g : 268~289℃, Wang Mingjing, PhD thesis of Dalian University of Technology, 2007; Chinese invention patent ZL03111540.3) resin, excellent comprehensive properties, especially outstanding high temperature mechanical properties, its glass transition temperature is adjustable between 230 and 305℃, and has good solubility, can be dissolved in a few polar aprotic organic solvents, and can be dissolved in epoxy resin and bismaleimide resin systems, and is used for toughening modification of epoxy resin and bismaleimide resin and their composites.

[0005] With the rapid development of aerospace, electronics and electrical fields, higher requirements are put forward for the heat resistance of bismaleimide resin and its composite materials. The heat resistance of traditional high-performance thermoplastic resin toughening agents can no longer match the heat resistance of high-temperature resistant bismaleimide resin. Therefore, it is of great practical application value to develop a new type of high-temperature resistant thermoplastic resin toughening agent to meet the heat resistance, toughness and processing performance requirements of bismaleimide resin and its resin-based composite materials and structural adhesives. In view of this, the present invention is specially proposed. Summary of the invention

[0006] The purpose of the present invention is to provide a bis(phthalazinone) structural polymer toughened bismaleimide resin and a preparation method and application thereof, so as to solve the above technical problems.

[0007] In order to achieve the above purpose, the following technical solutions are adopted: The first object of the present invention is to provide a bis(phthalazinone) structured polymer toughened bismaleimide resin, comprising the following raw materials in parts by weight: 100 parts of bismaleimide monomer, 5-90 parts of allyl compound, 1-30 parts of phthalazinone structure polymer, 0-30 parts of other thermoplastic resin toughening agent, 0-50 parts of co-curing component and 0-5 parts of curing agent.

[0008] Furthermore, on the basis of the above technical solution of the present invention, the diphthalazinone structured polymer includes one or a combination of a polymer having a structure as shown in the following formula (1), a polymer having a structure as shown in the following formula (2), or a polymer having a structure as shown in the following formula (3): (1); (2); (3); In formula (1), formula (2) and formula (3), the structure of —Ar1— is one or more of the following structures: ; ; ; ; ; ; ; ; ; ; ; 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 following; In formula (1), formula (2) and formula (3), 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), formula (2) and formula (3), The structure 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 .

[0009] Further, on the basis of the above technical solution of the present invention, the bismaleimide monomer includes one or more of the following structures: ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; , wherein R5, R6, R7, and R8 are independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group or an alkoxy group, and the structures of R5, R6, R7 and R8 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.

[0010] Further, on the basis of the above technical solution of the present invention, the allyl compound includes one or more of the following structures: ; ; ; ; ; ; ; ; ; ; ; ; .

[0011] Further, on the basis of the above technical solution of the present invention, the other thermoplastic resin toughening agent includes one or a combination of two or more of polyaryletherketone, polyethersulfone, polyarylethersulfone, thermoplastic polyimide or polyetherimide; and / or, the co-curing component comprises one or a combination of two or more of a cyanate resin, an allylphenoloxy resin, an epoxy resin or a benzoxazine resin; And / or, the curing agent includes one or a combination of two or more of aminophenylacetylene, imidazole curing agents or aromatic amine curing agents.

[0012] The second object of the present invention is to provide a method for preparing the above-mentioned bis(phthalazinone) structure polymer toughened bismaleimide resin, comprising the following steps: (a) heating an allyl compound until it is melted, adding a phthalazinone structural polymer, and optionally a co-curing component and optionally other thermoplastic resin toughening agents, and stirring until they are completely dissolved in the allyl compound to obtain a dissolved phase; (b) then adding bismaleimide monomer and optional curing agent into the dissolved phase, heating and stirring to perform blending or prepolymerization, and obtaining a bismaleimide resin toughened with a phthalazinone structured polymer.

[0013] Further, based on the above technical solution of the present invention, in step (a), the heating temperature is 30-160°C; And / or, in step (b), the heating and stirring temperature is 100-140° C., and the time is 0.1-3 h.

[0014] The third object of the present invention is to provide an application of the above-mentioned bis(phthalazinone) structure polymer toughened bis(malonate) resin in prepreg, wherein the bis(phthalazinone) structure polymer toughened bis(malonate) resin is used as a resin matrix in the prepreg.

[0015] Further, on the basis of the above technical solution of the present invention, the reinforcement in the prepreg includes one or a combination of two or more of continuous carbon fiber, continuous glass fiber, continuous quartz fiber, continuous basalt fiber, continuous aramid fiber, continuous polybenzimidazole fiber and continuous polybenzoxazole fiber; And / or, the resin glue mass content of the prepreg is 30-50%.

[0016] 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 bismaleimide resin toughened by a phthalazinone structure polymer, which is mainly made of a bismaleimide monomer, an allyl compound, a phthalazinone structure polymer, and optionally other thermoplastic resin toughening agents, an optional co-curing component, and an optional curing agent. The phthalazinone structure polymer has excellent heat resistance and good solubility, and its heat resistance matches the heat resistance of the high-temperature resistant bismaleimide resin. Therefore, it can be used as a toughening agent to significantly improve the impact toughness of the bismaleimide resin and its composite material, and maintain the excellent heat resistance of the bismaleimide resin, thereby making the bismaleimide resin suitable for more application scenarios.

