CN109971151B

CN109971151B - Bisphthalonitrile resin fiber reinforced material containing triaryl s-triazine structure and preparation method thereof

Info

Publication number: CN109971151B
Application number: CN201910251653.XA
Authority: CN
Inventors: 蹇锡高; 宗立率; 王锦艳; 刘程; 翁志焕
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 2016-11-03
Filing date: 2016-11-03
Publication date: 2021-09-17
Anticipated expiration: 2036-11-03
Also published as: CN106632274A; CN106632274B; CN109971151A

Abstract

The invention provides a bi-phthalonitrile resin fiber reinforced material containing a triaryl s-triazine structure, belonging to the technical field of polymer material science. The reinforced resin consists of glue and fiber materials, wherein the mass ratio of the glue to the fiber materials is 1.0-99.9: 100, respectively; the glue comprises a bis-phthalonitrile resin containing a triaryl s-triazine structure, has a structural general formula as shown in the following formula I, and also comprises the following components: curing agent, curing accelerator and filler. The preparation method of the bisphthalonitrile resin fiber reinforced material comprises the following steps: comprises the steps of glue preparation, glue dipping, molding and curing. The fiber reinforced material prepared by the invention has certain structural strength and high heat resistance grade.

Description

Bisphthalonitrile resin fiber reinforced material containing triaryl s-triazine structure and preparation method thereof

The application is a divisional application of a patent application with the filing date of 2016, 11 and 03, the filing number of 201610955196.9, and the title of "a bis-phthalonitrile resin fiber reinforced material containing a triaryl s-triazine structure and a preparation method thereof".

Technical Field

The invention belongs to the technical field of polymer material science, relates to a preparation technology of a high-performance composite material, and particularly relates to a bis-phthalonitrile resin reinforced fiber material containing an aryl s-triazine structure and a preparation method thereof.

Background

The phthalonitrile resin is a new thermosetting resin and has the advantages of good thermal stability, flame retardance, radiation resistance, corrosion resistance and the like. Has wide application prospect in the high-tech fields of aerospace, nuclear energy industry, electronic communication and the like. A report of the use of PHTHALONITRILE resin as a high temperature resistant material began in Keller et al, NASA navy research center, USA (KELLER T M, PRICE T R. AMINE-CURED BISPHSPHENOL-LINKED PHTHALONITRILE RESINS [ J ]. J Macrom Sci Chem,1982, A18(6): 931) 937.). Subsequently, various types of phthalonitrile resins having ether bonds of different structures were successively developed (KELLER T M. Synthesis and polymerization of multiple aromatic ether resins [ J ]. Chemical Materials,1994,6: 302-305.). In order to improve the processability of phthalonitrile resins, Liuxiabo et al (ZOU Y, YANG J, ZHAN Y, et al. Effect of curing behavors on the properties of poly (arylene ether nitrile) end-capped with a polymeric composition [ J ]. J Appl Polymer Sci,2012,125(5): 3829. beta. 3835; CHEN Z, GUO H, TANG H, et al. preparation and properties of bisphenol A-based bis-polymeric compositions [ J ]. Journal of Applied Polymer Science,2013,129(5): 2621. 2628.) introduce isopropyl or arylnitrile structures into the Polymer backbone, expanding the processing window of the resin. Meanwhile, the structure of phthalonitrile is also used to toughen and modify epoxy, benzoxazine resin (LIU X, XU M, YANG X. tetraphthalonitrile monomer partial bonding benzoxazine, its Polymers and preparation methods [ P ]. CN,102976972 A.2013-03-20; HARTON I, MCNAMARAL T, WLHOIN B J, et al. nanoparticles in Aromatic polycarbonate resins Using Thermoplastic Oligomers and Polymers [ J ]. Macromolecules 2014,47(6):1946 1958; ZHANG LUB, O Z, ZHHOU H, et al. addition-type benzoxazine-functional [ 24, 404 ] through physical blending or chemical modification etc.). Ferrocene, ferroferric oxide (DONG S, XU M, WEI J, et al. the preparation and with frequency microwave absorbing properties of three-substistuted-bisphthalimide/Fe 3O4Magnetic microspheres [ J ]. Journal of Magnetic Materials 2014,349: 15-20; YANG J, TANG H, ZHAN Y, et al. thermoelectric properties of poly (aryl ethylene copolymers) -copperphthalic compositions in a size polymerization [ J ]. Materials Letters 2012,72:42-45.) and the like are also introduced into the field of phthalonitrile resins and electromagnetic absorbing Materials. In addition, phthalonitrile structures can also be incorporated as pendant crosslinkable groups into the structure of commercially available resins, such as polyarylene ethers, polyamides (ZENG K, ZOU Y, YANG G. Synthesis and properties of Polymers derived from a new polyamide-containing diamine with high polymerization reactivity [ J ]. Designed Monomers and Polymers,2014,17(2): 186. 193.). At present, phthalonitrile resin is used as matrix resin to be compounded with reinforcing materials such as fibers and the like to prepare fiber reinforced composite materials. Composites that have been developed include carbon fiber reinforced Composites (SASTRIS S B, ARMISTEAD J P, KELLER T M. Thermosonitrile-carbon fiber Composites [ J ] Polymer Composites,1996,17:816-822.), glass fiber reinforced Composites (SASTRIS B, ARMISTEAD J P, KELLER T M, et al. Thermosonitrile-glass fibers Composites [ J ] Polymer Composites,1997,18(1): 48-54; ZHOU H, BADASHAH A, POLY Z, et al. preparation and property Composites of metal, and of organic polymeric Composites with an amino [ J ] Polymer for modified and property Composites, and carbon nanotube Composites [ 10, 2011-9. modifier ] phosphor Composites [ 10, 748-19. 10. thermoplastic nanotubes [ 10. 8 ] thermoplastic Polymers for modified and property Composites [ 10. 9. 8. 9. thermoplastic Polymers ] Composites [ 10. 9. 8. thermoplastic nanotubes; SKIN 748. 9. thermoplastic Composites [ 10. 9. thermoplastic resins ] carbon nanotubes [ 10. 9. thermoplastic Composites, 748. thermoplastic Composites [ 10. 9. thermoplastic copolymers of carbon nanotubes, 748. thermoplastic Composites [ 10. 748. 9. thermoplastic copolymers, 748-), has good application prospect in the fields of heat conduction, wave transmission, electric conduction and the like. However, the resins reported in the literature have low heat resistance, which limits their use at higher temperatures. However, the invention and the work do not relate to the preparation and the use of the bis-phthalonitrile resin-based composite material containing the triaryl s-triazine structure in the main chain by integrating the research work progress of the phthalonitrile resin at home and abroad.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a bis-phthalonitrile resin fiber reinforced material containing a triaryl s-triazine structure and a preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a bis-phthalonitrile resin fiber reinforced material containing a triaryl s-triazine structure comprises glue and a fiber material, wherein the mass ratio of the glue to the fiber material is 1.0-99.9: 100, respectively;

the glue comprises a bisphthalonitrile resin containing a triaryl s-triazine structure, wherein the bisphthalonitrile resin containing the triaryl s-triazine structure has a structural general formula shown as the following formula I:

wherein Ar1 is any one of the following structures (a) to (k):

ar2 and Ar3 have any one of the following structures (l) to (z):

ar2 and Ar3 are the same or different;

when Ar2 and/or Ar3 is (q), some of the ether linkages in the structure shown in formula I are correspondingly changed to C-N bonds depending on the nitrogen terminus in (q);

in the formulae: r1, R2, R3, R4, R5 and R6 are hydrogen, C1-C10 alkyl, aliphatic group, fluorinated aliphatic group, aromatic group, halogen and one of sulfonic groups, and R1, R2, R3, R4, R5 and R6 are the same or different; a + b is 1, 0< a is less than or equal to 1, 0< b is less than or equal to 1, wherein a and b are the molar percentage of the corresponding units respectively; n > 0; the number average molecular weight of the resin detected by GPC is 500-.

In the above-mentioned fiber reinforced material of the bisphthalonitrile resin, as a preferred embodiment, the mass fraction of the glue in the reinforced material is 30% to 50% (for example, 31%, 35%, 40%, 45%, 49%), in which the performance of the reinforced material is better, too little glue content may cause the loose bonding between fiber layers, and above 50% may cause the low fiber content, and the reinforcing effect is not obvious.

In the above-mentioned fiber reinforced material of bisphthalonitrile resin, as a preferred embodiment, the glue further comprises the following components: curing agent, curing accelerator and filler.

In the above-mentioned fibrous reinforcing material of a bis-phthalonitrile resin, as a preferred embodiment, the mass ratio of the bis-phthalonitrile resin containing a triaryl-s-triazine structure to the curing agent is 0.5 to 1000:1 (for example, 1%, 5%, 20%, 40%, 100%, 200%, 300%, 400%, 500%, 600%, 700%, 800%, 900%, 950%), and preferably, the mass ratio of the bis-phthalonitrile resin containing a triaryl-s-triazine structure to the curing agent is 10 to 40: 1 (e.g., 11%, 15%, 22%, 27%, 30%, 35%, 38%). The amount of the filler is 0 to 99.0% (e.g., 0.1%, 10%, 15%, 27%, 30%, 35%, 38%, 45%, 55%, 67%, 75%, 85%) of the total mass of the triaryl-s-triazine-structure-containing bisphthalonitrile resin, the curing agent, and the curing accelerator, and preferably 1 to 30% (e.g., 1.2%, 5%, 15%, 20%, 25%, 28%) of the total mass of the triaryl-s-triazine-structure-containing bisphthalonitrile resin, the curing agent, and the curing accelerator. In the reinforced material, the curing accelerator is used for accelerating the curing reaction, and the filler plays a modifying role, such as enhancing the thermal stability of the material or endowing the material with other functions, such as flame retardance, insulation, wave transmission, wave absorption and the like.

