Phthalazinone Structure Polymer Toughened Bismaleimide Resin, Preparation Method and Application

Abstract

The present invention provides a phthalazinone - structured polymer - toughened bismaleimide resin, a preparation method thereof and an application thereof, which relate to the technical field of synthesis of polymer materials. The phthalazinone - structured polymer - toughened bismaleimide resin is mainly prepared from bismaleimide monomers, allyl compounds, phthalazinone - structured polymers, and optionally other thermoplastic resin toughening agents, optionally co - curing components and optionally curing agents. Among them, the phthalazinone - structured polymer has excellent heat - resistant performance and good solubility, and its heat resistance matches that of high - temperature - resistant bismaleimide resins. It can be used as a toughening agent to significantly improve the impact toughness of bismaleimide resins and their composites, and maintain the excellent heat - resistant performance of bismaleimide resins, so that bismaleimide resins can be applicable to more application scenarios.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer material synthesis, and relates to a toughened bismaleimide resin with a phthalazinone structure polymer, a preparation method and an application thereof. Background Art

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

[0003] At present, the main methods for toughening modification of bismaleimide resin 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. The heat resistance grades of liquid rubber and thermotropic liquid crystal polymers are insufficient and it is difficult to match the heat resistance of bismaleimide resin. Nano-components are prone to agglomeration, with poor processing performance and high cost. High-performance thermoplastic resins have both a high heat resistance temperature matching that of bismaleimide resin and good processing performance, and are an important and effective toughening modifier for bismaleimide resin.

[0004] Polyarylether thermoplastic resins containing a phthalazinone biphenyl structure are a class of high-performance thermoplastic resins independently developed by Dalian University of Technology. For example, polyaryletherketones containing a phthalazinone biphenyl structure (glass transition temperature T g : 263 °C), polyarylethersulfones ( T g : 305 °C), polyarylethernitrileketones ( T g : 268 - 289 °C, Wang Mingjing, Ph.D. thesis of Dalian University of Technology, 2007; Chinese invention patent ZL03111540.3) resins have excellent comprehensive properties, especially outstanding high-temperature mechanical properties. Their glass transition temperatures can be adjusted between 230 and 305 °C, and they have good solubility, can be dissolved in a few polar aprotic organic solvents, and can also be dissolved in epoxy resin and bismaleimide resin systems, and are used for toughening modification of epoxy resin, bismaleimide resin and their composites.

[0005] With the rapid development of fields such as aerospace, electronics and electrical engineering, higher requirements are put forward for the heat resistance of bismaleimide resins and their composites. The heat resistance of traditional high-performance thermoplastic resin tougheners can no longer match that of high-temperature bismaleimide resins. Therefore, developing new high-temperature thermoplastic resin tougheners to meet the heat resistance, toughness and processing performance requirements of bismaleimide resins, their resin matrix composites and structural adhesives has important practical application value. In view of this, the present invention is specifically proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a phthalazinone-structured polymer toughened bismaleimide resin, its preparation method and application to solve the above technical problems.

[0007] In order to achieve the above purpose, the following technical solutions are adopted:

[0008] The first purpose of the present invention is to provide a phthalazinone-structured polymer toughened bismaleimide resin, which comprises the following raw materials in parts by mass:

[0009] 100 parts of bismaleimide monomer, 5 - 90 parts of allyl compound, 1 - 30 parts of phthalazinone-structured polymer, 0 - 30 parts of other thermoplastic resin tougheners, 0 - 50 parts of co-curing component and 0 - 5 parts of curing agent.

[0010] Further, on the basis of the above technical solution of the present invention, the phthalazinone-structured polymer includes one or a combination of several of the polymers with the structures shown in the following formula (1), formula (2) or formula (3):

[0011] (1);

[0012] (2);

[0013] (3);

[0014] In formula (1), formula (2) and formula (3), the structure of —Ar 1 — is one or several of the following structures:

[0015] ; ; ; ; ; ; ; ; ; ; ;

[0016] Among them, “X” 1 is one or more of the following structures:

[0017] ; ; ; ; ;

[0018] , 2, 2-position, 2, 3-position or 3, 3-position;

[0019] , 2, 2-position, 2, 3-position or 3, 3-position;

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

[0021] , 2, 2-position, 2, 3-position or 3, 3-position;

[0022] , 2, 2-position, 2, 3-position or 3, 3-position;

[0023] is 、 one or more of;

[0024] In formulas (1), (2) and (3), —Ar 2 — has a structure that is one or more of the following structures:

[0025] ; ; ; ; , 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;

[0026] In formulas (1), (2) and (3), has a structure that is one or more of the following structures:

[0027] , 1, 2-position, 1, 3-position or 1, 4-position;

[0028] , 2, 2′-position or 4, 4′-position;

[0029] , 1, 4-position, 1, 5-position, 1, 6-position, 2, 6-position or 2, 7-position;

[0030] at the 3, 3′-position or 4, 4′-position;

[0031] at the 3, 3′-position or 4, 4′-position;

[0032] at the 3, 3′-position or 4, 4′-position;

[0033] at the 3, 3′-position or 4, 4′-position;

[0034] at the 3, 3′-position or 4, 4′-position;

[0035] , R 1 , R 2 , R 3 , R 4 each independently selected from hydrogen, a halogen substituent, phenyl, phenoxy, alkyl or alkoxy, and R 1 , R 2 , R 3 and R 4 have the same or different structures, where the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing at least 1 carbon atom;

[0036] ; ; ; ; ; ; ; ; ; ; ; ; ; ;

[0037] wherein, is one or more of the following structures:

[0038] ; ; ; ; ; ;

[0039] at the 2, 2-position, 2, 3-position or 3, 3-position;

[0040] at the 2, 2-position, 2, 3-position or 3, 3-position;

[0041] , 2, 2-position, 2, 3-position or 3, 3-position;

[0042] , 2, 2-position, 2, 3-position or 3, 3-position;

[0043] , 2, 2-position, 2, 3-position or 3, 3-position;

[0044] is 、 one or more of the following.