[0017] (2) The present invention also provides a method for preparing the above-mentioned bis(phthalazinone) structured polymer toughened bis(malonate) resin. The preparation method is simple and has a stable process, and can achieve stable preparation of the bis(phthalazinone) structured polymer toughened bis(malonate) resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 is the infrared spectrum of PSUPS and PSUPNS in the present invention; Figure 2 The infrared spectra (a) and hydrogen nuclear magnetic resonance spectra (b) of PBPENS and PBPENS-DA in the present invention are shown; Figure 3 is the infrared spectrum of PPENS in the present invention; Figure 4 It is the hydrogen nuclear magnetic resonance spectrum of PPENS in the present invention. DETAILED DESCRIPTION

[0019] 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.

[0020] 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.

[0021] According to a first aspect of the present invention, a bis(phthalazinone) structured polymer toughened bis(malonium) resin is provided, comprising the following raw materials in parts by weight: 100 parts of bismaleimide monomer, 5-90 parts of allyl compound, 1-30 parts of phthalazinone structure polymer, 0-30 parts of other thermoplastic resin toughening agent, 0-50 parts of co-curing component and 0-5 parts of curing agent.

[0022] The bismaleimide monomer may be any bismaleimide commonly used in the art, which is not limited herein.

[0023] The introduction of the bis(phthalazinone) structure in the bis(phthalazinone) structure polymer makes it have excellent heat resistance and good solubility. Its heat resistance matches the heat resistance of the high-temperature resistant bismaleimide resin, so it can be used as a toughening agent to significantly improve the impact toughness of the bismaleimide resin and its composite materials, and maintain the excellent heat resistance of the bismaleimide resin. The amount of the bis(phthalazinone) structure polymer also affects the impact toughness and processing properties of the bismaleimide resin and its composite materials. If its amount is too low (less than 1 part), it is easy to cause the impact toughness of the bismaleimide resin to be not significantly improved. If its amount is too high (more than 30 parts), it is easy to cause the viscosity of the bismaleimide blended resin system to be too high and the processing performance is too poor. Therefore, typical but non-limiting weight fractions of the phthalazinone structure polymer are 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28 or 30 parts, etc., and numerical ranges between any two points.

[0024] The allyl compound acts as a toughening agent and curing agent in the co-curing system, and also acts to dissolve the bismaleimide resin and the thermoplastic resin toughening agent, thereby improving the processing properties of the bismaleimide resin matrix. Typical but non-limiting weight fractions of the allyl compound are 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts or 90 parts, and the range of values ​​between any two points.

[0025] In addition to the above-mentioned phthalazinone structural polymer and allyl compound, other thermoplastic resin toughening agents, co-curing components and curing agents may be selectively added as needed.

[0026] Other thermoplastic resin toughening agents are mainly used for joint toughening, and can be selected from high-performance thermoplastic resins commonly used in the art, such as polyester (PET), polyethersulfone (PES), polyaryletherketone (PAEK), polyimide (PI), polyetherketone (PEK), etc. Typical but non-limiting weight fractions of other thermoplastic resin toughening agents are 0 parts, 1 parts, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts or 30 parts, etc., and the numerical range between any two points.

[0027] The co-curing component can be used to adjust the processing performance, heat resistance, mechanical properties or dielectric properties of the bismaleimide resin curing system. Typical but non-limiting weight fractions of the co-curing component are 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50, etc., and the range of values ​​between any two points.

[0028] Curing agent, mainly used for cross-linking and curing of bismaleimide and co-curing components. Typical but non-limiting mass fractions of the curing agent are 0, 1, 2, 3, 4 or 5, etc., and the numerical range between any two points.

[0029] As an optional embodiment of the technical solution of the present invention, the diphthalazinone structure polymer includes a polymer having a structure shown in the following formula (1), a polymer having a structure shown in the following formula (2), or a polymer having a structure shown in the following formula (3), or a combination of the following: (1); (2); (3); In formula (1), formula (2) and formula (3), The use of a bridging structure containing a flexible group, a polar group or a ladder heterocycle in the structure is beneficial to adjusting the heat resistance of the phthalazinone structure polymer. The structure is specifically one or more of the following structures: ; ; ; ; ; ; ; ; ; ; ; in, One or more 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; for , One or more of the following; In formula (1), formula (2) and formula (3), 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), formula (2) and formula (3), 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; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 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 .

[0030] It should be noted that the structural formulas (1), (2) and (3) of the phthalazinone structure polymer of the present invention only show the repeating unit structure contained therein, and do not limit its molecular weight or degree of polymerization. As a high-temperature resistant thermoplastic resin toughening agent, the phthalazinone structure polymer can be selected with different molecular weights according to different application requirements of bismaleimide resin (for example, resin-based composite materials, coatings, adhesives, functional films and other different uses). The molecular weight of the phthalazinone structure polymer can be regulated according to the molar ratio of the polymerized monomers.

[0031] The present invention provides a bismaleimide resin toughened by a phthalazinone structure polymer having both excellent heat resistance and good impact toughness. The phthalazinone structure polymer is mainly introduced as a toughening agent to improve the impact toughness of the bismaleimide resin without reducing the heat resistance of the bismaleimide resin. The maximum unnotched impact strength can reach 28.8 kJ / m 2 ; Furthermore, other thermoplastic resin toughening agents can be appropriately added to jointly toughen the bismaleimide resin and its composite materials. The processing properties of the bismaleimide resin system can also be flexibly adjusted by adding other thermoplastic resin toughening agents, co-curing components and / or curing agents, and the heat resistance, mechanical properties and dielectric properties of its cured products and composite materials can be adjusted, so that it can meet the needs of more different application scenarios.