In the above-mentioned fibrous reinforcing material of a bisphthalonitrile resin, as a preferred embodiment, the curing accelerator is used in an amount of 0% to 3.0% (e.g., 0.1%, 0.5%, 1%, 1.5%, 2.2%, 2.8%) by weight based on the total weight of the phthalonitrile resin containing a triaryl-s-triazine structure, and preferably, the ratio is 0.1% to 2%.

In the above-mentioned bis-phthalonitrile resin fiber reinforcement, as a preferred embodiment, the curing agent is selected from one or more of metals, metal salts, organic amines, organic acids, and organic anhydrides. Specifically, metals such as zinc, aluminum, manganese, iron, nickel, etc.; metal salts such as zinc chloride, cobalt chloride, copper fluoride, cuprous chloride, ferric chloride, ferrous chloride, etc.; organic amines such as diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, 2, 6-bis (4-aminophenoxy) benzonitrile, bis [4- (4-aminophenoxy) benzene ] sulfone, 2, 4-bis 4- (4-aminophenoxy) phenyl-6-phenyl-1, 3, 5-triazine, 4- (4-aminophenoxy) phthalonitrile, and the like; organic acids such as phthalic acid, terephthalic acid, isophthalic acid, and the like; organic anhydrides such as phthalic anhydride, nadic anhydride, and the like.

In the above-mentioned fibrous reinforcement of a bisphthalonitrile resin, as a preferred embodiment, the curing accelerator is selected from one or more of tetrabutylammonium bromide, tri-2-ethylhexanoate of DMP-30, imidazole, 2-methylimidazole, 2, 4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1,3, 5-triethyl-hexahydro-s-triazine, 1,3, 5-trimethyl-hexahydro-s-triazine, triethylamine, triethanolamine, benzyldimethylamine, triphenylphosphine, triethylphosphine, acetylacetone transition metal compounds and phthalein acetone rare earth compounds; preferably, the acetylacetone transition metal compound is cobalt acetylacetonate.

In the above-mentioned fibrous reinforcing material of bisphthalonitrile resin, as a preferred embodiment, the filler is one or both of an inorganic filler and a functionalized filler; more preferably, the inorganic filler is selected from one or more of graphite, simple metal, alloy, metal oxide, metal hydroxide, metal nitride and metal salt; more preferably, the functionalized filler is selected from one or more of non-metallic oxides, non-metallic nitrides, non-metallic carbides, and ores. Specifically, a simple metal or an alloy, such as gold, silver, copper, iron, or an alloy of each, etc.; metal or nonmetal oxides such as aluminum oxide, magnesium oxide, titanium dioxide, iron sesquioxide, ferroferric oxide, silver oxide, zinc oxide, silicon dioxide, and the like; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, etc.; metal or nonmetal nitrides such as aluminum nitride, silicon nitride, boron nitride, etc.; non-metallic carbides such as silicon carbide, boron carbide, and the like; metal salts including metal carbonates, silicates, sulfates, phosphates, etc., such as calcium carbonate, barium sulfate, calcium sulfate, silver chloride, aluminum phosphate, zinc phosphate, etc.; minerals such as asbestos, talc, kaolin, mica, feldspar, wollastonite, montmorillonite, etc.

In the above-mentioned fibrous reinforcement of a bisphthalonitrile resin, as a preferred embodiment, the fibrous material is selected from one or more of glass fibers, carbon fibers, boron fibers, silicon carbide fibers, graphene oxide, graphene fibers, carbon nanotubes, basalt fibers, silica fibers, alumina fibers, aromatic polyamide fibers, polyvinyl acetate fibers and cellulose fibers; or the fiber material is a fabric or a fiber mesh made of glass fibers, carbon fibers, boron fibers, silicon carbide fibers, graphene oxide, graphene fibers, carbon nanotubes, basalt fibers, silica fibers, alumina fibers, aromatic polyamide fibers, polyvinyl acetate fibers or cellulose fibers.

The preparation method of the bi-phthalonitrile resin fiber reinforced material comprises a glue preparation step, a glue dipping step, a forming step and a curing step.

In the above preparation method, as a preferred embodiment, in the glue compounding step, the bis-phthalonitrile resin containing a triaryl-s-triazine structure, the curing agent, the curing accelerator, and the filler are added to an organic solvent and dissolved to prepare an organic solution (i.e., a dipping solution). More preferably, the bis-phthalonitrile resin containing a triaryl s-triazine structure, the curing agent and the curing accelerator are mixed and heated to a molten state to react for 1-60 min (such as 2min, 8min, 12min, 15min, 25min, 30min, 35min, 40min, 45min, 50min and 55min) to form a B-stage resin, the B-stage resin is cooled to room temperature and then added with an organic solvent and a filler, and the mixture is fully stirred to obtain an organic solution stable at room temperature, wherein the mass ratio of the B-stage resin to the organic solvent is 1:1.25-100 (such as 1:1.5, 1:9, 1:15, 1:20, 1:30, 1:35, 1:45, 1:55, 1:65, 1:75, 1:85, 1:95 and 1:99), and the mass of the filler is 0-99% of the B-stage resin; the dosage of the curing accelerator is 0 to 3.0 percent of the total weight of the phthalonitrile resin containing the triaryl s-triazine structure; more preferably, the temperature in the molten state is 100 to 300 ℃ (e.g., 110 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃,200 ℃, 220 ℃, 250 ℃, 270 ℃, 290 ℃). Wherein, it is not necessary that the bis-phthalonitrile resin containing the triaryl s-triazine structure, the curing agent and the curing accelerator are mixed and heated to a molten state, and the resin does not need to be molten because the molecular weight of some resins is too high to reach the molten state. For the bi-phthalonitrile resin which has higher molecular weight and can not be melted and contains the triaryl s-triazine structure, the resin and the curing agent can also be directly dissolved in a solvent to prepare the dipping solution. Whether the filler is added or not is determined according to the application of the composite material, and the filler is required to be added when the composite material is used in some functional occasions or the application requirement cannot be met without the filler.

In the above production method, as a preferred embodiment, the organic solvent is one or more of halogenated alkane, ethyl acetate, tetrahydrofuran, benzene, toluene, ethylbenzene, chlorobenzene, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone.

In the above preparation method, as a preferred embodiment, in the step of dipping, the fiber material is passed through a dipping tank containing the organic solution at a speed of 0.01m/s to 1m/s to ensure that the fiber is fully dipped to obtain a fiber prepreg sheet, and then the fiber prepreg sheet is dried; preferably, the drying temperature is 40-200 ℃, so that the content of volatile components is less than 0.2 wt%; more preferably, the temperature of the drying is 150 ℃.

In the above production method, as a preferred embodiment, in the molding step, a plurality of layers of the fiber prepreg are laid in a mold and molded by autoclave, lamination or resin transfer molding technique to obtain a bisphthalonitrile resin fiber reinforced material prepreg containing a triaryl s-triazine structure; preferably, in the forming step, the forming temperature is 250-350 ℃, the forming pressure is 0.1-10.0 MPa, and the pressure holding time is 0.5-8 h; more preferably, the molding temperature is 250 ℃, the molding pressure is 0.5MPa, and the pressure holding time is 2 h.

In the above production method, as a preferred embodiment, in the curing step, the curing conditions of the preform are: carrying out gradient temperature rise at 200-425 ℃, wherein the temperature rise is carried out for 4-12 times, preferably 6 times, and the temperature is kept for 0.5-16 h at each stage, so as to obtain the phthalonitrile resin fiber reinforced material containing the triaryl s-triazine structure; preferably, the curing condition is that the temperature of the pre-pressed sheet is firstly raised to 250 ℃, the temperature is kept for 3h, then raised to 285 ℃, the temperature is kept for 1h, then raised to 325 ℃, the temperature is kept for 3h, then raised to 350 ℃, then kept for 2h, then raised to 375 ℃, kept for 4h, finally raised to 400 ℃, and kept for 4 h.

Compared with the prior art, the invention has the beneficial effects that:

the fiber reinforced material prepared by the invention has certain structural strength and high heat resistance grade. The invention introduces the triaryl s-triazine structure with excellent thermal stability into the main chain of the phthalonitrile resin, can effectively improve the heat resistance of the resin, and further widens the application of the fiber reinforced material in the fields of structural materials, adhesives and the like. Meanwhile, the functional filler is introduced, so that the prepared composite material product has the potential of being used as a material with heat conduction, wave transmission, electric conduction and the like, and can also be used as a structural material under severe conditions such as high temperature, high irradiation and the like.

The composite material containing the novel phthalonitrile resin has a plurality of excellent properties. The triazine content in the resin is obviously increased, so that the heat resistance and the strength of the material are greatly improved, the glass transition temperature is about 400 ℃ through a Dynamic Mechanical Analysis (DMA) test, and the use requirement of a high-temperature environment of 350 ℃ and above can be met. Meanwhile, the dielectric property, the insulating property and the like of the composite material are also kept at a certain level, and the composite material can be applied to the fields of various functional polymers as a material. Mechanical property tests show that the bending strength of the phthalonitrile resin-based continuous carbon fiber composite material containing the triaryl s-triazine structure is higher than 1700MPa, the interlaminar shear strength is higher than 70MPa, the composite material can be used as a structural material, a composite material matrix resin, a high-temperature-resistant coating and the like, and the composite material has a wide application prospect in the field of advanced resin-based composite materials represented by aerospace.