[0045] Further, based on the above technical solution of the present invention, the bismaleimide monomer includes one or more of the following structures:

[0046] ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;

[0047] ; ;

[0048] ; ;

[0049] , in the structural formula, R 5 、R 6 、R 7 、R 8 are each independently selected from hydrogen, halogen substituents, phenyl, phenoxy, alkyl or alkoxy, and the structures of R 5 、R 6 、R 7 and R 8 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.

[0050] Further, based on the above technical solution of the present invention, the allyl compound includes one or more of the following structures:

[0051] ; ; ; ; ; ; ; ; ; ; ; ; .

[0052] Further, based on 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;

[0053] And / or, the co-curing component includes one or a combination of two or more of cyanate resin, allylphenoloxy resin, epoxy resin or benzoxazine resin;

[0054] And / or, the curing agent includes one or a combination of two or more of aminophenylacetylene, imidazole curing agent or aromatic amine curing agent.

[0055] The second object of the present invention is to provide a method for preparing the above-mentioned bisphthalazinone structure polymer toughened bismaleimide resin, comprising the following steps:

[0056] (a) Heating the allyl compound to melting, adding the bisphthalazinone structure polymer, and optionally the co-curing component and optionally the other thermoplastic resin toughening agent, and stirring until it is completely dissolved in the allyl compound to obtain a dissolved phase;

[0057] (b) Then adding the bismaleimide monomer and optionally the curing agent to the dissolved phase, and heating and stirring for blending or prepolymerization to obtain the bisphthalazinone structure polymer toughened bismaleimide resin.

[0058] Further, based on the above technical solution of the present invention, in step (a), the heating temperature is 30-160 °C;

[0059] And / or, in step (b), the heating and stirring temperature is 100-140 °C, and the time is 0.1-3 h.

[0060] The third object of the present invention is to provide an application of the above-mentioned bisphthalazinone structure polymer toughened bismaleimide resin of the present invention in a prepreg, and the bisphthalazinone structure polymer toughened bismaleimide resin is used as a resin matrix in the prepreg.

[0061] Further, based on the above technical solution of the present invention, the reinforcing body 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;

[0062] and / or, the resin sizing mass content of the prepreg is 30-50%.

[0063] Compared with the prior art, the technical solution of the present invention has at least the following technical effects:

[0064] (1) The present invention provides a phthalazinone-based polymer toughened bismaleimide resin, which is mainly made of bismaleimide monomer, allyl compound, phthalazinone-based polymer, and optionally other thermoplastic resin tougheners, optionally co-curing components, and optionally curing agents. Among them, the phthalazinone-based polymer has excellent heat resistance and good solubility, and its heat resistance matches that of the high-temperature-resistant bismaleimide resin. Therefore, it can be used as a toughener to significantly improve the impact toughness of the bismaleimide resin and its composites, and maintain the excellent heat resistance of the bismaleimide resin, so that the bismaleimide resin can be applied to more application scenarios.

[0065] (2) The present invention also provides a preparation method of the phthalazinone-based polymer toughened bismaleimide resin. The preparation method has a simple process and stable process, and can realize the stable preparation of the phthalazinone-based polymer toughened bismaleimide resin. Description of the Drawings

[0066] Figure 1 It is the infrared spectrum of PSUPS and PSUPNS in the present invention;

[0067] Figure 2 It is the infrared spectrum (a) of PBPENS and PBPENS-DA and the nuclear magnetic resonance hydrogen spectrum (b) of PBPENS and PBPENS-DA in the present invention;

[0068] Figure 3 It is the infrared spectrum of PPENS in the present invention;

[0069] Figure 4 It is the nuclear magnetic resonance hydrogen spectrum of PPENS in the present invention. Detailed Embodiments

[0070] To make the objectives, technical solutions and advantages of the present invention clearer, the following will, in conjunction with the embodiments of the present invention, clearly and completely describe the technical solutions in 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.

[0071] In the present invention, the endpoints and any values within the disclosed ranges are not limited to the exact ranges or values. 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. Additionally, "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.

[0072] According to the first aspect of the present invention, there is provided a bisphthalazinone - structured polymer - toughened bismaleimide resin, comprising the following raw materials in parts by mass:

[0073] 100 parts of bismaleimide monomer, 5 - 90 parts of allyl compound, 1 - 30 parts of bisphthalazinone - structured polymer, 0 - 30 parts of other thermoplastic resin toughening agent, 0 - 50 parts of co - curing component, and 0 - 5 parts of curing agent.

[0074] The bismaleimide monomer can adopt common bismaleimides in the art, which is not limited herein.

[0075] The introduction of the bisphthalazinone structure in the bisphthalazinone - structured polymer endows it with excellent heat - resistant performance and good solubility. Its heat resistance matches that of high - temperature bismaleimide resin. Therefore, it can be used as a toughening agent to significantly improve the impact toughness of bismaleimide resin and its composites, and maintain the excellent heat - resistant performance of bismaleimide resin. The dosage of the bisphthalazinone - structured polymer also affects the impact toughness and processing performance of bismaleimide resin and its composites. If its dosage is too low (less than 1 part), it is likely to result in an insignificant improvement in the impact toughness of bismaleimide resin. If its dosage is too high (more than 30 parts), it is likely to cause too high a viscosity of the bismaleimide blend resin system and poor processing performance. Therefore, the typical but non - restrictive parts by mass of the bisphthalazinone - structured polymer are 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, etc., and the numerical ranges between any two points.

[0076] The allyl compound acts as both a toughening agent and a curing agent in the co-curing system, and also acts as a solvent for dissolving the bismaleimide resin and the thermoplastic resin toughening agent, improving the processing performance of the bismaleimide resin matrix. The typical but non-limiting mass fraction of the allyl compound is 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts or 90 parts, etc., and the numerical range between any two points.