[0032] As an optional implementation of the technical solution of the present invention, a method for preparing a phthalazinone structure polymer having a structure shown in formula (1) comprises the following steps: A diphenylamine structure-containing monomer, an aromatic dihalogen monomer, and optionally other bisphenols or bisphenol-like monomers are mixed as polycondensation monomers, mixed with a solvent, an azeotropic water-carrying agent and a catalyst, and copolymerized under a protective gas atmosphere, the reaction solution obtained after the reaction is precipitated in a precipitant, and the precipitated solid product is washed, filtered and dried to obtain a diphenylamine structure polymer.

[0033] As an optional implementation of the technical solution of the present invention, a method for preparing a (amino-terminated) phthalazinone structure polymer of the structure shown in formula (2) comprises the following steps: A mixture of a diphenylamine structure-containing monomer, an aromatic dihalogen monomer, any other bisphenol or bisphenol-like monomer, and p-aminophenol as a condensation monomer is mixed with a solvent, an azeotropic water-carrying agent, and a catalyst, and copolymerization is carried out under a protective gas atmosphere. The reaction solution obtained after the reaction is precipitated in a precipitant, and the precipitated solid product is washed, filtered, and dried to obtain an amino-terminated diphenylamine structure polymer having a structure shown in formula (2).

[0034] As an optional implementation of the technical solution of the present invention, a method for preparing a (maleimide-terminated) phthalazinone structure polymer of the structure shown in formula (3) comprises the following steps: A monomer containing a phthalazinone structure, an aromatic dihalogen monomer, any other bisphenol or bisphenol-like monomer, and p-aminophenol are mixed as polycondensation monomers, mixed with a solvent, an azeotropic water-carrying agent, and a catalyst, and copolymerized under a protective gas atmosphere, the reaction solution obtained after the reaction is precipitated in a precipitant, and the precipitated solid product is washed, filtered, and dried to obtain an amino-terminated phthalazinone structure polymer having a structure shown in formula (2); The amino-terminated phthalazinone structure polymer of the structure shown in formula (2) and maleic anhydride are used as reaction monomers, mixed with a solvent, an azeotropic water-carrying agent, a catalyst and p-toluenesulfonic acid, and a capping reaction is carried out under a protective gas atmosphere. The reaction solution obtained after the reaction is precipitated in a precipitant, and the precipitated solid product is washed, filtered and dried to obtain a maleimide-terminated phthalazinone structure polymer of the structure shown in formula (3).

[0035] As an optional implementation of the technical solution of the present invention, the monomer containing the diphthalazinone structure corresponds to The structure is one or more of the following structures: ; ; ; ; ; ; ; ; ; ; ; 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 .

[0036] As an optional implementation of the technical solution of the present invention, the aromatic dihalogen monomer, that is, the structure corresponding to —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; X is a halogen, including F or Cl.

[0037] As an optional implementation of the technical solution of the present invention, other bisphenol or bisphenol-like monomers correspond to The structure 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 .

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] As an optional implementation scheme of the technical scheme 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 diphenylamine structure monomers, other bisphenol monomers and bisphenol-like monomers in the reaction feed.

[0044] As an optional implementation manner of the technical solution of the present invention, the mass of the solvent is 0.2-50 times (for example, 0.2 times, 1 times, 2 times, 4 times, 5 times, 6 times, 8 times, 10 times, 12 times, 15 times, 16 times, 18 times, 20 times, 25 times, 28 times, 30 times, 32 times, 35 times, 38 times, 40 times, 42 times, 45 times, 48 ​​times or 50 times the total mass of the reaction feed bisphthalazinone monomers, other bisphenol monomers and bisphenol-like monomers and aromatic dihalogen monomers).

[0045] 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.

[0046] As an optional implementation manner of the technical scheme of the present invention, the temperature of the polymerization reaction is 80-300°C (for example, 80°C, 100°C, 110°C, 120°C, 140°C, 150°C, 160°C, 180°C, 190°C, 200°C, 220°C, 240°C, 250°C, 260°C, 280°C or 300°C, etc.), and the time of the polymerization reaction is 4-60h (for example, 4h, 10h, 12h, 20h, 24h, 30h, 36h, 40h, 48h, 50h, 55h or 60h, etc.).

[0047] 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.

[0048] As an optional embodiment of the technical solution of the present invention, bismaleimide includes one or more of the following structures: ; ; ; ; ; ; ; ; ; ; ; , ; ; ; ; ; ; ; ; ; ; ; ; ; , R5, R6, R7, and R8 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 R5, R6, R7 and R8 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.

[0049] As an optional implementation of the technical solution of the present invention, the allyl compound includes one or more of the following structures: ; ; ; ; ; ; , n is the number of repeating units, and there is no limitation on the value range of n. Polymers with different numbers of repeating units can be selected according to actual needs; , m is the number of repeating units, and there is no limitation on the value range of m. Polymers with different numbers of repeating units can be selected according to actual needs; ; ; ; ; .

[0050] As an optional implementation of the technical solution of the present invention, other thermoplastic resin toughening agents include one or a combination of two or more of polyaryletherketone, polyethersulfone, polyarylethersulfone, thermoplastic polyimide or polyetherimide.

[0051] As an optional implementation of the technical solution of the present invention, the co-curing component includes one or a combination of two or more of cyanate resin, allyl phenol oxide resin, epoxy resin or benzoxazine resin.