Detailed Description

The concrete preparation method of the reinforced material comprises the following steps: heating a composition consisting of the bis-phthalonitrile resin containing the triaryl s-triazine structure, the curing agent and the curing accelerator to a molten state (150-300 ℃) to react for 1-60 min to form B-stage resin, cooling to room temperature, adding an organic solvent, an inorganic filler or a functional filler, and fully stirring to obtain an organic solution stable at room temperature. Since some resins have too high a molecular weight to reach a molten state, it is not necessary to go through the molten state. For the bi-phthalonitrile resin which has higher molecular weight and can not be melted and contains the triaryl s-triazine structure, the resin and the curing agent can also be directly dissolved in a solvent to prepare the dipping solution. Whether the filler is added or not is determined according to the application of the composite material, and the filler is required to be added when the composite material is used in some functional occasions or the application requirement cannot be met without the filler. In the mixture ratio of all raw materials, the mass ratio of the B-stage resin containing the triaryl s-triazine structure to the organic solvent is 1:1.25-100, and the mass of the inorganic filler or the functionalized filler is 0-99% of that of the B-stage resin. The fiber material is fully soaked in an organic solution, mixed and dried, then, according to the process procedures of the conventional thermosetting composite material, the autoclave, winding, mould pressing and laminating technologies are used for forming to obtain a bisphthalonitrile resin-based preforming sheet with the inorganic particle and/or fiber content of 1-99.9% based on the total weight, and the thermosetting composite material containing the triaryl s-triazine structure is obtained after high-temperature (350 ℃) postcuring.

The phthalonitrile resin containing the triaryl s-triazine structure is prepared according to the following method:

the method comprises the following steps:

the preparation method comprises the following steps of (1) preparing a phenoxy salt terminated polyarylether containing triaryl s-triazine, namely adding the bisphenol monomer, the dihalogen monomer containing the triaryl s-triazine structure, the dihalogen monomer without the triaryl s-triazine structure, the alkali catalyst, a first reaction solvent and a dehydrating agent into a reaction kettle in sequence, firstly heating to 120-150 ℃ (such as 125 ℃, 130 ℃, 135 ℃, 140 ℃ and 145 ℃) for dehydrating for 1-7 h (such as 1.5h, 2.5h, 4h, 5.5h and 6.5h), and steaming out the dehydrating agent; continuously heating to 160-220 ℃ (such as 165 ℃, 170 ℃, 180 ℃, 190 ℃,200 ℃, 210 ℃ and 215 ℃) for reacting for 1-30 h (such as 2h, 5h, 10h, 15h, 20h, 25h and 28h), and continuously adding a second reaction solvent along with the increase of the viscosity of the reaction system in the reaction process until the viscosity of the reaction system is not increased; and after the reaction is finished, cooling the reaction liquid to room temperature to obtain the reaction liquid of the polyarylether containing the triaryl s-triazine terminated by the phenoxy salt. The first reaction solvent and the second reaction solvent are the same, the dosage of the first reaction solvent is calculated according to the solid content of a reaction system, namely the content of bisphenol monomers and dihalogen monomers, in order to reduce the generation of small molecular cyclization products in the polymerization reaction, the second reaction solvent is required to be continuously added in the reaction process, and the dosage of the second reaction solvent is added according to the viscosity of the reaction system, has no specific dosage and is completely determined according to the progress of the reaction.

The method comprises the steps of end capping of phthalonitrile resin, adding 4-nitrophthalonitrile into reaction liquid of polyarylether containing triaryl s-triazine and end capped by phenoxy salt, heating to 60-120 ℃ (such as 65 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ and 105 ℃) to react for 1-30 h (such as 2h, 5h, 10h, 15h, 20h, 25h and 28h), then adding a precipitator into a reaction system to precipitate polymer, and filtering, separating, cleaning and drying to obtain the bisphthalonitrile resin with the main chain containing the triaryl s-triazine structure, namely prepolymer resin.

Wherein in the step of preparing the aryloxide-terminated triaryl s-triazine-containing polyarylether, the dihalogen monomer containing the triaryl s-triazine structure is one or more of 2, 4-bis (4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 2, 4-bis (3-methyl-4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 2, 4-bis (3, 5-dimethyl-4-fluorophenyl) -6-phenyl-1, 3, 5-triazine and 2, 4-bis (4-fluorophenyl) -6- (4-sulfophenyl) -1,3, 5-triazine; the bisphenol monomer is one or more of hydroquinone, resorcinol, 4 '-biphenol, 2-bis (4, 4' -dihydroxydiphenyl) propane, 2-bis (4,4 '-dihydroxydiphenyl) hexafluoropropane, 4- (4-hydroxy-phenyl) -2H-naphthyridin-1-one, 4' -dihydroxydiphenylmethane, 2, 6-naphthalenediol, 1, 7-naphthalenediol, 1, 8-naphthalenediol, 1, 6-naphthalenediol, 1, 5-naphthalenediol, phenolphthalein and phenolphthalein; the double-halogen monomer without the triaryl s-triazine structure is one or more of 4,4 '-difluorobenzophenone, 4' -difluorodiphenyl sulfone, 4 '-dichlorobenzophenone, 4' -dichlorodiphenyl sulfone, 2, 6-dichloronaphthalene, 2, 6-difluoronaphthalene, 1, 4-bis (4-fluorobenzoyl) benzene, 1, 3-bis (4-fluorobenzoyl) benzene, bis (4-fluorophenyl) phenylphosphine oxide, 4 '-bis (4-fluorobenzoyl) biphenyl, 4' -bis (4-fluorobenzoyl) benzophenone, 4 '-bis (4-fluorobenzoyl) phenyl ether and 4, 4' -bis (4-fluorobenzoyl) diphenylmethane.

In the preparation step of the aryloxide terminated polyarylether containing triaryl s-triazine, the molar ratio of the bisphenol monomer to the dihalogen monomer containing triaryl s-triazine structure is 1.01-4: 1 (e.g., 1.1:1, 1.3:1, 1.5:1, 1.8:1, 2.2:1, 2.5:1, 2.8:1, 3.2:1, 3.5:1, 3.8: 1); the molar ratio of the bis-halogen monomer containing a triaryl s-triazine structure to the bis-halogen monomer not containing a triaryl s-triazine structure is 1: 0-99 (e.g., 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:90, 1: 98); the first reaction solvent and the second reaction solvent are one or more of dimethyl sulfoxide, sulfolane, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and diphenylsulfone; in the preparation step of the aryloxide terminated polyarylether containing triaryl s-triazine, the amount of the first reaction solvent is 0.1-100.0 ml of the first reaction solvent per gram of the mixture of bisphenol and dihalogen monomer; the dehydrating agent is one or more of benzene, toluene, xylene and chlorobenzene; the dosage of the dehydrating agent is 0.1-100.0 ml of first reaction solvent/ml of dehydrating agent; the alkali catalyst is one or more of sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate; the molar ratio of the bisphenol monomer to the base catalyst is 1: 1-6 (for example, 1:2, 1:3, 1:4, 1:5, 1: 5.8).

In the end capping step of the phthalonitrile resin, the precipitator is one or more of ethanol, methanol and water; the molar ratio of the 4-nitrophthalonitrile to the bisphenol monomer is 0.03-10: 1 (such as 0.05:1, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 9.5: 1).

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for the purpose of the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.

The reagents and raw materials used in the following examples are all commercially available products except for the phthalonitrile resin having a triaryl-s-triazine structure.

Examples 1 to 9 below are preparation examples of phthalonitrile resins containing a triaryl-s-triazine structure, and examples 10 to 20 are preparation examples of reinforcing materials.

Example 1 preparation of a phthalonitrile resin having a triaryl-s-triazine Structure (abbreviated as resin A) shown in formula a

Wherein, Ar3 group adopts a (q) structure, R1-R6 groups are all-H, a is 1, b is 0, the molecular weight of the polymer is 1820 detected by GPC, and the number of repeated structural units n is 2.4.

The preparation method comprises the following steps:

(1) in a 500mL three-necked flask equipped with mechanical stirring, a water-dividing condenser, and a nitrogen inlet was charged 47.6492g of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one, 34.5108g of 2, 4-bis (4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 35.8572g of anhydrous potassium carbonate, 100mL of N-methylpyrrolidone, and 50mL of toluene; refluxing with water at 150 ℃ for 3h, and evaporating toluene; continuously heating to 190 ℃ for reaction for 7h, supplementing a solvent according to the viscosity of the reaction system in the reaction process until the viscosity of the reaction system is not increased any more, wherein the amount of the supplemented solvent is 3 mL; and cooling to room temperature to obtain reaction liquid of the phenoxy salt terminated intermediate.

(2) 38.0888g of 4-nitrophthalonitrile was added to the reaction solution of the phenoxide-terminated intermediate contained in step (1), and the temperature was raised to 100 ℃ to react for 12 hours. After the reaction is finished, adding the reaction solution into 1500mL of boiling water with hydrochloric acid concentration of 15%, continuously stirring, stirring at 100 ℃ for 30min, cooling to room temperature, filtering, and collecting solids to obtain the brown short-strip prepolymer. The molar yield of the prepolymer was 94%.

Washing the brown short strip prepolymer with distilled water for several times, then placing the prepolymer in a vacuum drying oven at 80 ℃ for drying for 24h, soxhlet extracting the prepolymer with acetone for 24h, vacuum drying at 110 ℃ for 24h, dissolving the prepolymer in N, N-dimethylacetamide, precipitating the solution into ethanol after filtering, washing the solution with distilled water for several times, and vacuum drying at 110 ℃ for 24h to obtain a brown product which is the target polymer, namely the resin A. This purification removes small molecule impurities as well as cyclics.