[0077] In addition to adding the above-mentioned phthalazinone structure polymer and allyl compound, other thermoplastic resin toughening agents, co-curing components and curing agents can be selectively added as needed.

[0078] Other thermoplastic resin toughening agents are mainly used for co-toughening, and high-performance thermoplastic resins common in the art can be selected, such as polyester (PET), polyethersulfone (PES), polyaryletherketone (PAEK), polyimide (PI), polyetherketone (PEK), etc. The typical but non-limiting mass fraction of other thermoplastic resin toughening agents is 0 part, 1 part, 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.

[0079] 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. The typical but non-limiting mass fraction of the co-curing component is 0 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts, etc., and the numerical range between any two points.

[0080] The curing agent is mainly used for crosslinking and curing of the bismaleimide and the co-curing component. The typical but non-limiting mass fraction of the curing agent is 0 part, 1 part, 2 parts, 3 parts, 4 parts or 5 parts, etc., and the numerical range between any two points.

[0081] As an optional implementation mode of the technical solution of the present invention, the phthalazinone structure polymer includes one or a combination of several of the polymers having the structure shown in the following formula (1), the polymer having the structure shown in formula (2) or the polymer having the structure shown in formula (3):

[0082] (1);

[0083] (2);

[0084] (3);

[0085] In formula (1), formula (2) and formula (3), The structure adopts a bridging structure containing a flexible group, a polar group or a ladder heterocycle, which is beneficial to adjusting the heat resistance of the phthalazinone structure polymer. The structure is specifically one or more of the following structures:

[0086] ; ; ; ; ; ; ; ; ; ; ;

[0087] Among them, is one or more of the following structures:

[0088] ; ; ; ; ;

[0089] , 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, and is an isomer generated by the reaction of the thiophene compound. There are 3 structures, and these three structures can also be separated, polymerized separately, or directly polymerized. The following structures are all in this case and will not be elaborated later;

[0090] , at the 2, 2 position, 2, 3 position or 3, 3 position;

[0091] , at the 2, 2 position, 2, 3 position or 3, 3 position;

[0092] , at the 2, 2 position, 2, 3 position or 3, 3 position;

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

[0094] is 、 one or more of;

[0095] In formulas (1), (2) and (3), —Ar 2 — has a structure that is one or more of the following structures:

[0096] ; ; ; ; , 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;

[0097] In formula (1), formula (2) and formula (3), The structure of is one or more of the following structures:

[0098] , at the 1, 2-position, 1, 3-position or 1, 4-position; wherein, the 1, 2-position, 1, 3-position, 1, 4-position are the connection positions of oxygen on 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 generating the 1, 2-position, 1, 3-position or 1, 4-position, and the subsequent structures are similar and will not be elaborated;

[0099] , at the 2, 2'-position or 4, 4'-position;

[0100] , at the 1, 4-position, 1, 5-position, 1, 6-position, 2, 6-position or 2, 7-position;

[0101] , at the 3, 3'-position or 4, 4'-position;

[0102] , at the 3, 3'-position or 4, 4'-position;

[0103] , at the 3, 3'-position or 4, 4'-position;

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

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

[0106] , R 1 、R 2 、R 3 、R 4 are each independently selected from hydrogen, halogen substituents, phenyl, phenoxy, alkyl or alkoxy, and the structures of R 1 、R 2 、R 3 and R 4 are the same or different, wherein the alkyl or alkoxy is a straight-chain or branched alkyl or alkoxy containing at least 1 carbon atom;

[0107] ; ; ;

[0108] ; ; ; ; ; ; ; ; ; ; ;

[0109] Among them, is one or more of the following structures:

[0110] ; ; ; ; ; ;

[0111] , 2, 2-position, 2, 3-position or 3, 3-position;

[0112] , 2, 2-position, 2, 3-position or 3, 3-position;

[0113] , 2, 2-position, 2, 3-position or 3, 3-position;

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

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

[0116] is 、 one or more of.

[0117] It should be noted that in the structural formulas (1), (2) and (3) of the quinazoline dione structure polymer of the present invention, only the repeating unit structures contained are shown, and the molecular weight or degree of polymerization is not limited. As a toughening agent for high-temperature thermoplastic resins, the quinazoline dione structure polymer can be selected according to different application requirements of the bismaleimide resin (such as different uses in resin matrix composites, coatings, adhesives, functional films, etc.). The molecular weight of the quinazoline dione structure polymer can be adjusted according to the molar ratio of the polymerization monomers.

[0118] The present invention provides a toughened bismaleimide resin with both excellent heat resistance and good impact toughness, mainly by introducing a bisphthalazinone - structured polymer as a toughening agent to improve the impact toughness of the bismaleimide resin without reducing its heat - resistant performance. Its notched - impact strength can reach up to 28.8 kJ / m 2 ; Further, other thermoplastic resin toughening agents can be appropriately added to toughen the bismaleimide resin and its composites together. The processing performance of the bismaleimide resin system can also be flexibly regulated by adding other thermoplastic resin toughening agents, co - curing components, and / or curing agents, and the heat - resistant performance, mechanical properties, and dielectric properties of its cured products and composites can be adjusted, enabling it to meet the requirements of more different application scenarios.

[0119] As an optional implementation mode of the technical solution of the present invention, the preparation method of the bisphthalazinone - structured polymer with the structure shown in formula (1) includes the following steps:

[0120] Mix the bisphthalazinone - structured monomer - containing, aromatic dihalide monomer, and optionally other bisphenol or bisphenol - like monomers as polycondensation monomers, mix them with a solvent, azeotropic water - carrying agent, and a catalyst, carry out a copolymerization reaction under a protective gas atmosphere, settle the reaction solution obtained after the reaction in a precipitant, and wash, filter, and dry the precipitated solid product to obtain the bisphthalazinone - structured polymer.