[0052] As an optional implementation of the technical solution of the present invention, the curing agent includes one or a combination of two or more of aminophenylacetylene, imidazole curing agents or aromatic amine curing agents.

[0053] By further limiting the specific types of other thermoplastic resin toughening agents, co-curing components and curing agents, the impact properties, processing properties and heat resistance of the bis(phthalazinone) structural polymer toughened bis(malonium) resin are further improved.

[0054] According to a second aspect of the present invention, there is also provided a method for preparing the above-mentioned bis(phthalazinone) structured polymer toughened bismaleimide resin, comprising the following steps: (a) heating an allyl compound until it is melted, adding a phthalazinone structural polymer, and optionally a co-curing component and optionally other thermoplastic resin toughening agents, and stirring until they are completely dissolved in the allyl compound to obtain a dissolved phase; (b) then adding bismaleimide monomer and optional curing agent into the dissolved phase, heating and stirring to perform blending or prepolymerization, and obtaining a bismaleimide resin toughened with a phthalazinone structured polymer.

[0055] Specifically, in step (a), "optional co-curing component" means that the co-curing component may or may not be added. Similarly, "optional other thermoplastic resin toughening agent" means that other thermoplastic resin toughening agents may or may not be added.

[0056] In step (b), "optional curing agent" means that the curing agent may or may not be added.

[0057] The invention provides a method for preparing a bismaleimide resin toughened by a bismaleimide structure polymer, which has a simple preparation process and a stable process. In the preparation process, a bismaleimide structure polymer is used as a toughening agent, and the toughening agent not only has excellent heat resistance, but also does not reduce the heat resistance of the bismaleimide resin and its composite material by adding the bismaleimide structure polymer, and can significantly improve the impact toughness of the bismaleimide and its composite material by adding a small amount; in addition, the toughening agent can also be dissolved in the bismaleimide resin system, meeting the processing technology requirements of the bismaleimide resin and its composite material.

[0058] As an optional implementation scheme of the technical scheme of the present invention, in step (a), the heating temperature is 30-160°C, and typical but non-limiting temperatures are 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C or 160°C, etc., and the numerical range between any two points.

[0059] As an optional embodiment of the technical solution of the present invention, in step (b), the temperature of heating and stirring is 100-140°C, and the time is 0.1-3h. Typical but non-limiting temperatures are 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C or 140°C, etc. Typical but non-limiting heating and stirring time is 0.1h, 0.5h, 1h, 1.5h, 1.8h, 2h, 2.5h or 3h, etc.

[0060] According to the third aspect of the present invention, there is also provided an application of the bismaleimide resin toughened by the phthalazinone structure polymer provided by the first aspect of the present invention in a prepreg, wherein the bismaleimide resin toughened by the phthalazinone structure polymer is used as a resin matrix in the prepreg.

[0061] As an optional implementation of the technical solution of the present invention, the reinforcement in the prepreg includes one or a mixture of two or more of continuous carbon fiber, continuous glass fiber, continuous quartz fiber, continuous basalt fiber, continuous aramid fiber, continuous polybenzimidazole fiber or continuous polybenzoxazole fiber.

[0062] As an optional implementation of the technical solution of the present invention, the mass content of the resin glue of the prepreg is 30-50%, for example, 30%, 35%, 40%, 45% or 50%.

[0063] The present invention will be further described in detail below with reference to specific embodiments and comparative examples.

[0064] It should be noted that the test methods in the following examples are conventional methods unless otherwise specified and can be carried out according to the techniques or conditions described in the literature in the art or according to the product instructions. The types and structures of the raw materials used in the following examples or comparative examples are specifically shown in Table 1 below.

[0065] Table 1 The preparation method of diphenyl sulfone phthalazinone structure polyaromatic nitrile sulfone (PSUPNS) comprises the following steps: In a reactor equipped with a nitrogen protection device, a mechanical stirring device, and a reflux water separation device, 0.12 mol of diphenyl sulfone phthalazinone structural monomer, 0.06 mol of 2,6-difluorobenzonitrile, 0.06 mol of 4,4'-difluorodiphenyl sulfone, 0.168 mol of anhydrous potassium carbonate, 60 mL of cyclopentane, and 30 mL of toluene were added. Under nitrogen protection, the temperature was raised to 145°C and azeotropic dehydration was performed for 2 hours; the reflux device was removed, the temperature was raised to 175°C to remove all toluene in the system, the temperature was raised to 195°C, the reaction was performed for 4 hours, the temperature was raised to 200°C, and the reaction was performed for 8 hours; then 60 mL of sulfolane was added, and after the system temperature dropped to 145°C, the polymer solution was poured into hot water containing hydrochloric acid to obtain a crude polymer product; the crude polymer product was boiled with deionized water for 2-3 times to remove inorganic salts and residual solvents, filtered, and dried; then dissolved with chloroform, filtered with cotton and diatomaceous earth as filter elements, the filtrate was precipitated into ethanol, filtered, and dried to obtain refined PSUPNS, whose infrared spectrum is shown as follows: Figure 1 shown.

[0066] The preparation method of diphenyl sulfone phthalazinone structure polyaryl sulfone (PSUPS) is as follows: except that "2,6-difluorobenzonitrile 0.06 mol, 4,4'-difluorodiphenyl sulfone 0.06 mol" in the preparation method of PSUPNS is replaced by "4,4'-difluorodiphenyl sulfone 0.12 mol", the other ingredients remain unchanged. The infrared spectrum of PSUPS is shown in Figure 1 shown.