The structure of the polymer is consistent with that of the polymer through infrared and nuclear magnetism characterization, and the infrared spectrum is 1250cm^-1A characteristic absorption peak of ether bond in the vicinity; at 1510cm^-1And 1360cm^-1Characteristic absorption peaks of triazine ring appear nearby; the characteristic absorption peak of the cyano group appears at 2230cm^-1A vicinity of the device. In a nuclear magnetic spectrum, a resonance peak belonging to proton hydrogen on a benzene ring in a diphenyl fluorenyl group appears near a chemical shift delta-7.1, a hydrogen proton resonance peak adjacent to the triazine ring appears on the benzene ring at the position delta-8.3-8.6, proton hydrogen on a p-phenylene group respectively appears near delta-7.3 and delta-7.6, and a characteristic resonance peak of peri hydrogen of a heteronaphthalene biphenyl appears at the position delta-8.9. Proton peaks belonging to the phthalonitrile group occur in the vicinity of δ ═ 7.4 and δ ═ 7.8. The above structural characterization demonstrated that the synthesized prepolymer was consistent with the assumptions.

After adding curing agent diaminodiphenyl ether, the prepolymer is cured by reaction at 250 ℃ for 3h, 285 ℃ for 1h, 325 ℃ for 3h, 350 ℃ for 2h, 375 ℃ for 4h and 400 ℃ for 4h to obtain black cast-like cured product. In N of₂In the temperature range, the residual carbon rate at 900 ℃ is 78%, the 5% thermal weight loss temperature is 539 ℃, and the glass transition temperature is 478 ℃.

Example 2 preparation of a phthalonitrile resin having a triaryl-s-triazine Structure (abbreviated as resin B) shown in formula B

Wherein, R1-R3 groups are all-H, a is 1, b is 0, Ar3 group adopts (n) structure, the molecular weight of the polymer is 1297 detected by GPC, and the number of repeated structural units n is 1.6.

The preparation method comprises the following steps:

(1) in a 100mL three-necked flask equipped with mechanical stirring, a water-dividing condenser, and a nitrogen inlet, 1.4896g of biphenol, 1.3804g of 2, 4-bis (4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 1.3456g of anhydrous potassium carbonate, 5mL of sulfolane, and 20mL of toluene were charged; refluxing with water at 150 ℃ for 3h, and evaporating toluene; continuously heating to 190 ℃ for reaction for 7h, supplementing a solvent according to the viscosity of the reaction system in the reaction process until the viscosity of the reaction system is not increased any more, wherein the amount of the supplemented solvent is 3 mL; and cooling to room temperature to obtain reaction liquid of the phenoxy salt terminated intermediate.

(2) 1.1620g of 4-nitrophthalonitrile was added to the reaction solution of the phenoxide-terminated intermediate contained in step (1), and the temperature was raised to 100 ℃ to react for 18 hours. After the reaction is finished, adding the reaction solution into 500mL of boiling water with 15% hydrochloric acid concentration, continuously stirring, stirring at 100 ℃ for 30min, cooling to room temperature, filtering, and collecting solids to obtain the brown short-strip prepolymer.

The brown short strip prepolymer is washed by distilled water for several times, then is dried in a vacuum drying oven at 80 ℃ for 24 hours, is subjected to soxhlet extraction by acetone for 24 hours, and is dried in vacuum at 110 ℃ for 24 hours, and the molar yield of the prepolymer is 96 percent.

And dissolving the prepolymer in N, N-dimethylacetamide, filtering, precipitating the solution into ethanol, filtering, washing with distilled water for several times, and vacuum drying at 110 ℃ for 24 hours to obtain a brown product, namely the resin B. This purification removes small molecule impurities as well as cyclics.

The structure of the polymer is consistent with that of the polymer through infrared and nuclear magnetism characterization, and the infrared spectrum is 1250cm^-1Characteristic absorption peak of ether bond; at 1510cm^-1And 1360cm^-1A characteristic absorption peak of the triazine ring appears; the characteristic absorption peak of the cyano group appears at 2230cm^-1To (3). In a nuclear magnetic spectrum, a resonance peak belonging to proton hydrogen on a benzene ring in a diphenyl fluorenyl group appears near a chemical shift delta-7.1, a hydrogen proton resonance peak adjacent to the triazine ring appears at a position delta-8.3-8.6, and proton hydrogen on a p-phenylene group respectively appears near delta-7.3 and delta-7.6. Proton peaks belonging to the phthalonitrile group occur in the vicinity of δ ═ 7.4 and δ ═ 7.8. The above structural characterization demonstrated that the synthesized prepolymer was consistent with the assumptions.

After adding curing agent diamino diphenyl sulfone, the prepolymer is cured through reaction at 250 deg.c for 3 hr, reaction at 285 deg.c for 1 hr, reaction at 325 deg.c for 3 hr, reaction at 350 deg.c for 2 hr and reaction at 375 deg.c for 8 hr to obtain black cast cured product. In N of₂Middle, 90The carbon residue rate at 0 ℃ is up to 76%, the 5% thermal weight loss temperature is 574 ℃, and the glass transition temperature is 453 ℃.

Example 3 preparation of a phthalonitrile resin containing a triaryl-s-triazine Structure, of the formula C (referred to as resin C for short)

Wherein, the groups from R1 to R3 are all-H, a is 0.5, b is 0.5, the group Ar3 is (n), the group Ar2 is (l), and the group Ar1 is (a). The molecular weight of the polymer was determined by GPC as 1980 and the number of repeating structural units, n, was 4.4.

The preparation method comprises the following steps:

(1) in a 100mL three-necked flask equipped with mechanical stirring, a water-dividing condenser, and a nitrogen inlet were charged 1.1173g of biphenyldiol, 0.4404g of hydroquinone, 0.5564g of 2, 6-difluorobenzonitrile, and 1.3804g of 2, 4-bis (4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 1.9308g of anhydrous potassium carbonate, 10mL of dimethyl sulfoxide, and 20mL of toluene; refluxing with water at 150 ℃ for 3h, and evaporating toluene; continuously heating to 190 ℃ for reaction for 7h, supplementing a solvent according to the viscosity of the reaction system in the reaction process until the viscosity of the reaction system is not increased any more, wherein the amount of the supplemented solvent is 2 mL; and cooling to room temperature to obtain reaction liquid of the phenoxy salt terminated intermediate.

(2) 0.8230g of 4-nitrophthalonitrile was added to the reaction solution of the phenoxide-terminated intermediate contained in step (1), and the temperature was raised to 100 ℃ to react for 18 hours. After the reaction is finished, adding the reaction solution into boiling water containing 500mL hydrochloric acid with the concentration of 15%, continuously stirring, stirring at 100 ℃ for 30min, cooling to room temperature, filtering, and collecting a solid to obtain a brown strip-shaped prepolymer.

The brown long-strip prepolymer is washed by distilled water for several times, then is dried in a vacuum drying oven at 80 ℃ for 24 hours, is subjected to soxhlet extraction by acetone for 24 hours, and is dried in vacuum at 110 ℃ for 24 hours, and the molar yield of the prepolymer is 94%.

And dissolving the prepolymer in N-methyl pyrrolidone, filtering, precipitating the solution into ethanol, filtering, washing with distilled water for several times, and vacuum-drying at 110 ℃ for 24 hours to obtain a brown product which is the target polymer. This purification removes small molecule impurities as well as cyclics.

The infrared spectrum is 1246cm^-1Characteristic absorption peaks of ether bonds appear. At 1508cm^-1And 1362cm^-1The characteristic absorption peak of the triazine ring appears. The characteristic absorption peak of the cyano group appears at 2234cm^-1To (3). In a nuclear magnetic spectrum, a resonance peak belonging to proton hydrogen on a benzene ring in a diphenyl fluorenyl group appears near a chemical shift delta-7.1, hydrogen proton resonance peaks adjacent to the triazine ring on the benzene ring appear at positions delta-8.3-8.6, and proton hydrogen on a p-phenylene group respectively appears near a low field delta-6.9. The hydrogen proton on the benzene ring with the cyano group is present at a low field, i.e., δ 7.9. Proton peaks belonging to the phthalonitrile group occur in the vicinity of δ ═ 7.4 and δ ═ 7.8. The above structural characterization demonstrated that the synthesized prepolymer was consistent with the assumptions.

Adding curing agent diaminodiphenylmethane, reacting at 250 deg.C for 3h, 285 deg.C for 1h, 325 deg.C for 3h, 350 deg.C for 2h, and 375 deg.C for 8h to obtain black cast-like cured product. In N of₂In the temperature range of 900 ℃, the carbon residue rate is up to 77%, the 5% thermal weight loss temperature is 582 ℃, and the glass transition temperature is 412 ℃.

Example 4 preparation of a phthalonitrile resin containing a triaryl-s-triazine Structure, which is represented by the formula D (referred to as resin D for short)

Wherein, the groups R1 to R3 are all-H, a is 0.5, b is 0.5, the group Ar3 is of the (z) structure, Ar2 is of the (b) structure, and Ar1 is of the (n) structure. The molecular weight of the polymer was measured by GPC and found to be 5820, and the number of repeating structural units n was 10.2.

The preparation method comprises the following steps:

(1) in a 100mL three-necked flask equipped with mechanical stirring, a water-dividing condenser, and a nitrogen inlet were charged 1.1173g of biphenyldiol, 1.7507g of 9, 9-bis (4-hydroxyphenyl) fluorene (BHF), 1.4358g of 4, 4' -dichlorodiphenyl sulfone, and 1.7255g of 2, 4-bis (4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 1.9721g of anhydrous potassium carbonate, 18mL of N-methylpyrrolidone, and 30mL of toluene; refluxing with water at 150 ℃ for 3h, and evaporating toluene; continuously heating to 190 ℃ for reacting for 8h, supplementing a solvent according to the viscosity of the reaction system in the reaction process until the viscosity of the reaction system is not increased any more, wherein the amount of the supplemented solvent is 5 mL; and cooling to room temperature to obtain reaction liquid of the phenoxy salt terminated intermediate.