[0121] As an optional implementation mode of the technical solution of the present invention, the preparation method of the (amino - terminated) bisphthalazinone - structured polymer with the structure shown in formula (2) includes the following steps:

[0122] Mix the bisphthalazinone - structured monomer - containing, aromatic dihalide monomer, optionally other bisphenol or bisphenol - like monomers, and p - aminophenol as polycondensation monomers, mix them with a solvent, azeotropic water - carrying agent, and a catalyst, carry out a copolymerization reaction under a protective gas atmosphere, settle the reaction solution obtained after the reaction in a precipitant, and wash, filter, and dry the precipitated solid product to obtain the amino - terminated bisphthalazinone - structured polymer with the structure shown in formula (2).

[0123] As an optional implementation mode of the technical solution of the present invention, the preparation method of the (maleimide - terminated) bisphthalazinone - structured polymer with the structure shown in formula (3) includes the following steps:

[0124] Mix monomers containing phthalazinone structure monomers, aromatic dihalogen monomers, optional other bisphenol or bisphenol-like monomers, and p-aminophenol as polycondensation monomers, mix with solvents, azeotropic water-carrying agents and catalysts, and carry out copolymerization reaction under a protective gas atmosphere. Settle the reaction solution obtained after the reaction in a precipitant, and wash, filter and dry the precipitated solid product to obtain an amino-terminated phthalazinone structure polymer with the structure shown in formula (2);

[0125] Use the amino-terminated phthalazinone structure polymer with the structure shown in formula (2) and maleic anhydride as reaction monomers, mix with solvents, azeotropic water-carrying agents, catalysts and p-toluenesulfonic acid, and carry out end-capping reaction under a protective gas atmosphere. Settle the reaction solution obtained after the reaction in a precipitant, and wash, filter and dry the precipitated solid product to obtain a maleimide-terminated phthalazinone structure polymer with the structure shown in formula (3).

[0126] As an optional implementation mode of the technical solution of the present invention, the monomers containing phthalazinone structure monomers correspond to the following structures, and are one or more of the following structures:

[0127] ; ; ; ; ;

[0128] ; ; ; ; ; ;

[0129] Among them, is one or more of the following structures:

[0130] ; ; ; ; ;

[0131] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0132] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0133] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0134] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0135] ,2, 2 - position, 2, 3 - position or 3, 3 - position;

[0136] is 、 one or more of the following.

[0137] As an optional embodiment of the technical solution of the present invention, the aromatic dihalo monomer, i.e., corresponding to —Ar 2 —, has one or more of the following structures:

[0138] ; ; ; ; , 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 a halogen, including F or Cl.

[0139] As an optional embodiment of the technical solution of the present invention, other bisphenol or bisphenol - like monomers, i.e., corresponding to the structure, has one or more of the following structures:

[0140] , 1, 2 - position, 1, 3 - position or 1, 4 - position;

[0141] , 2, 2′ - position or 4, 4′ - position;

[0142] , 1, 4 - position, 1, 5 - position, 1, 6 - position, 2, 6 - position or 2, 7 - position;

[0143] , 3, 3′ - position or 4, 4′ - position;

[0144] , 3, 3′ - position or 4, 4′ - position;

[0145] , 3, 3′ - position or 4, 4′ - position;

[0146] , 3, 3′ - position or 4, 4′ - position;

[0147] , 3, 3′ - position or 4, 4′ - position;

[0148] , R 1 、R 2 、R 3 、R4 Each independently selected from hydrogen, a halogen substituent, phenyl, phenoxy, alkyl or alkoxy, R 1 , R 2 , R 3 and R 4 have the same or different structures, wherein the alkyl or alkoxy is a straight-chain or branched-chain alkyl or alkoxy containing at least 1 carbon atom;

[0149] ; ; ;

[0150] ; ; ; ; ; ; ; ; ; ; ;

[0151] wherein, is one or more of the following structures:

[0152] ; ; ; ; ; ;

[0153] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0154] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0155] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0156] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0157] , at the 2, 2-position, 2, 3-position or 3, 3-position;

[0158] is , one or more of.

[0159] As an optional implementation mode 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.

[0160] As an optional implementation mode 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.

[0161] As an optional implementation mode 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.

[0162] As a preferred implementation mode 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.

[0163] As an optional implementation mode 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.

[0164] As an optional implementation mode 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 monomers containing the phthalazinone structure, other bisphenol monomers and bisphenol-like monomers in the reaction feedstock.

[0165] As an optional implementation mode of the technical solution of the present invention, the mass of the solvent is 0.2-50 times (such as 0.2 times, 1 time, 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, etc.) the total mass of the phthalazinone-based monomers, other bisphenol monomers, bisphenol-like monomers and aromatic dihalogen monomers in the reaction feedstock.

[0166] 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.

[0167] As an alternative embodiment of the technical solution of the present invention, the temperature of the polymerization reaction is 80 to 300 °C (such as 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 to 60 h (such as 4 h, 10 h, 12 h, 20 h, 24 h, 30 h, 36 h, 40 h, 48 h, 50 h, 55 h or 60 h, etc.).

[0168] 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.

[0169] As an alternative embodiment of the technical solution of the present invention, the bismaleimide includes one or several of the following structures:

[0170] ; ; ; ; ; ; ; ; ; ; ; , ; ; ; ; ; ; ; ; ;

[0171] ; ;

[0172] ; ;

[0173] , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen, a halogen substituent, a phenyl group, a phenoxy group, an alkyl group or an alkoxy group, and R 5, R 6 , R 7 and R 8 have the same or different structures, wherein the alkyl or alkoxy group is a straight-chain or branched alkyl or alkoxy group containing at least 1 carbon atom.

[0174] As an alternative embodiment of the technical solution of the present invention, the allyl compound includes one or more of the following structures:

[0175] ; ; ; ; ; ; , where n is the number of repeating units, and there is no limit on the value range of n. Polymers with different numbers of repeating units can be selected according to actual needs;

[0176] , where m is the number of repeating units, and there is no limit on the value range of m. Polymers with different numbers of repeating units can be selected according to actual needs; ; ; ; ; .