[0067] The preparation method of diphenyl ether phthalazinone structure poly (arylether nitrile sulfone) (PBPENS) is the same as that of PSUPNS except that the "diphenyl sulfone phthalazinone structure monomer" is replaced by "diphenyl ether phthalazinone structure monomer". Figure 2 As shown in (a), the H NMR spectrum is Figure 2 As shown in (b).

[0068] The preparation method of diphenyl sulfone phthalazinone structure copolymer biphenol type polyarylethersulfone (PSUBPS) is as follows: except that "0.12 mol of diphenyl sulfone phthalazinone structure monomer, 0.06 mol of 2,6-difluorobenzonitrile, 0.06 mol of 4,4'-difluorodiphenyl sulfone" in the preparation method of PSUPNS is replaced by "0.06 mol of diphenyl sulfone phthalazinone structure monomer, 0.06 mol of 4,4'-biphenol, 0.12 mol of 4,4'-difluorodiphenyl sulfone", the other ingredients remain unchanged.

[0069] The preparation method of amino-terminated diphenyl ether bis(phthalazinone) structure poly(arylether nitrile sulfone) (PBPENS-DA) comprises the following steps: In a reactor equipped with a nitrogen protection device, a mechanical stirring device, and a reflux water separation device, 0.2 mol of diphenyl ether phthalazinone structural monomer, 0.1079 mol of 2,6-difluorobenzonitrile, 0.1079 mol of 4,4'-difluorodiphenyl sulfone (in order to halogen-terminate for further reaction with p-aminophenol, the amounts of 2,6-difluorobenzonitrile and 4,4'-difluorodiphenyl sulfone are slightly excessive here), 0.26 mol of anhydrous potassium carbonate, 110 mL of cyclopentane sulfone, and 55 mL of toluene were added. Under nitrogen protection, the temperature was raised to 145°C and azeotropic dehydration was performed for 2 hours; the reflux device was removed, the temperature was raised to 175°C to remove all toluene in the system, the temperature was raised to 195°C, the reaction was continued for 4 hours, the temperature was raised to 200°C, and the reaction was continued. The reaction mixture was stirred for 8 hours; then the temperature was lowered to 145°C, 0.04 mol p-aminophenol, 0.06 mol anhydrous potassium carbonate and 55 mL toluene were added, and the mixture was azeotropically dehydrated for 1 hour; the reflux device was removed, the temperature was raised to 175°C until all toluene in the system was removed, and the temperature was raised to 195°C for reaction for 8 hours; then 110 mL sulfolane was added, and after the system temperature was lowered to 145°C, the polymer solution was poured into hot water containing hydrochloric acid to obtain a crude polymer product; the crude polymer product was boiled with deionized water for 2-3 times to remove inorganic salts and residual solvents, filtered and dried; then the product was dissolved with chloroform, filtered with cotton and diatomaceous earth as filter elements, the filtrate was precipitated into ethanol, filtered and dried to obtain refined PBPENS-DA, the infrared spectrum of which is shown in FIG. Figure 2 As shown in (a), the H NMR spectrum is Figure 2 As shown in (b).

[0070] The preparation method of bis(MA-terminated) diphenyl ether bis(phthalazinone) structure poly(arylether nitrile sulfone) (PBPENS-MI) comprises the following steps: The preparation method of PBPENS-DA is the same as above. In a reactor equipped with a reflux water separation device, a mechanical stirring device, a constant pressure funnel and a nitrogen protection device, 10g of PBPENS-DA, 0.1g of p-toluenesulfonic acid, 75mL of NMP and 50mL of toluene are added. 2.5g of maleic anhydride is dissolved in 25mL of NMP and added dropwise to the reaction system through a constant pressure funnel. Azeotropic dehydration is carried out at 145°C for 3h. The reflux device is removed to remove all toluene in the system and the reaction is continued for 3h. The product is immersed in hot water while hot, filtered and dried. After drying, a bis(hydroxy)-terminated diphenyl ether type bis(phthalazinone) structure poly(arylether nitrile sulfone) (PBPENS-MI) is obtained.

[0071] The preparation method of the poly(phenyl ether nitrile sulfone) (PPENS) resin with a phthalazinone structure is unchanged except that "0.12 mol of diphenyl sulfone phthalazinone structure monomer" is replaced with "0.12 mol of phthalazinone biphenol" in the preparation method of PSUPNS. The infrared spectrum and H NMR spectrum of PPENS are shown as follows: Figure 3 and Figure 4 shown.

[0072] Example 1 This embodiment provides a bis(phthalazinone) structured polymer (diphenyl ether phthalazinone structured poly(arylether nitrile sulfone, PBPENS) toughened bis(maleimide) resin, comprising the following raw materials of the following quality: 6kg of bismaleimide monomer, 4.5kg of allyl compound and 0.26kg of bis(phthalazinone) structured polyarylether resin.

[0073] The bismaleimide monomer is diphenylmethane bismaleimide (BDM), the allyl compound is 2,2'-diallyl bisphenol A (DABPA), and the phthalazinone structure polymer is diphenyl ether phthalazinone structure polyarylether nitrile sulfone (PBPENS).