(2) 0.4156g of 4-nitrophthalonitrile was added to the reaction solution of the phenoxide-terminated intermediate contained in step (1), and the temperature was raised to 100 ℃ to react for 12 hours. After the reaction is finished, adding the reaction solution into 500mL of boiling water with 15% hydrochloric acid concentration, continuously stirring, stirring at 100 ℃ for 30min, cooling to room temperature, and filtering to obtain a white strip-shaped prepolymer.

The white strip-shaped prepolymer is washed by distilled water for several times, then is dried in a vacuum drying oven at 80 ℃ for 24 hours and is subjected to soxhlet extraction by acetone for 24 hours, and is dried in vacuum at 110 ℃ for 24 hours, and the molar yield of the prepolymer is 94%.

And dissolving the prepolymer in N-methyl pyrrolidone, filtering, precipitating the solution into ethanol, filtering, washing with distilled water for several times, and vacuum-drying at 110 ℃ for 24 hours to obtain a white product serving as a target polymer. This purification removes small molecule impurities as well as cyclics.

The infrared spectrum is 1246cm^-1Characteristic absorption peaks of ether bonds appear. At 1512cm^-1And 1364cm^-1The characteristic absorption peak of the triazine ring appears. The characteristic absorption peak of the cyano group appears at 2234cm^-1To (3). 1310cm^-1，1150cm^-1Symmetric stretching vibration and asymmetric stretching vibration peaks of the sulfone group appear at the position. In a nuclear magnetic spectrum, a resonance peak belonging to proton hydrogen on a benzene ring in a diphenyl fluorenyl group appears near a chemical shift δ ═ 7.1, a hydrogen proton resonance peak adjacent to a triazine ring appears on the benzene ring at δ ═ 8.3 to 8.6, a resonance peak belonging to proton hydrogen on the benzene ring in the diphenyl fluorenyl group appears near the chemical shift δ ═ 7.1, and proton peaks belonging to a phthalonitrile group appear near δ ═ 7.4 and δ ═ 7.8. The above structural characterization demonstrated that the synthesized prepolymer was consistent with the assumptions.

Because the structure contains a bisphenylfluorene structure, the series of prepolymers have good solubility, can be dissolved in NMP, chloroform and tetrahydrofuran, and provide favorable conditions for preparing composite material prepreg sheets and preparing coatings by a solution impregnation method.

After adding curing agent diaminodiphenyl ether, the prepolymer is cured by reaction at 250 ℃ for 3h, 285 ℃ for 1h, 325 ℃ for 3h, 350 ℃ for 2h and 375 ℃ for 8h to obtain black cast-like cured product. In N of₂In the temperature range of 900 ℃, the carbon residue rate is up to 73 percent, the 5 percent thermal weight loss temperature is 591 ℃, and the glass transition temperature is 424 ℃.

EXAMPLE 5 preparation of a phthalonitrile resin containing a triaryl-s-triazine Structure, of the formula E (referred to as resin E for short)

Wherein the R1 and R2 groups are-CH₃And R3 radicals are all-SO₃H, a ═ 0.3, b ═ 0.7, the Ar3 group selected from the (z) structure, Ar2 selected from the (q) structure, R4 to R6 were all — H, and Ar1 selected from the (a) structure. The molecular weight of the polymer was 5500 by GPC, and the number of repeating structural units n was 10.3.

(1) In a 500mL three-necked flask equipped with mechanical stirring, a water-dividing condenser, and a nitrogen inlet, 16.68g of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one, 14.01g of 9, 9-bis (4-hydroxyphenyl) fluorene, 9.74g of 2,6 difluorobenzonitrile, and 14.44g of 2, 4-bis (3, 5-dimethyl-4-fluorophenyl) -6- (4-sulfophenyl) -1,3, 5-triazine, 17.93g of anhydrous potassium carbonate, 100mL of N-methylpyrrolidone, and 100mL of toluene were charged; refluxing with water at 150 ℃ for 3h, and evaporating toluene; continuously heating to 190 ℃ for reacting for 8h, supplementing a solvent according to the viscosity of the reaction system in the reaction process until the viscosity of the reaction system is not increased any more, wherein the amount of the supplemented solvent is 35 mL; and cooling to room temperature to obtain reaction liquid of the phenoxy salt terminated intermediate.

(2) 4.16g of 4-nitrophthalonitrile was added to the reaction solution of the phenoxide-terminated intermediate contained in step (1), and the temperature was raised to 80 ℃ to react for 12 hours. After the reaction is finished, adding the reaction solution into 2000mL of boiling water with hydrochloric acid concentration of 15%, continuously stirring, stirring at 100 ℃ for 30min, cooling to room temperature, and filtering to obtain a brown yellow strip prepolymer.

The brown yellow strip-shaped prepolymer is washed by distilled water for several times, then is dried in a vacuum drying oven at 80 ℃ for 24 hours, is subjected to soxhlet extraction by acetone for 24 hours, and is dried in vacuum at 110 ℃ for 24 hours, and the molar yield of the prepolymer is 92 percent.

And dissolving the prepolymer in N-methyl pyrrolidone, filtering, precipitating the solution into ethanol, filtering, washing with distilled water for several times, and vacuum-drying at 110 ℃ for 24 hours to obtain a brown yellow product as a target polymer. This purification removes small molecule impurities as well as cyclics.

In the infrared spectrum at 1251cm^-1Characteristic absorption peaks of ether bonds appear. At 1510cm^-1And 1358cm^-1The characteristic absorption peak of the triazine ring appears. The characteristic absorption peak of the cyano group appears at 2230cm^-1To (3). The characteristic absorption peak of methyl appears at 2900cm^-1A vicinity of the device. 1178cm^-1And 1007cm^-1The peak at (A) is a characteristic peak of the sulfonic acid group. In a nuclear magnetic spectrum, a resonance peak belonging to proton hydrogen on a benzene ring in a diphenyl fluorenyl group appears near a chemical shift δ of 7.1, a hydrogen proton resonance peak adjacent to a triazine ring appears on the benzene ring at δ of 8.3-8.6, and a hydrogen proton peak of a sulfonic acid group appears near the chemical shift δ of 11.0. A resonance peak belonging to proton hydrogen on the benzene ring in the biphenylfluorenyl group appears in the vicinity of a chemical shift δ ═ 7.1, and proton peaks belonging to the phthalonitrile group appear in the vicinity of δ ═ 7.4 and δ ═ 7.8. The hydrogen proton on the cyano-bearing benzene ring appears at a low field, i.e., δ ═ 7.9. The above structural characterization demonstrated that the synthesized prepolymer was consistent with the assumptions.

And reacting the prepolymer at 250 ℃ for 3h and at 280 ℃ for 12h under the protection of nitrogen, and curing to obtain a dark green cast condensate. The series of cured materials can be dissolved in NMP and can be paved into a film by a solution casting method. In N of₂Middle, 900 ℃ residueThe carbon rate reaches 73 percent, the 5 percent thermal weight loss temperature is 487 ℃, which is because the thermal stability of the polymer is reduced by the existence of sulfonic acid groups. The glass transition temperature was 357 ℃.

Example 6 preparation of a phthalonitrile resin containing a triaryl-s-triazine Structure, resin F for short

Formula f;

wherein the R1-R2 groups are-CH₃And R3 is-H. The a is 1, the b is 0, the Ar3 group adopts the (l) structure, and the Ar1 and Ar2 structures are not started. The molecular weight of the polymer was 997 by GPC, and the number of repeating structural units n was 1.5.

The preparation method comprises the following steps:

(1) in a 1000mL three-necked flask equipped with mechanical stirring, a water-dividing condenser, and a nitrogen inlet, 44.0g of hydroquinone, 80.3g of 2, 4-bis (3, 5-dimethyl-4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 66.2g of anhydrous potassium carbonate, 250mL of sulfolane, and 200mL of toluene were charged; refluxing with water at 150 ℃ for 6h, and evaporating toluene; continuously heating to 190 ℃ for reacting for 8h, supplementing a solvent according to the viscosity of the reaction system in the reaction process until the viscosity of the reaction system is not increased any more, wherein the amount of the supplemented solvent is 50 mL; and cooling to room temperature to obtain reaction liquid of the phenoxy salt terminated intermediate.

(2) 69.2g of 4-nitrophthalonitrile was added to the reaction solution of the phenoxide-terminated intermediate contained in step (1), and the temperature was raised to 80 ℃ to react for 12 hours. After the reaction is finished, adding the reaction solution into 3L of boiling water with hydrochloric acid concentration of 15%, continuously stirring, stirring at 100 ℃ for 30min, cooling to room temperature, and filtering to obtain light brown short strip-shaped prepolymer.

The crude product, namely the light brown short strip prepolymer, is washed for a plurality of times by distilled water, then is dried in a vacuum drying oven at 80 ℃ for 24h, is subjected to soxhlet extraction by acetone for 24h, and is dried in vacuum at 110 ℃ for 24h, and the molar yield of the prepolymer is 95%.

The structure of the polymer is consistent with that of the polymer through infrared and nuclear magnetism characterization, and the infrared spectrum is 1250cm^-1Characteristic absorption peaks of ether bonds appear. At 1511cm^-1And 1362cm^-1The characteristic absorption peak of the triazine ring appears. The characteristic absorption peak of the cyano group appears at 2235cm^-1To (3). In a nuclear magnetic spectrum, a resonance peak belonging to proton hydrogen on a benzene ring in a diphenyl fluorenyl group appears near a chemical shift delta-7.1, hydrogen proton resonance peaks adjacent to the triazine ring on the benzene ring appear at positions delta-8.3-8.6, and proton hydrogen on a p-phenylene group respectively appears near a low field delta-7.3. Proton peaks belonging to the phthalonitrile group occur in the vicinity of δ ═ 7.4 and δ ═ 7.8. The above structural characterization demonstrated that the synthesized prepolymer was consistent with the assumptions.