[0177] As an alternative embodiment of the technical solution of the present invention, other thermoplastic resin tougheners include one or a combination of two or more of polyaryletherketone, polyethersulfone, polyarylethersulfone, thermoplastic polyimide or polyetherimide.

[0178] As an alternative embodiment of the technical solution of the present invention, the co-curing component includes one or a combination of two or more of cyanate ester resin, allylphenoloxy resin, epoxy resin or benzoxazine resin.

[0179] As an alternative embodiment of the technical solution of the present invention, the curing agent includes one or a combination of two or more of aminophenylacetylene, imidazole-based curing agent or aromatic amine-based curing agent.

[0180] By further defining the specific types of other thermoplastic resin tougheners, co-curing components and curing agents, the impact performance, processing performance and heat resistance of the bisphthalazinone structure polymer toughened bismaleimide resin are further improved.

[0181] According to the second aspect of the present invention, a preparation method for preparing the above-mentioned bisphthalazinone structure polymer toughened bismaleimide resin is also provided, including the following steps:

[0182] (a)Heat the allyl compound to melting, add the phthalazinone - structured polymer, as well as optional co - curing components and optional other thermoplastic resin toughening agents, and stir until it is completely dissolved in the allyl compound to obtain a dissolved phase;

[0183] (b)Then add the bismaleimide monomer and optional curing agent to the dissolved phase, and heat and stir for blending or prepolymerization to obtain the phthalazinone - structured polymer toughened bismaleimide resin.

[0184] Specifically, in step (a), the "optional co - curing components" means that the co - curing components can be added or not. Similarly, the "optional other thermoplastic resin toughening agents" means that the other thermoplastic resin toughening agents can be added or not.

[0185] In step (b), the "optional curing agent" means that the curing agent can be added or not.

[0186] The preparation method of the phthalazinone - structured polymer toughened bismaleimide resin provided by the present invention has a simple preparation process and stable process. In this preparation process, the phthalazinone - structured polymer is used as a toughening agent. This type of toughening agent not only has excellent heat - resistant performance, but also its addition does not reduce the heat - resistant performance of the bismaleimide resin and its composites. Moreover, a small amount of addition can significantly improve the impact toughness of the bismaleimide and its composites; in addition, this type of toughening agent can also be dissolved in the bismaleimide resin system, meeting the processing requirements of the bismaleimide resin and its composites.

[0187] As an optional implementation manner of the technical solution of the present invention, in step (a), the heating temperature is 30 - 160 °C, and typical but non - restrictive 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., as well as the numerical range between any two points.

[0188] As an optional implementation manner of the technical solution of the present invention, in step (b), the heating and stirring temperature is 100 - 140 °C, and the time is 0.1 - 3 h. Typical but non - restrictive 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 - restrictive heating and stirring times are 0.1 h, 0.5 h, 1 h, 1.5 h, 1.8 h, 2 h, 2.5 h or 3 h, etc.

[0189] According to the third aspect of the present invention, there is also provided an application of the bisphthalazinone-structured polymer toughened bis-maleimide resin provided by the first aspect of the present invention in prepreg, and the bisphthalazinone-structured polymer toughened bis-maleimide resin is used as a resin matrix in the prepreg.

[0190] As an alternative embodiment of the technical solution of the present invention, the reinforcing body in the prepreg includes one or more mixtures of continuous carbon fiber, continuous glass fiber, continuous quartz fiber, continuous basalt fiber, continuous aramid fiber, continuous polybenzimidazole fiber or continuous polybenzoxazole fiber.

[0191] As an alternative embodiment of the technical solution of the present invention, the mass content of the resin sizing in the prepreg is 30% to 50%, such as 30%, 35%, 40%, 45% or 50%, etc.

[0192] The present invention will be further described in detail below with reference to specific examples and comparative examples.

[0193] It should be noted that in the test methods in the following examples, unless otherwise specified, they are all conventional methods, which can be carried out according to the techniques or conditions described in the literature in this field or according to the product specifications. The types and structures of the raw materials used in the following examples or comparative examples are specifically shown in Table 1 below.

[0194] Table 1

[0195]

[0196]

[0197] Among them, the preparation method of diphenyl sulfone bisphthalazinone-structured polyarylonitrile sulfone (PSUPNS) includes the following steps:

[0198] 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 bisphthalazinone-structured 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 sulfolane and 30 mL of toluene are added. Under nitrogen protection, the temperature is raised to 145 °C and azeotropic dehydration is carried out for 2 h; the reflux device is removed, the temperature is raised to 175 °C to remove toluene in the system, the temperature is raised to 195 °C and the reaction is carried out for 4 h, and the temperature is raised to 200 °C and the reaction is carried out for 8 h; then 60 mL of sulfolane is added. After the system temperature drops to 145 °C, the polymer solution is poured into hot water containing hydrochloric acid to obtain a polymer crude product; the polymer crude product is boiled with deionized water 2-3 times to remove inorganic salts and residual solvents, filtered and dried; then it is dissolved in chloroform, filtered with cotton and diatomite as the filter element, the filtrate is precipitated into ethanol, filtered and dried to obtain refined PSUPNS, and its infrared spectrum is as Figure 1as shown

[0199] The preparation method of diphenyl sulfone bisphthalazinone-structured polyarylsulfone (PSUPS) is the same as that of PSUPNS except that "0.06 mol of 2,6-difluorobenzonitrile and 0.06 mol of 4,4'-difluorodiphenyl sulfone" in the preparation method of PSUPNS is replaced by "0.12 mol of 4,4'-difluorodiphenyl sulfone". The infrared spectrum of PSUPS is as Figure 1 as shown