[0074] The preparation method of the bis(phthalazinone) structure polymer toughened bis(maleimide) resin of this embodiment comprises the following steps: (a) 4.5 kg of an allyl compound (DABPA) was added to a mixer, heated and stirred until melted, and when the temperature reached 125° C., 0.26 kg of diphenyl ether bis(phthalazinone) structured poly(arylether nitrile sulfone) (PBPENS) was added, and stirring was continued until PBPENS was completely dissolved in the allyl compound (DABPA) to obtain a dissolved phase; (b) Then, 6 kg of diphenylmethane bismaleimide (BDM) was added to the dissolved phase and the mixture was stirred for about 30 minutes. The mixture was vacuum degassed at 110° C. until no bubbles were emitted, thereby obtaining a diphenyl ether bis(phthalazinone) structured poly(arylether nitrile sulfone) toughened bismaleimide resin.

[0075] Example 2 This embodiment provides a diphenyl phthalazinone structure polymer (diphenyl sulfone diphenyl phthalazinone structure polyaromatic nitrile sulfone, PSUPNS) toughened bismaleimide resin and a preparation method thereof, except that the specific type of the diphenyl phthalazinone structure polymer is replaced by diphenyl ether diphenyl phthalazinone structure polyaromatic ether nitrile sulfone to diphenyl sulfone diphenyl phthalazinone structure polyaromatic nitrile sulfone, and the remaining raw materials, amounts and preparation methods are the same as those in Example 1.

[0076] Example 3 This embodiment provides a bis(phthalazinone) structured polymer (diphenyl ether phthalazinone structured poly(arylether nitrile sulfone, PBPENS) toughened bis(maleimide) resin, comprising the following raw materials of the following quality: 10 kg of bismaleimide monomer, 6.45 kg of allyl compound and 0.41 kg of bis(phthalazinone) structure polymer.

[0077] The bismaleimide monomer is diphenylmethane bismaleimide (BDM), the allyl compound is 3,3'-diallylbiphenylphenol (DABP), and the phthalazinone structure polymer is diphenyl ether phthalazinone structure polyarylether nitrile sulfone (PBPENS).

[0078] The preparation method of the bis(phthalazinone) structure polymer toughened bis(maleimide) resin of this embodiment comprises the following steps: (a) 6.45 kg of allyl compound (DABP) was added to a mixer, heated and stirred until melted, and when the temperature reached 125° C., 0.41 kg of diphenyl ether bis(phthalazinone) structured poly(arylether nitrile sulfone) (PBPENS) was added, and stirring was continued until PBPENS was completely dissolved in the allyl compound (DABP) to obtain a dissolved phase; (b) Then, 10 kg of diphenylmethane bismaleimide (BDM) was added to the dissolved phase and stirred for about 30 minutes to obtain a uniform liquid with a certain viscosity. The liquid was vacuum degassed at 110° C. until no bubbles emerged to obtain a diphenyl ether bis(phthalazinone) structured poly(arylether nitrile sulfone) toughened bismaleimide resin.

[0079] Example 4 The present embodiment provides a bis(phthalazinone) structural polymer (diphenyl sulfone phthalazinone structured polyaryl sulfone, PSUPS) toughened bis(malonate) resin and a preparation method thereof, except that the specific type of the phthalazinone structural polymer in Example 1 is replaced by diphenyl ether phthalazinone structured polyaryl ether nitrile sulfone with diphenyl sulfone phthalazinone structured polyaryl sulfone, and the remaining raw materials, amounts and preparation methods are the same as those in Example 1.

[0080] Example 5 This embodiment provides a bis(phthalazinone) structured polymer (diphenylsulfone bis(phthalazinone) structured polyaromatic nitrile sulfone, PSUPNS) toughened bis(malonium) resin, comprising the following raw materials of the following quality: 6kg of bismaleimide monomer, 4.5kg of allyl compound, 0.26kg of bis(phthalazinone) structural polymer and 0.13kg of curing agent.

[0081] The bismaleimide monomer is diphenylmethane bismaleimide (BDM), the allyl compound is 2,2'-diallyl bisphenol A (DABPA), the phthalazinone structure polymer is diphenyl sulfone phthalazinone structure polyaromatic nitrile sulfone (PSUPNS), and the curing agent is 2-aminophenylacetylene.

[0082] The preparation method of the bis(phthalazinone) structure polymer toughened bis(maleimide) resin of this embodiment comprises the following steps: (a) 4.5 kg of an allyl compound (DABPA) was added to a mixer, heated and stirred until it was melted, and when the temperature reached 125° C., 0.26 kg of diphenyl sulfone phthalazinone structured polyaromatic nitrile sulfone (PSUPNS) was added, and stirring was continued until it was completely dissolved in the allyl compound (DABPA) to obtain a dissolved phase; (b) Then, 6 kg of diphenylmethane bismaleimide (BDM) and 0.13 kg of curing agent 2-aminophenylacetylene were added to the dissolved phase and stirred for about 30 minutes to obtain a uniform amber liquid with a certain viscosity. The mixture was vacuum degassed at 110° C. until no bubbles emerged to obtain a diphenyl sulfone bis(phthalazinone) structured polyaromatic nitrile sulfone toughened bismaleimide resin.

[0083] Example 6 The present embodiment provides a bis(phthalazinone) structural polymer (diphenyl sulfone bis(phthalazinone) structural copolymerized biphenyl phenol type polyarylether sulfone, PSUBPS) toughened bismaleimide resin and a preparation method thereof, except that the specific type of the bis(phthalazinone) structural polymer in Example 1 is replaced by diphenyl ether bis(phthalazinone) structural polyarylether nitrile sulfone with diphenyl sulfone bis(phthalazinone) structural copolymerized biphenyl phenol type polyarylether sulfone, and the remaining raw materials, amounts and preparation methods are the same as those in Example 1.