After adding curing agent diamino diphenyl sulfone, the prepolymer is cured through reaction at 250 deg.c for 3 hr, reaction at 285 deg.c for 1 hr, reaction at 325 deg.c for 3 hr, reaction at 350 deg.c for 2 hr, reaction at 375 deg.c for 4 hr and reaction at 400 deg.c for 4 hr to obtain black cast cured product. In N of₂In the temperature range of 900 ℃, the carbon residue rate is as high as 81%, the 5% thermal weight loss temperature is 569 ℃, and the glass transition temperature is 447 ℃. It is worth mentioning that the melting point of the prepolymer is 165 ℃ because the prepolymer structure contains methyl, p-phenylene and other flexible groups, the viscosity at 200 ℃ is 0.8 Pa.S, and the gel time at 200 ℃ is higher than 180min after the curing agent is added, so that the resin is suitable for resin transfer molding, resin vacuum infusion and other processes, and provides conditions for manufacturing large and complex devices by using the resin.

Example 7 preparation of a phthalonitrile resin containing a triaryl-s-triazine Structure, represented by the formula G (referred to as resin G for short)

Wherein, the R1-R3 groups are all-H, a is 0.5, b is 0.5, the Ar3 group adopts a structure (o), Ar1 adopts a structure (d), and Ar2 adopts a structure (n). The molecular weight of the polymer was 6750 by GPC, and the number of repeating structural units n was 7.5.

The preparation method comprises the following steps:

(1) in a 500mL three-necked flask equipped with mechanical stirring, a water-dividing condenser, and a nitrogen inlet, 9.1246g of bisphenol A (bisphenol A is 2, 2-bis (4, 4' -dihydroxybiphenyl) propane), 9.3150g of biphenyldiol, 13.8043g of 2, 4-bis (4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 7.8823g of 2, 6-dichloronaphthalene, 17.9286g of anhydrous potassium carbonate, 30mL of LN-methylpyrrolidone, and 100mL of toluene were charged; refluxing with water at 150 ℃ for 4h, and evaporating toluene; continuously heating to 190 ℃ for reacting for 8h, supplementing a solvent according to the viscosity of the reaction system in the reaction process until the viscosity of the reaction system is not increased any more, wherein the amount of the supplemented solvent is 30 mL; and cooling to room temperature to obtain reaction liquid of the phenoxy salt terminated intermediate.

(2) 4.1552g of 4-nitrophthalonitrile was added to the reaction solution of the phenoxide-terminated intermediate contained in step (1), and the temperature was raised to 100 ℃ to react for 12 hours. After the reaction is finished, adding the reaction solution into 1000mL of boiling water with 15% hydrochloric acid concentration, continuously stirring, stirring at 100 ℃ for 30min, cooling to room temperature, filtering, and collecting solids to obtain the brown short-strip prepolymer.

The structure of the polymer is consistent with that of the polymer through infrared and nuclear magnetism characterization, and the infrared spectrum is 1250cm^-1Characteristic absorption peak of ether bond; at 1512cm^-1And 1364cm^-1A characteristic absorption peak of the triazine ring appears; the characteristic absorption peak of the cyano group appears at 2234cm^-1To (3). In a nuclear magnetic spectrum, a resonance peak of proton hydrogen on an isopropyl group in bisphenol A appears near a chemical shift delta & lt 3.0 & gt, and a resonance peak of proton hydrogen on a benzene ring appears at a position delta & lt 8.3-8.6 & gtAnd hydrogen proton resonance peaks at the ortho position of the triazine ring and hydrogen protons in naphthyl respectively appear in the vicinity of 7.6-7.9 in a low field. The proton hydrogen on the biphenyl group occurs in the range of 7.2 to 7.5. Proton peaks belonging to the phthalonitrile group occur in the vicinity of δ ═ 7.4 and δ ═ 7.8. The above structural characterization demonstrated that the synthesized prepolymer was consistent with the assumptions.

After adding curing agent diamino diphenyl sulfone, the prepolymer is cured through reaction at 250 deg.c for 3 hr, reaction at 285 deg.c for 1 hr, reaction at 325 deg.c for 3 hr, reaction at 350 deg.c for 2 hr and reaction at 375 deg.c for 8 hr to obtain black cast cured product. In N of₂In the method, the residual carbon rate at 900 ℃ reaches 69%, the 5% thermal weight loss temperature is 579 ℃, and the glass transition temperature is 449 ℃. Because the bisphenol A is used in the synthetic monomer, the preparation cost of the structural thermosetting resin is reduced, and the structural thermosetting resin is a high-temperature-resistant material with relatively good cost performance and can be used as a high-temperature-resistant adhesive, a composite material basic resin, a high-temperature-resistant shape memory material, a wave-transmitting material and the like.

EXAMPLE 8 preparation of a phthalonitrile resin having a triaryl-s-triazine Structure (abbreviated as resin H) of the formula H

Wherein, the R1-R3 groups are all-H, a is 0.5, b is 0.5, the Ar3 group adopts a structure (p), Ar2 adopts a structure (u), and Ar1 adopts a structure (e). The molecular weight of the polymer was 11000 as determined by GPC, and the number n of repeating structural units was 10.2.

The preparation method comprises the following steps:

(1) in a 500mL three-necked flask equipped with mechanical stirring, a water-dividing condenser, and a nitrogen inlet, 9.6103g of 2, 6-naphthalenediol, 15.9164g of phenolphthalein, 16.1155g of 1, 4-bis (4-fluorobenzoyl) benzene, 17.2554g of 2, 4-bis (4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 19.3077g of anhydrous potassium carbonate, 40mL of dimethyl sulfoxide, and 100mL of toluene were charged; refluxing with water at 150 ℃ for 3h, and evaporating toluene; continuously heating to 190 ℃ for reaction for 7h, supplementing a solvent according to the viscosity of the reaction system in the reaction process until the viscosity of the reaction system is not increased any more, wherein the amount of the supplemented solvent is 20 mL; and cooling to room temperature to obtain reaction liquid of the phenoxy salt terminated intermediate.

(2) 4.1551g of 4-nitrophthalonitrile was added to the reaction solution of the phenoxide-terminated intermediate contained in step (1), and the temperature was raised to 100 ℃ to react for 18 hours. After the reaction is finished, adding the reaction solution into boiling water containing 1500mL hydrochloric acid with the concentration of 15%, continuously stirring, stirring at 100 ℃ for 30min, cooling to room temperature, filtering, and collecting solids to obtain a brown strip-shaped prepolymer.

The brown long-strip prepolymer is washed by distilled water for several times, then is dried in a vacuum drying oven at 80 ℃ for 24 hours, is subjected to soxhlet extraction by acetone for 24 hours, and is dried in vacuum at 110 ℃ for 24 hours, and the molar yield of the prepolymer is 95%.

And dissolving the prepolymer in N-methyl pyrrolidone, filtering, precipitating into ethanol, filtering, washing with distilled water for several times, and vacuum drying at 110 ℃ for 24h to obtain a brown product serving as a target polymer. This purification removes small molecule impurities as well as cyclics.

The infrared spectrum is 1246cm^-1Characteristic absorption peaks of ether bonds appear. At 1508cm^-1And 1362cm^-1The characteristic absorption peak of the triazine ring appears. The characteristic absorption peak of the cyano group appears at 2234cm^-1To (3). 1715cm^-1At which a ketone carbonyl absorption peak appears at 1750cm^-1An ester carbonyl absorption peak appears.

Adding curing agent diamino diphenyl sulfone, reacting the prepolymer at 250 ℃ for 3h, 285 ℃ for 1h, 325 ℃ for 3h, 350 ℃ for 2h and 375 ℃ for 8h to obtain black cast-shaped cured product. In N of₂In the method, the carbon residue rate at 900 ℃ is up to 82%, the 5% thermal weight loss temperature is 593 ℃, and the glass transition temperature is 498 ℃. The series of the high-temperature-resistant composite material has excellent thermal performance and can be used as a high-temperature-resistant adhesive, composite material matrix resin, a high-temperature-resistant shape memory material, a wave-transmitting material, a toughening agent and the like.

Example 9 preparation of a phthalonitrile resin having a triaryl-s-triazine Structure (abbreviated as resin I) of the formula I

Wherein R1-R2 groups are all-CF₃And R3 is-H. The a is 0.5, the b is 0.5, the Ar3 group is (v), the Ar2 group is (r), and the Ar1 group is (g). The molecular weight of the polymer was 3220 by GPC, and the number of repeating structural units, n, was about 2.3.

The preparation method comprises the following steps:

(1) in a 500mL three-necked flask equipped with mechanical stirring, a water-dividing condenser, and a nitrogen inlet, 10.0817g of bisphenol AF (bisphenol AF is 2, 2-bis (4, 4' -dihydroxydiphenyl) hexafluoropropane), 6.4069g of phenolphthalein, 6.2854g of bis (4-fluorophenyl) phenylphosphine oxide and 12.3469g of 2, 4-bis (2, 5-bistrifluoromethyl-4-fluorophenyl) -6-phenyl-1, 3, 5-triazine, 6.8956g of anhydrous potassium carbonate, 50mL of N, N-dimethylformamide, and 100mL of toluene were charged; refluxing with water at 150 ℃ for 3h, and evaporating toluene; and continuously heating to 190 ℃ for reaction for 6h, and cooling to room temperature to obtain reaction liquid of the phenoxy salt terminated intermediate.

(2) 3.8088g of 4-nitrophthalonitrile was added to the reaction solution of the phenoxide-terminated intermediate contained in step (1), and the temperature was raised to 100 ℃ to react for 12 hours. After the reaction is finished, adding the reaction solution into 500mL of boiling water with 15% hydrochloric acid concentration, continuously stirring, stirring at 100 ℃ for 30min, cooling to room temperature, and filtering to obtain a white strip-shaped prepolymer.