[0200] The preparation method of diphenyl ether bisphthalazinone-structured polyarylether nitrile sulfone (PBPENS) is the same as that of PSUPNS except that "diphenyl sulfone bisphthalazinone-structured monomer" in the preparation method of PSUPNS is replaced by "diphenyl ether bisphthalazinone-structured monomer". The infrared spectrum of PBPENS is as shown in (a) of Figure 2 and the proton nuclear magnetic resonance spectrum is as shown in (b) of Figure 2 as shown

[0201] The preparation method of diphenyl sulfone bisphthalazinone-structured copolymerized biphenol-based polyarylethersulfone (PSUBPS) is the same as that of PSUPNS except that "0.12 mol of diphenyl sulfone bisphthalazinone-structured monomer, 0.06 mol of 2,6-difluorobenzonitrile, and 0.06 mol of 4,4'-difluorodiphenyl sulfone" in the preparation method of PSUPNS is replaced by "0.06 mol of diphenyl sulfone bisphthalazinone-structured monomer, 0.06 mol of 4,4'-biphenol, and 0.12 mol of 4,4'-difluorodiphenyl sulfone".

[0202] The preparation method of amino-terminated diphenyl ether bisphthalazinone-structured polyarylether nitrile sulfone (PBPENS-DA) includes the following steps:

[0203] In a reactor equipped with a nitrogen protection device, a mechanical stirring device, and a reflux and water separation device, 0.2 mol of a diphenyl ether bisphthalazinone structural monomer, 0.1079 mol of 2,6-difluorobenzonitrile, 0.1079 mol of 4,4'-difluorodiphenyl sulfone (the amounts of 2,6-difluorobenzonitrile and 4,4'-difluorodiphenyl sulfone are slightly excessive here for halogen capping to further react with p-aminophenol), 0.26 mol of anhydrous potassium carbonate, 110 mL of sulfolane, and 55 mL of toluene are added. Under nitrogen protection, the temperature is raised to 145 °C and azeotropic dehydration is carried out for 2 h; the reflux device is removed, the temperature is raised to 175 °C to remove all toluene in the system, the temperature is raised to 195 °C, and the reaction is carried out for 4 h, then the temperature is raised to 200 °C and the reaction is carried out for 8 h; then the temperature is lowered to 145 °C, 0.04 mol of p-aminophenol, 0.06 mol of anhydrous potassium carbonate, and 55 mL of toluene are added, and azeotropic dehydration is carried out for 1 h; the reflux device is removed, the temperature is raised to 175 °C to remove all toluene in the system, the temperature is raised to 195 °C, and the reaction is carried out for 8 h; then 110 mL of sulfolane is added. After the temperature of the system is lowered to 145 °C, the polymer solution is poured into hot water containing hydrochloric acid to obtain a crude polymer product; the crude polymer product is boiled with deionized water 2 - 3 times to remove inorganic salts and residual solvents, filtered, and dried; then it is dissolved in chloroform, filtered with cotton and diatomaceous earth as the filter element, the filtrate is precipitated into ethanol, and after filtration and drying, the refined PBPENS-DA is obtained, and its infrared spectrum is as shown in Figure 2 as shown in (a) therein, and the nuclear magnetic resonance hydrogen spectrum is as shown in Figure 2 as shown in (b) therein.

[0204] A preparation method of bismaleimide-capped diphenyl ether bisphthalazinone-structured polyarylether nitrile sulfone (PBPENS-MI) includes the following steps:

[0205] The preparation method of PBPENS-DA is the same as above. In a reactor equipped with a reflux and water separation device, a mechanical stirring device, a constant pressure funnel, and a nitrogen protection device, 10 g of PBPENS-DA, 0.1 g of p-toluenesulfonic acid, 75 mL of NMP, and 50 mL of toluene are added. 2.5 g of maleic anhydride is dissolved in 25 mL of NMP and added dropwise to the reaction system through the constant pressure funnel, and azeotropic dehydration is carried out at 145 °C for 3 h; the reflux device is removed, all toluene in the system is removed, and the reaction is continued for 3 h. The product is quickly precipitated into hot water while it is hot, filtered, and dried, and after drying, bismaleimide-capped diphenyl ether-type bisphthalazinone-structured polyarylether nitrile sulfone (PBPENS-MI) is obtained.

[0206] The preparation method of phthalazinone-structured polyarylether nitrile sulfone (PPENS) resin is not changed except that "0.12 mol of diphenyl sulfone bisphthalazinone structural monomer" in the preparation method of PSUPNS is replaced with "0.12 mol of phthalazinone-linked phenol". The infrared spectrum and nuclear magnetic resonance hydrogen spectrum of PPENS are respectively as shown in Figure 3 and Figure 4 shown.

[0207] Example 1

[0208] This example provides a toughened bismaleimide resin with a phthalazinone structure polymer (poly(aryl ether nitrile sulfone) with a diphenyl ether phthalazinone structure, PBPENS), which comprises the following raw materials by mass:

[0209] 6 kg of bismaleimide monomer, 4.5 kg of allyl compound, and 0.26 kg of phthalazinone structure polyarylether resin.

[0210] The bismaleimide monomer is diphenylmethane type bismaleimide (BDM), the allyl compound is 2,2'-diallylbisphenol A (DABPA), and the phthalazinone structure polymer is poly(aryl ether nitrile sulfone) with a diphenyl ether phthalazinone structure (PBPENS).

[0211] The preparation method of the toughened bismaleimide resin with the phthalazinone structure polymer in this example comprises the following steps:

[0212] (a) Add 4.5 kg of allyl compound (DABPA) to a mixer, heat and stir until molten. When the temperature rises to 125 °C, add 0.26 kg of poly(aryl ether nitrile sulfone) with a diphenyl ether phthalazinone structure (PBPENS), and continue stirring until it is completely dissolved in the allyl compound (DABPA) to obtain a dissolved phase;

[0213] (b) Then add 6 kg of diphenylmethane type bismaleimide (BDM) to the dissolved phase and continue stirring for about 30 minutes, and perform vacuum degassing at 110 °C until no bubbles emerge to obtain a toughened bismaleimide resin with poly(aryl ether nitrile sulfone) with a diphenyl ether phthalazinone structure.