[0084] Example 7 The present embodiment provides a bis(phthalazinone) structural polymer (amino-terminated diphenyl sulfone bis(phthalazinone) structural poly(arylether nitrile sulfone, PBPENS-DA) toughened bis(maleimide) resin and a preparation method thereof, except that the specific type of the bis(phthalazinone) structural polymer in Example 1 is replaced by diphenyl ether bis(phthalazinone) structural poly(arylether nitrile sulfone) with amino-terminated diphenyl sulfone bis(phthalazinone) structural poly(arylether nitrile sulfone), the remaining raw materials, amounts and preparation methods are the same as those in Example 1.

[0085] Example 8 The present embodiment provides a bis(phthalazinone) structural polymer (bis(maleic acid-terminated diphenyl ether phthalazinone) structured poly(arylether nitrile sulfone, PBPENS-MI) toughened bis(maleic acid) resin and a preparation method thereof, except that the specific type of the bis(phthalazinone) structural polymer in Example 1 is replaced by diphenyl ether phthalazinone structured poly(arylether nitrile sulfone) with bis(maleic acid-terminated diphenyl ether phthalazinone) structured poly(arylether nitrile sulfone), and the remaining raw materials, amounts and preparation methods are the same as those in Example 1.

[0086] Example 9 This embodiment provides a bis(phthalazinone) structured polymer (diphenylsulfone bis(phthalazinone) structured polyaromatic nitrile sulfone, PSUPNS) toughened bis(malonium) resin, comprising the following raw materials of the following quality: 6 kg of bismaleimide monomer, 3.87 kg of allyl compound, 0.26 kg of bis(phthalazinone) structural polymer and 3 kg of co-curing component.

[0087] The bismaleimide monomer is diphenylmethane bismaleimide (BDM), the allyl compound is 3,3'-diallylbiphenylphenol (DABP), the phthalazinone structure polymer is diphenyl sulfone phthalazinone structure polyaromatic nitrile sulfone (PSUPNS), and the co-curing component is benzoxazine (BOZ).

[0088] The preparation method of the bis(phthalazinone) structure polymer toughened bis(maleimide) resin of this embodiment comprises the following steps: (a) 3.87 kg of allyl compound (DABP) was added to a mixer, heated and stirred until melted, and when the temperature reached 125°C, 0.26 kg of diphenyl sulfone phthalazinone structure polyaromatic nitrile sulfone (PSUPNS) was added, and stirring was continued until PSUPNS was completely dissolved in the allyl compound (DABP) to obtain a dissolved phase; (b) Then, 6 kg of diphenylmethane bismaleimide (BDM) and 3 kg of co-curing component benzoxazine (BOZ) were added to the dissolved phase and stirred for about 30 minutes to obtain a uniform amber liquid with a certain viscosity. The mixture was vacuum degassed at 110°C until no bubbles emerged to obtain a diphenyl sulfone bis(phthalazinone) structured polyaromatic nitrile sulfone toughened benzoxazine copolymer bismaleimide resin.

[0089] Comparative Example 1 This comparative example provides a phthalazinone structured polymer (phthalazinone polyarylether nitrile sulfone, PPENS) toughened bismaleimide resin, including the following raw materials of the following quality: 10 kg of bismaleimide monomer, 6.45 kg of allyl compound and 0.41 kg of phthalazinone structure polymer.

[0090] The bismaleimide monomer is diphenylmethane bismaleimide (BDM), the allyl compound is 3,3'-diallylbiphenylphenol (DABP), and the phthalazinone structure polymer is phthalazinone structure polyarylethernitrilesulfone (PPENS).

[0091] This comparative example provides a method for preparing a phthalazinone polyarylether nitrile sulfone (PPENS) toughened bismaleimide resin, comprising the following steps: (a) Add 6.45 kg of allyl compound (DABP) into a mixer, heat and stir until it is melted, and when the temperature rises to 125° C., add 0.41 kg of diazolinone structure polymer (PPENS), and continue stirring until it is completely dissolved in the allyl compound (DABP) to obtain a dissolved phase; (b) Then, 10 kg of diphenylmethane bismaleimide (BDM) was added to the dissolved phase and stirred for about 30 minutes to obtain a uniform liquid with a certain viscosity. The solution was vacuum degassed at 110° C. until no bubbles emerged to obtain diazonium phthalide poly (arylether nitrile sulfone) (PPENS) toughened bismaleimide resin.

[0092] Comparative Example 2 This comparative example provides a bismaleimide resin, except that the bis(phthalazinone) structure polymer is not added to the raw materials, and the amounts of other raw materials are the same as those in Example 3.

[0093] The preparation method of the bismaleimide resin of this comparative example comprises the following steps: Add 6.45 kg of allyl compound (DABP) into the mixer, heat and stir until melted, and when the temperature rises to 125°C, add 10 kg of diphenylmethane bismaleimide (BDM), and continue stirring for about 30 minutes to obtain a uniform liquid with a certain viscosity. Vacuum degassing is performed at 110°C until no bubbles emerge to obtain bismaleimide resin.

[0094] In order to compare the technical effects of the embodiments and comparative examples, the following experimental examples are specially set up.

[0095] Experimental Example 1 The bismaleimide resin toughened with the phthalazinone structure polymer provided in each embodiment and the bismaleimide resin toughened with the phthalazinone structure polymer or the bismaleimide resin provided in the comparative example were made into cast solids according to standard GB / T 2567-2021, and their unnotched impact strength was tested. The specific results are shown in Table 2.