The white strip-shaped prepolymer is washed by distilled water for several times, then is dried in a vacuum drying oven at 80 ℃ for 24 hours and is subjected to soxhlet extraction by acetone for 24 hours, and is dried in vacuum at 110 ℃ for 24 hours, and the molar yield of the prepolymer is 92%.

And dissolving the prepolymer in N-methyl pyrrolidone, filtering, precipitating into ethanol, filtering, washing with distilled water for several times, and vacuum drying at 110 ℃ for 24h to obtain a white product serving as a target polymer. This purification removes small molecule impurities as well as cyclics.

In the infrared spectrum at 1251cm^-1Characteristic absorption peaks of ether bonds appear. At 1513cm^-1And 1362cm^-1The characteristic absorption peak of the triazine ring appears. The characteristic absorption peak of the cyano group appears at 2232cm^-1To (3). 1760cm^-1Shows a vibration peak of carboxyl group, 1270cm^-1The C-F peak stretching vibration peak is generated at 1150cm^-1And a P ═ O bond stretching vibration peak appears at the position. In a nuclear magnetic spectrum, a resonance peak belonging to proton hydrogen on a benzene ring in a diphenyl fluorenyl group appears near a chemical shift δ ═ 7.1, a hydrogen proton resonance peak adjacent to a triazine ring appears at δ ═ 8.3 to 8.6, a characteristic single peak of carboxyl hydrogen appears near δ ═ 13.5, and proton peaks belonging to a phthalonitrile group appear near δ ═ 7.4 and δ ═ 7.8. The above structural characterization demonstrated that the synthesized prepolymer was consistent with the assumptions.

After adding curing agent diaminodiphenyl ether, the prepolymer is cured by reaction at 250 ℃ for 3h, 285 ℃ for 1h, 325 ℃ for 3h, 350 ℃ for 2h and 375 ℃ for 8h to obtain black cast-like cured product. In N of₂In the temperature range of 900 ℃, the carbon residue rate is as high as 84%, the 5% thermal weight loss temperature is 598 ℃, and the glass transition temperature is 464 ℃. This is due to the introduction of-CF into the structure₃Increases intermolecular forces, and restricts the movement of the polymer backbone. The dielectric property test shows that the dielectric constant of the series of cured materials is 2.6-2.7, and the series of cured materials belong to ultra-low dielectric materials. Therefore, the series of resins have the potential of being used as high-temperature-resistant adhesives, composite material matrix resins, high-temperature-resistant shape memory materials, wave-transparent materials and the like.

Examples 10 to 18

Examples 10-18 are examples of the preparation of reinforcements A-I using resins A-I, respectively.

The preparation processes of examples 10 to 18 were the same except that the resins were different, and the specific preparation methods were as follows:

1) the method comprises the steps of dissolving phthalonitrile resin containing a triaryl s-triazine structure and a curing agent 4, 4' -diaminodiphenyl sulfone in an N-methylpyrrolidone (NMP) solvent according to a mass ratio of 20:1 to prepare a suspension resin solution, namely a glue solution, of which the total mass percentage concentration of the two solutes is 35%. According to the physical properties of the resin, if the resin can be melted at a temperature below 250 ℃ (such as A, B, C, F), the resin and the curing agent are heated to 250 ℃ to melt and react for 10min, and then NMP (N-methyl pyrrolidone) is added after cooling and stirred until a glue solution is formed; if the resin can not be melted at a temperature below 250 ℃ because of high molecular weight (such as resin D, E, G, H, I), the resin and the curing agent are directly mixed, dissolved and dispersed in solvent NMP to prepare glue solution.

2) Dipping a continuous T800 type carbon fiber bundle in glue solution, winding the glue solution on a steel frame in a one-way mode, wherein the dipping time is 10-50 s, and then drying the steel frame at 180 ℃ for 36 h; obtaining a prepreg;

3) naturally cooling to room temperature, and cutting into 100 × 60mm²The test piece of (1) was placed in a mold coated with a mold release agent (model RVU-3580, DINO-CATE) and heated. If the resin can be melted at a temperature of 250 ℃ or below (such as resin A, B, C, F), heating to 250 ℃; if the resin cannot be melted at a temperature of 250 ℃ or lower (e.g., resin D, E, G, H, I) due to its high molecular weight, the temperature is raised to 300 ℃. And meanwhile, pressurizing to 2.5MPa, keeping the pressure for 2h, and cooling and demolding to obtain the fiber reinforced resin matrix pre-cured sheet.

4) Curing according to the curing process of 250 ℃/1h +285 ℃/2h +325 ℃/3h +350 ℃/2h +375 ℃/8h to finally obtain the phthalonitrile resin-based continuous carbon fiber composite material laminated plate (100 multiplied by 60 multiplied by 2 mm) with the main chain containing the triaryl s-triazine structure³). In the composite material, the weight ratio of the glue to the fiber material is in the range of 3: 7-4: 6.

The mechanical properties of the composite material are tested according to ASTM D790 and ISO 14130 standards, and the material size is 80X 10X 2mm³And taking the average value of 5 groups of parallel experiments as an experiment result. The resin mass content of the composite material is according to ASTM D3171-11 test standard. Respectively placing the samples at 450 ℃ for 20min, and testing the high-temperature mechanical property of the material according to the standard.

The properties of the composite reinforcements obtained in examples 10 to 18 are shown in Table 1.

Example 19

1) Putting the resin B and the curing agent 4,4 '-diaminodiphenylmethane in a three-neck flask according to the mass ratio of 20:1, heating to 250 ℃ for reaction for 10min to generate B-stage resin, cooling, adding the B-stage resin into an N-methylpyrrolidone (NMP) solvent, stirring until the B-stage resin is dissolved, adding a certain mass of alumina powder, and preparing 35% (the total mass fraction of the resin B, the curing agent 4, 4' -diaminodiphenylmethane and the alumina) of a suspended resin solution, namely a glue solution.

2) Cutting to obtain a product with a size of 100 × 100mm²And (3) soaking the glass fiber in the glue solution for 10-50 s, and drying to obtain the pre-cured sheet.

3) Placing in a mold coated with composite material release agent (model RVU-3580, DINO-CATE), heating to 250 deg.C, pressurizing for 2.4MPa, maintaining pressure for 1.5 hr, cooling, and demolding to obtain fiber reinforced resin based prepreg.

4) And curing the raw materials sequentially according to the curing process of 250 ℃/1h +285 ℃/2h +325 ℃/3h +350 ℃/2h +375 ℃/8h to finally obtain the phthalonitrile resin-based glass fiber composite material with the main chain containing the triaryl s-triazine structure, wherein the weight ratio of the rubber to the fiber material in the composite material is 34: 66.

The properties of the fiber composite reinforced material of this example were measured in the same manner as in example 10, and the results are shown in Table 1.

Example 20

1) Putting the resin C and the curing agent 4, 4' -diaminodiphenyl methyl ether in a three-neck flask according to the mass ratio of 20:1, heating to 250 ℃ to react for 10min to generate B-stage resin, and grinding into powder. And adding 15 percent of filler silicon nitride and 50mL of solvent N, N-dimethylacetamide based on the total mass of the resin and the curing agent. Then adding 10 mass percent of T300 chopped carbon fiber based on the total mass of the resin, the curing agent and the inorganic filler, and uniformly mixing. The solvent was evaporated off and dried at 180 ℃ for 36h to obtain a pre-pressed tablet.

2) Adding into a mold coated with a mold release agent (model RVU-3580, DINO-CATE), and performing a certain mold pressing process (at 250 ℃, under 1.5MPa and under 1h of pressure holding time) to obtain a carbon fiber reinforced resin-based pre-cured sheet;

3) and curing according to the curing process of 250 ℃/1h +285 ℃/2h +325 ℃/3h +350 ℃/2h +375 ℃/8h to finally obtain the phthalonitrile resin-based carbon fiber composite material with the main chain containing the triaryl s-triazine structure.

The dielectric constant of the composite material obtained in this example was 3.7, and it was a good wave-transmitting material.

Example 21

1) Resin F, curing agent 4, 4' -diaminodiphenyl sulfone and curing accelerator cobalt acetylacetonate are mixed according to the weight ratio of 20: 1: placing the mixture into a three-neck flask according to the mass ratio of 0.02, heating to 250 ℃ to react for 10min to generate B-stage resin, cooling, and adding 30mLN, N-dimethylformamide. And adding filler boron nitride accounting for 15 percent of the total mass of the resin, the curing agent and the curing accelerator and carbon nano tubes accounting for 30 percent of the total mass of the resin, the curing agent, the curing accelerator and the filler, and uniformly mixing. The solvent was then distilled off and dried at 160 ℃ for 36 h. The raw materials are evenly mixed.

2) Adding into a mold coated with a mold release agent (model RVU-3580, DINO-CATE), and obtaining a resin-based prepreg according to a certain mold pressing process;

3) and curing according to the curing process of 250 ℃/1h +285 ℃/2h +325 ℃/3h +350 ℃/2h +375 ℃/8h to finally obtain the phthalonitrile resin-based carbon nanotube composite material with the main chain containing the triaryl s-triazine structure.

The dielectric constant of the composite material obtained in this example was 3.4, and it was a good wave-transmitting material.

Example 22

1) Dissolving resin A, curing agent 2, 6-bis (4-aminophenoxy) benzonitrile and curing accelerator cobalt acetylacetonate in 30mL of dimethyl sulfoxide according to the mass ratio of 20g:1g:0.02g, adding inorganic filler silicon dioxide accounting for 30% of the total mass of the resin, the curing agent and the curing accelerator, and heating and stirring to prepare a suspension resin solution, namely glue solution. Mixing 6 layers of 100 × 60mm²And (3) soaking the quartz fiber with the size in the glue solution for 10-50 s, taking out, and drying at 190 ℃ for 36h to obtain the prepreg sheet.