[0214] Example 2

[0215] This example provides a toughened bismaleimide resin with a phthalazinone structure polymer (poly(aryl nitrile sulfone) with a diphenyl sulfone phthalazinone structure, PSUPNS) and its preparation method. Except that the specific type of the phthalazinone structure polymer is replaced from poly(aryl ether nitrile sulfone) with a diphenyl ether phthalazinone structure to poly(aryl nitrile sulfone) with a diphenyl sulfone phthalazinone structure, the other raw materials, dosages and preparation methods are the same as those in Example 1.

[0216] Example 3

[0217] This example provides a toughened bismaleimide resin with a phthalazinone structure polymer (poly(aryl ether nitrile sulfone) with a diphenyl ether phthalazinone structure, PBPENS), which comprises the following raw materials by mass:

[0218] 10 kg of bismaleimide monomer, 6.45 kg of allyl compound, and 0.41 kg of phthalazinone structure polymer.

[0219] The bismaleimide monomer is diphenylmethane type bismaleimide (BDM), the allyl compound is 3,3'-diallyl biphenol (DABP), and the phthalazinone structure polymer is diphenyl ether phthalazinone structure polyarylether nitrile sulfone (PBPENS).

[0220] The preparation method of the phthalazinone structure polymer toughened bismaleimide resin in this example includes the following steps:

[0221] (a) Add 6.45 kg of allyl compound (DABP) into a mixer, heat and stir until it melts. When the temperature rises to 125 °C, add 0.41 kg of diphenyl ether phthalazinone structure polyarylether nitrile sulfone (PBPENS), and continue to stir until it completely dissolves in the allyl compound (DABP) to obtain a dissolved phase;

[0222] (b) Then add 10 kg of diphenylmethane type bismaleimide (BDM) into the dissolved phase and continue to stir for about 30 minutes to obtain a uniform liquid with a certain viscosity. Perform vacuum degassing at 110 °C until no bubbles emerge to obtain diphenyl ether phthalazinone structure polyarylether nitrile sulfone toughened bismaleimide resin.

[0223] Example 4

[0224] This example provides a phthalazinone structure polymer (diphenyl sulfone phthalazinone structure polyarylsulfone, PSUPS) toughened bismaleimide resin and its preparation method. Except that the specific type of the phthalazinone structure polymer in Example 1 is replaced by diphenyl sulfone phthalazinone structure polyarylsulfone, the other raw materials, dosages and preparation methods are the same as those in Example 1.

[0225] Example 5

[0226] This example provides a phthalazinone structure polymer (diphenyl sulfone phthalazinone structure polyarylnitrile sulfone, PSUPNS) toughened bismaleimide resin, which includes the following raw materials in mass:

[0227] 6 kg of bismaleimide monomer, 4.5 kg of allyl compound, 0.26 kg of phthalazinone structure polymer and 0.13 kg of curing agent.

[0228] The bismaleimide monomer is diphenylmethane type bismaleimide (BDM), the allyl compound is 2,2'-diallyl bisphenol A (DABPA), the phthalazinone structure polymer is diphenyl sulfone phthalazinone structure polyarylnitrile sulfone (PSUPNS), and the curing agent is 2-aminophenylacetylene.

[0229] The preparation method of the phthalazinone - structured polymer toughened bis - maleimide resin in this embodiment includes the following steps:

[0230] (a) Add 4.5 kg of allyl compound (DABPA) into a mixer, heat and stir until it melts. When the temperature rises to 125 °C, add 0.26 kg of diphenylsulfone phthalazinone - structured polyaryl nitrile sulfone (PSUPNS), and continue stirring until it completely dissolves in the allyl compound (DABPA) to obtain a dissolved phase;

[0231] (b) Then add 6 kg of diphenylmethane - type bismaleimide (BDM) and 0.13 kg of curing agent 2 - aminophenylacetylene into the dissolved phase, continue stirring for about 30 minutes to obtain a uniform, amber - colored liquid with a certain viscosity, and conduct vacuum degassing at 110 °C until no bubbles emerge to obtain diphenylsulfone phthalazinone - structured polyaryl nitrile sulfone toughened bis - maleimide resin.

[0232] Example 6

[0233] This example provides a phthalazinone - structured polymer (diphenylsulfone phthalazinone - structured copolymerized biphenol - type polyarylether sulfone, PSUBPS) toughened bis - maleimide resin and its preparation method. Except that the specific type of the phthalazinone - structured polymer in Example 1 is replaced by diphenylsulfone phthalazinone - structured copolymerized biphenol - type polyarylether sulfone, the other raw materials, dosages, and preparation methods are the same as those in Example 1.

[0234] Example 7

[0235] This example provides a phthalazinone - structured polymer (amino - terminated diphenylsulfone phthalazinone - structured polyaryl nitrile sulfone, PBPENS - DA) toughened bis - maleimide resin and its preparation method. Except that the specific type of the phthalazinone - structured polymer in Example 1 is replaced by amino - terminated diphenylsulfone phthalazinone - structured polyaryl nitrile sulfone, the other raw materials, dosages, and preparation methods are the same as those in Example 1.

[0236] Example 8

[0237] This example provides a phthalazinone - structured polymer (bis - maleimide - terminated diphenyl ether phthalazinone - structured polyaryl nitrile sulfone, PBPENS - MI) toughened bis - maleimide resin and its preparation method. Except that the specific type of the phthalazinone - structured polymer in Example 1 is replaced by bis - maleimide - terminated diphenyl ether phthalazinone - structured polyaryl nitrile sulfone, the other raw materials, dosages, and preparation methods are the same as those in Example 1.

[0238] Example 9

[0239] This embodiment provides a toughened bismaleimide resin with a phthalazinone structure polymer (phthalazinone-containing poly(arylene nitrile sulfone), PSUPNS), which comprises raw materials with the following masses:

[0240] 6 kg of bismaleimide monomer, 3.87 kg of allyl compound, 0.26 kg of phthalazinone structure polymer, and 3 kg of co-curing component.