[0096] At the same time, the bismaleimide resin toughened by the bis(phthalazinone) structure polymer provided in each embodiment and the bismaleimide resin toughened by the bis(phthalazinone) structure polymer provided in the comparative example are used as the matrix resin, T800H carbon fiber is used as the reinforcing fiber, and the prepreg is prepared by hot melt method, and then the continuous carbon fiber reinforced bismaleimide resin-based composite material is prepared by vacuum hot pressing of the prepreg, and the volume content of the carbon fiber is 63%. Then, the post-impact compressive strength is tested according to the ASTM D7137 / D7137M test standard, and the specific results are shown in Table 2.

[0097] Table 2 It can be seen from the data in Table 2 that the unnotched impact strength of the cast body solidified product and the post-impact compressive strength of the composite material made by toughening the bismaleimide resin with the diphenylphthalazinone structure polymer of the present invention are greatly improved. By comparing Example 3 with Comparative Example 2, it can be seen that after adding the diphenylphthalazinone structure polymer, the unnotched impact strength of the cast body solidified product and the post-impact compressive strength of the composite material are significantly improved.

[0098] Experimental Example 2 The heat resistance of the bis(phthalazinone) structure polymer toughened bis(maleimide) resin provided in each embodiment and the bis(phthalazinone) structure polymer toughened bis(maleimide) resin or bis(maleimide) resin provided in the comparative example was tested, and the specific results are shown in Table 3. Among them, the glass transition temperature T g The test method is based on GB / T 19466.2-2004 "Plastics Differential Scanning Calorimetry (DSC) Part 2: Determination of Glass Transition Temperature".

[0099] Table 3 It can be seen from the data in Table 3 that the present invention introduces the bis(phthalazinone) structure polymer into the high temperature resistant bismaleimide resin to maintain the excellent heat resistance of the bismaleimide resin.

[0100] 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 bis(phthalazinone) structural polymer toughened bis(maleic acid) resin, characterized in that: Including the following raw materials in parts by weight: 100 parts of bismaleimide monomer, 5-90 parts of allyl compound, 1-30 parts of phthalazinone structure polymer, 0-30 parts of other thermoplastic resin toughening agent, 0-50 parts of co-curing component and 0-5 parts of curing agent; The phthalazinone structure polymer includes one or a combination of a polymer having a structure represented by the following formula (1), a polymer having a structure represented by the following formula (2), or a polymer having a structure represented by the following formula (3): （1）； （2）； （3）； In formula (1), formula (2) and formula (3), the structure of —Ar1— is one or more of the following structures: ； ； ； ； ； ； ； ； ； ； ； 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 following; In formula (1), formula (2) and formula (3), 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), formula (2) and formula (3), 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; ； ； ； ； ； ； ； ； ； ； ； ； ； ； Wherein, "X3" 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 .

2. The bis(phthalazinone) structural polymer toughened bismaleimide resin according to claim 1, characterized in that: The bismaleimide monomer includes one or more of the following structures: ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; , wherein R5, R6, R7 and R8 are independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group or an alkoxy group, and the structures of R5, R6, R7 and R8 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.

3. The bis(phthalazinone) structural polymer toughened bismaleimide resin according to claim 1, characterized in that: The allyl compound includes one or more of the following structures: ； ； ； ； ； ； ； ； ； ； ； ； 。 4. The bis(phthalazinone) structural polymer toughened bismaleimide resin according to claim 1, characterized in that: The other thermoplastic resin toughening agent includes one or a combination of two or more of polyaryletherketone, polyethersulfone, polyarylethersulfone, thermoplastic polyimide or polyetherimide; and / or, the co-curing component comprises one or a combination of two or more of a cyanate resin, an allylphenoloxy resin, an epoxy resin or a benzoxazine resin; And / or, the curing agent includes one or a combination of two or more of aminophenylacetylene, imidazole curing agents or aromatic amine curing agents.

5. A method for preparing the toughened bismaleimide resin of the phthalazinone structure polymer according to any one of claims 1 to 4, characterized in that: The following steps are involved: (a) heating an allyl compound until it is melted, adding a phthalazinone structural polymer, and optionally a co-curing component and optionally other thermoplastic resin toughening agents, and stirring until they are completely dissolved in the allyl compound to obtain a dissolved phase; (b) then adding bismaleimide monomer and optional curing agent into the dissolved phase, heating and stirring to perform blending or prepolymerization, and obtaining a bismaleimide resin toughened with a phthalazinone structured polymer.

6. The method according to claim 5, characterized in that In step (a), the heating temperature is 30-160°C; And / or, in step (b), the heating and stirring temperature is 100-140° C., and the time is 0.1-3 h.

7. Use of the bis(phthalazinone) structured polymer toughened bismaleimide resin according to any one of claims 1 to 4 in prepreg, characterized in that: The bis(phthalazinone) structural polymer toughened bismaleimide resin is used as a resin matrix in the prepreg.

8. The use according to claim 7, characterized in that: The reinforcement in the prepreg comprises one or a combination of two or more of continuous carbon fiber, continuous glass fiber, continuous quartz fiber, continuous basalt fiber, continuous aramid fiber, continuous polybenzimidazole fiber and continuous polybenzoxazole fiber; And / or, the resin glue mass content of the prepreg is 30-50%.

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