2) And (3) placing the 6 layers of sheets into a mold coated with a release agent (model RVU-3580, DINO-CATE), heating to 300 ℃, pressurizing for 2.5MPa, keeping for 30min, and demolding to obtain the fiber reinforced resin-based pre-cured sheet.

3) And curing according to the curing process of 250 ℃/3h +285 ℃/2h +325 ℃/3h +350 ℃/4h +375 ℃/4h +400 ℃/4h to finally obtain the quartz fiber reinforced composite material.

The dielectric constant of the material is 3.9, and the material is a good wave-transmitting material.

Example 23

1) Mixing resin D and curing agent bis [4- (4-aminophenoxy) benzene]Sulfone and 1.5g of the sulfone are placed in a three-neck flask according to the mass ratio of 20g to 1.5g, 50mL of N-methyl pyrrolidone (NMP) solvent is added, the mixture is heated and stirred until the mixture is dissolved, silicon carbide powder accounting for 10 percent of the total mass of the resin and the curing agent is added, and the stirring is continued to obtain a suspension-shaped resin solution, namely a glue solution. Cutting 12 layers into 100 × 100mm²And (3) soaking the T300 fiber cloth in the glue solution for 10-50 s, and drying for 36h at 200 ℃ to obtain a prepreg.

2) And (3) placing the 12 layers of pre-cured sheets into a mold coated with a release agent (model RVU-3580, DINO-CATE), heating to 250 ℃, pressurizing to 3.5MPa, keeping the pressure for 2.0h, and demolding to obtain the pre-cured plate.

3) And then curing according to the curing process of 250 ℃/1h +325 ℃/3h +350 ℃/2h +375 ℃/8h to finally obtain the phthalonitrile resin reference ceramic material.

The properties of the fiber composite reinforced material of this example were measured in the same manner as in example 10, and the results are shown in Table 1. It has good heat resistance and mechanical property. Meanwhile, the thermal conductivity of the material is 5.86W/mK, and the material is a good heat conduction material.

TABLE 1 Performance data for composite reinforcements obtained in examples 10-23

Claims

1. The bis-phthalonitrile resin fiber reinforced material containing the triaryl s-triazine structure is characterized by consisting of glue and a fiber material, wherein the mass ratio of the glue to the fiber material is 1.0-99.9: 100, respectively;

wherein Ar1 is any one of the following structures (a) and (d):

ar2 and Ar3 have any one of the following structures (l), (n), (o) and (z):

ar2 and Ar3 are the same or different;

in the formulae: r1, R2 and R3 are hydrogen or alkyl of C1-C10, and R1, R2 and R3 are the same or different; a + b is 1, and 0< a <1, 0< b <1, wherein a and b are the molar percentage content of the corresponding units respectively; n > 0; the number average molecular weight of the resin detected by GPC is 500-;

or the bis-phthalonitrile resin containing the triaryl s-triazine structure has a structural general formula as follows:

，

formula d, n is 10.2.

2. The bisphthalonitrile resin fiber reinforced material of claim 1, wherein the mass fraction of the glue in the reinforced material is 30-50%.

3. The bisphthalonitrile resin fiber reinforced material of claim 1, wherein the glue further comprises the following components: curing agent, curing accelerator and filler.

4. The bisphthalonitrile resin fiber reinforcement material of claim 3, wherein the curing agent is selected from one or more of metals, metal salts, organic amines, organic acids and organic anhydrides.

5. The bisphthalonitrile resin fiber reinforcement material according to claim 3, the curing accelerator is selected from one or more of tetrabutylammonium bromide, tri-2-ethylhexanoate of DMP-30, imidazole, 2-methylimidazole, 2, 4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1,3, 5-triethyl-hexahydro-s-triazine, 1,3, 5-trimethyl-hexahydro-s-triazine, triethylamine, triethanolamine, benzyldimethylamine, triphenylphosphine, triethylphosphine, acetylacetone transition metal compounds and phthalein acetone rare earth compounds.

6. The bisphthalonitrile resin fiber reinforcement material of claim 5, wherein the acetylacetonato transition metal compound is cobalt acetylacetonate.

7. The bisphthalonitrile resin fiber reinforcement material of claim 3, wherein the filler is one or both of an inorganic filler and a functionalized filler.

8. The bisphthalonitrile resin fiber reinforcement material according to claim 7, wherein the inorganic filler is selected from one or more of graphite, elemental metals, alloys, metal oxides, metal hydroxides, metal nitrides and metal salts.

9. The bisphthalonitrile resin fiber reinforcement material of claim 7, wherein the functionalized filler is selected from one or more of non-metallic oxides, non-metallic nitrides, non-metallic carbides, and minerals.

10. The bisphthalonitrile resin fiber reinforced material of claim 1, wherein the alkyl group having from C1 to C10 is a methyl group.

11. The bisphthalonitrile resin fiber reinforced material of claim 3, wherein the mass ratio of the bisphthalonitrile resin containing a triaryl s-triazine structure to the curing agent is 0.5-1000: 1; the amount of the filler is 0-99.0% of the total mass of the bis-phthalonitrile resin containing the triaryl s-triazine structure, the curing agent and the curing accelerator, wherein 0 is excluded; the dosage of the curing accelerator is 0-3.0% of the total weight of the phthalonitrile resin containing the triaryl s-triazine structure, wherein 0% is excluded.

12. The bisphthalonitrile resin fiber reinforced material of claim 11, wherein the mass ratio of the bisphthalonitrile resin containing the triaryl s-triazine structure to the curing agent is 10-40: 1.

13. the fibrous reinforcement of a bisphthalonitrile resin according to claim 11, wherein the filler is used in an amount of 1 to 30% by mass based on the total mass of the bisphthalonitrile resin having a triaryl-s-triazine structure, the curing agent and the curing accelerator.

14. The bis-phthalonitrile resin fibrous reinforcement according to claim 11, wherein the curing accelerator is used in an amount of 0.1 to 2% by weight based on the total weight of the tris-aryl-s-triazine structure-containing phthalonitrile resin.

15. The bisphthalonitrile resin fiber reinforcement material of claim 1, wherein the fiber material is selected from one or more of glass fibers, carbon fibers, boron fibers, silicon carbide fibers, carbon nanotubes, basalt fibers, silica fibers, alumina fibers, aramid fibers, polyester fibers, and cellulose fibers; or the fiber material is a fabric or a fiber web made of glass fibers, carbon fibers, boron fibers, silicon carbide fibers, carbon nanotubes, basalt fibers, silica fibers, alumina fibers, aramid fibers, polyester fibers, or cellulose fibers.

16. A process for producing a fibrous reinforcement of a bisphthalonitrile resin as claimed in any one of claims 1 to 15, which comprises a step of compounding a rubber, a step of dipping a rubber, a step of molding and a step of curing.

17. The production method according to claim 16, wherein in the step of compounding the paste, a bis-phthalonitrile resin having a triaryl-s-triazine structure, a curing agent, a curing accelerator, and a filler are added to an organic solvent and dissolved to produce an organic solution.

18. The preparation method of the compound of the formula I, wherein the compound is prepared by mixing a bis-phthalonitrile resin containing a triaryl s-triazine structure, a curing agent and a curing accelerator, heating to a molten state, reacting for 1-60 min to form a B-stage resin, cooling to room temperature, adding an organic solvent and a filler, and fully stirring to obtain an organic solution stable at room temperature, wherein the mass ratio of the B-stage resin to the organic solvent is 1:1.25-100, and the mass of the filler is 0-99% of that of the B-stage resin, except for 0%; the dosage of the curing accelerator is 0-3.0% of the total weight of the phthalonitrile resin containing the triaryl s-triazine structure, wherein 0% is excluded.

19. The method of claim 18, wherein the temperature in the molten state is 100 to 300 ℃.

20. The method according to claim 17, wherein the organic solvent is one or more of halogenated alkane, ethyl acetate, tetrahydrofuran, benzene, toluene, ethylbenzene, chlorobenzene, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone.

21. The preparation method according to claim 16, wherein in the impregnation step, the fiber material is passed through a impregnation tank containing the organic solution at a speed of 0.01m/s to 1m/s to ensure sufficient impregnation of the fibers to obtain a fiber prepreg sheet, and then the fiber prepreg sheet is dried.

22. The method according to claim 21, wherein the drying temperature is 40 to 200 ℃ so that the volatile component content is less than 0.2 wt%.

23. The method of claim 22, wherein the drying temperature is 150 ℃.

24. The production method according to claim 21, wherein in the molding step, a plurality of the fiber prepreg sheets are laid in a mold and molded by autoclave, lamination or resin transfer molding technique to obtain a prepreg sheet of a fiber-reinforced bis-phthalonitrile resin containing a triaryl-s-triazine structure.

25. The method according to claim 24, wherein in the molding step, the molding temperature is 250 to 350 ℃, the molding pressure is 0.1 to 10.0MPa, and the pressure holding time is 0.5 to 8 hours.

26. The method according to claim 25, wherein the molding temperature is 250 ℃, the molding pressure is 0.5MPa, and the pressure holding time is 2 hours.

27. The production method according to claim 24, wherein in the curing step, the curing conditions of the preform are: the temperature is increased in a gradient manner between 200 ℃ and 425 ℃ for 4 to 12 times.

28. The preparation method of claim 27, wherein the temperature is raised for 6 times, and the temperature is maintained for 0.5-16 h in each stage, so as to obtain the phthalonitrile resin fiber reinforced material containing the triaryl s-triazine structure.

29. The method of claim 27, wherein the curing conditions are pre-tabletting temperature is raised to 250 ℃ and held for 3 hours, then to 285 ℃ and held for 1 hour, then to 325 ℃ and held for 3 hours, then to 350 ℃ and held for 2 hours, then to 375 ℃ and held for 4 hours, and finally to 400 ℃ and held for 4 hours.