[0241] The bismaleimide monomer is diphenylmethane type bismaleimide (BDM), the allyl compound is 3,3'-diallyl biphenol (DABP), the phthalazinone structure polymer is phthalazinone-containing poly(arylene nitrile sulfone) (PSUPNS), and the co-curing component is benzoxazine (BOZ).

[0242] The preparation method of the toughened bismaleimide resin with a phthalazinone structure polymer in this embodiment comprises the following steps:

[0243] (a) Add 3.87 kg of allyl compound (DABP) into a mixer, heat and stir until it melts. When the temperature rises to 125 °C, add 0.26 kg of phthalazinone-containing poly(arylene nitrile sulfone) (PSUPNS), and continue to stir until it completely dissolves in the allyl compound (DABP) to obtain a dissolved phase;

[0244] (b) Then add 6 kg of diphenylmethane type bismaleimide (BDM) and 3 kg of co-curing component benzoxazine (BOZ) into the dissolved phase, continue to stir for about 30 minutes to obtain a uniform amber liquid with a certain viscosity, and perform vacuum degassing at 110 °C until no bubbles emerge to obtain a phthalazinone-containing poly(arylene nitrile sulfone) toughened benzoxazine copolymerized bismaleimide resin.

[0245] Comparative Example 1

[0246] This comparative example provides a toughened bismaleimide resin with a phthalazinone structure polymer (phthalazinone-containing poly(arylene ether nitrile sulfone), PPENS), which comprises raw materials with the following masses:

[0247] 10 kg of bismaleimide monomer, 6.45 kg of allyl compound, and 0.41 kg of phthalazinone structure polymer.

[0248] The bismaleimide monomer is diphenylmethane type bismaleimide (BDM), the allyl compound is 3,3'-diallyl biphenol (DABP), and the phthalazinone structure polymer is phthalazinone-containing poly(arylene ether nitrile sulfone) (PPENS).

[0249] The preparation method of the toughened bismaleimide resin with phthalazinone-containing poly(arylene ether nitrile sulfone) (PPENS) provided by this comparative example comprises the following steps:

[0250] (a) Add 6.45 kg of allyl compound (DABP) to a mixer, heat and stir until melted. When the temperature rises to 125 °C, add 0.41 kg of phthalazinone - containing polymer (PPENS), and continue stirring until it is completely dissolved in the allyl compound (DABP) to obtain a dissolved phase;

[0251] (b) Then add 10 kg of diphenylmethane - type bismaleimide (BDM) to the dissolved phase and continue stirring for about 30 minutes to obtain a uniform liquid with a certain viscosity. Perform vacuum degassing at 110 °C until no bubbles emerge to obtain a toughened bismaleimide resin of phthalazinone - containing polyarylether nitrile sulfone (PPENS).

[0252] Comparative Example 2

[0253] This comparative example provides a bismaleimide resin. Except that the phthalazinone - containing polymer is not added in the raw materials, the dosages of the remaining raw materials are the same as those in Example 3.

[0254] The preparation method of the bismaleimide resin in this comparative example includes the following steps:

[0255] Add 6.45 kg of allyl compound (DABP) to a mixer, heat and stir until melted. When the temperature rises to 125 °C, add 10 kg of diphenylmethane - type bismaleimide (BDM), and continue stirring for about 30 minutes to obtain a uniform liquid with a certain viscosity. Perform vacuum degassing at 110 °C until no bubbles emerge to obtain a bismaleimide resin.

[0256] In order to compare the technical effects of each example and comparative example, the following experimental examples are specially set up.

[0257] Experimental Example 1

[0258] Casting body cured products are made from the toughened bismaleimide resin with phthalazinone - containing polymer provided in each example and the toughened bismaleimide resin or bismaleimide resin provided in the comparative example according to the standard GB / T 2567 - 2021, and their notched impact strengths are detected. The specific results are shown in Table 2.

[0259] At the same time, the toughened bismaleimide resin with phthalazinone - containing polymer provided in each example and the toughened bismaleimide resin or bismaleimide resin provided in the comparative example are respectively used as matrix resins, and T800H carbon fiber is used as the reinforcing fiber. Prepregs are prepared by the hot - melt method, and then continuous carbon fiber - reinforced bismaleimide resin - based composites are prepared by vacuum hot - pressing the prepregs. The volume content of carbon fiber is 63%. Then, according to the ASTM D7137 / D7137M test standard, their compressive strength after impact is detected. The specific results are shown in Table 2.

[0260] Table 2

[0261]

[0262] As can be seen from the data in Table 2, both the notch - free impact strength of the cast solid cured with the phthalazinone - structured polymer toughened bismaleimide resin of the present invention and the compressive strength after impact of the composite material have been greatly improved. Comparing Example 3 with Comparative Example 2, it can be seen that after adding the phthalazinone - structured polymer, the notch - free impact strength of the cast solid cured and the compressive strength after impact of the composite material are significantly improved.

[0263] Experimental Example 2

[0264] The heat - resistant properties of the phthalazinone - structured polymer toughened bismaleimide resin provided in each example and the phthalazinone - structured polymer toughened bismaleimide resin or bismaleimide resin provided in the comparative examples were tested. The specific results are shown in Table 3. Among them, the glass transition temperature T g was tested according to GB / T 19466.2 - 2004 "Plastics - Differential scanning calorimetry (DSC) - Part 2: Determination of the glass transition temperature".

[0265] Table 3

[0266]

[0267] As can be seen from the data in Table 3, introducing the phthalazinone - structured polymer into the high - temperature - resistant bismaleimide resin of the present invention can maintain the excellent heat - resistant properties of the bismaleimide resin.

[0268] The above - mentioned 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 principles of the present invention are within the scope of the claims of the present invention pending approval.

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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