A perylene-based nitrogen-containing organic derivative, a modified resin, a preparation method, a composite material, and an application

Abstract

The application provides a perylene-based nitrogen-containing organic derivative, a modified resin and a preparation method, a composite material and application, relates to the technical field of materials, and the structural formula of the derivative is shown as formula I: R is a substituent group containing a cyano group or an amino group or an N-containing heterocycle. The application also provides a preparation method, application, modified resin, preparation method, composite material and application of the perylene-based nitrogen-containing organic derivative. The perylene-based nitrogen-containing organic derivative, the modified resin and the preparation method, the composite material and the application provided by the application can improve the poor mechanical property of bismaleimide resin.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of resin modification, in particular to a perylene-based nitrogen-containing organic derivative, a modified resin, a preparation method, a composite material and application. BACKGROUND

[0002] Bismaleimide resin (BMI) is a kind of bifunctional compound with maleimide (MI) as an active end group, and is a kind of widely used thermosetting polymer. The bismaleimide resin has excellent high-temperature resistance, radiation resistance, moisture resistance and flame resistance, and the like, and has better heat resistance than epoxy resin (EP) and better processability than polyimide. The bismaleimide resin has good compatibility with other high-performance resins, and is widely used in aerospace, electronics, machinery and the like. However, the bismaleimide resin has poor toughness, and has high crosslinking density after curing, which leads to high brittleness and poor impact resistance of the material, and greatly limits the application of the bismaleimide resin in many important fields, and therefore the bismaleimide resin needs to be toughened and modified. SUMMARY

[0003] The application aims to provide a perylene-based nitrogen-containing organic derivative.

[0004] The application further aims to provide a perylene-based nitrogen-containing organic nanosheet.

[0005] The application further aims to provide a preparation method of the perylene-based nitrogen-containing organic nanosheet.

[0006] The application further aims to provide application of the perylene-based nitrogen-containing organic nanosheet.

[0007] The application further aims to provide a modified resin.

[0008] The application further aims to provide a preparation method of the modified resin.

[0009] The application further aims to provide a composite material.

[0010] The application further aims to provide application of the modified resin.

[0011] In order to achieve the above-mentioned purposes, the application provides the following technical solutions.

[0012] In a first aspect, the application provides a perylene-based nitrogen-containing organic derivative, and a structural formula of the derivative is shown as formula I:

[0013]

[0014] Formula I

[0015] The R is a substituent containing a cyano group or an amino group or an N-containing heterocyclic ring.

[0016] Further, in some embodiments of the present application, the structure of the perylenyl nitrogen-containing organic derivative is:

[0017]

[0018]

[0019] In a second aspect, the present application also provides a perylenyl nitrogen-containing organic nanosheet composed of the compound of the first aspect.

[0020] Further, in some embodiments of the present application, the perylenyl nitrogen-containing organic nanosheet is a crystalline nanosheet with rigid conjugated planar structure.

[0021] Further, in some embodiments of the present application, the perylenyl nitrogen-containing organic nanosheet has a width of 50-100 nm and a length of 100-550 nm.

[0022] In a third aspect, the present application also provides a method for preparing a perylenyl nitrogen-containing organic nanosheet, wherein the perylenyl nitrogen-containing organic nanosheet is prepared by condensation of a perylene derivative and a nitrogen-containing compound.

[0023] Further, in some embodiments of the present application, the method for preparing a perylenyl nitrogen-containing organic nanosheet comprises:

[0024] providing a perylene derivative, a nitrogen-containing compound, and a first solvent;

[0025] mixing the perylene derivative, the nitrogen-containing compound, and the first solvent, and performing a solvothermal reaction at a temperature of 180-220°C for 40-80 h;

[0026] after the solvothermal reaction is completed, removing the first solvent, and freeze-drying to obtain a perylenyl nitrogen-containing organic nanosheet.

[0027] Further, in some embodiments of the present application, the perylene derivative is 3,4,9,10- perylenetetracarboxylic dianhydride, 2,9-bis(9H-purin-6-yl)anthracene[2,1,9-def:6,5-10-def']diisoquinoline- 1,3,8,10(2H,9H)-tetraone, 2,9-bis(4,6-diamino-1,3,5-triazin-2-yl)anthracene[2,19-def:6,5-10-def']diisoquinoline- 1,3,8,10(2H,9H)-tetraone, 2,9-bis([1,2,4]triazolo[4,3-b][1,2,4,5]tetrazin-3-yl)anthracene[2,1,9-def:6,5,10-def']diisoquinoline- 1,3,8,10(2H,9H)-tetraone, 2,9-bis(5-amino-4H-1,2,3-triazol-4-yl)anthracene[2,19-def:6,5-10-def']diisoquinoline- 1,3,8,10(2H,9H)-tetraone, 3,3'-(1,3,8,10-tetraoxo-1,3,8,10-tetrahydroanthracene[2,1,9-def:6,5-10-def']diisoquinoline-2,9-diyl)bis(1H-pyrazole-4-carbonitrile), 2,9-bis(3,5-dinitro-1H-pyrazol-4-yl)anthracene[2,19-def:6,5-10-def']diisoquinoline- 1,3,8,10(2H,9H)-tetraone, 2,9-bis(4-methyl-1,2,5-oxadiazol-3-yl)anthracene[2,19-def:6,5-10-def']diisoquinoline- 1,3,8,10(2H,9H)-tetraone, 2,9-bis(4-amino-3,6-dinitropyrazolo[4,3-c]pyrazol-1(4H)-yl)anthracene[2,19-def:6,5-10-def']diisoquinoline- 1,3,8,10(2H,9H)-tetraone, 2,9-bis(1-vinyl-1H-tetrazol-5-yl)anthracene[2,1,9-def:6,5-10-def']diisoquinoline- 1,3,8,10(2H,9H)-tetraone, 4,4'-(1,3,8,10-tetraoxo-1,3,8,10-tetrahydroanthracene[2,1,9-def:6,5-10-def']diisoquinoline-2,9-diyl)dibenzonitrile.

[0028] The nitrogen-containing compound is one or more of dicyandiamide, 6-methyladenosine, melamine, [1,2,4]triazolo[4,3-b][1,2,4,5]tetrazin-3-amine, tetrazole-1,5-diamine, 3-amino-4-cyanopyrazole, 3,5-dinitro-1H-pyrazole-4-amine, 4-methyl-1,2,5-oxadiazole-3-amine, 3,6-dinitropyrazolo[4,3-c]pyrazole-1,4-diamine, 1-vinyl-1H-tetrazole-5-amine, 4-aminophthalonitrile, or a mixture of two or more thereof.

[0029] The first solvent is at least one selected from N,N-dimethylformamide, ethylene glycol, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylaniline, 1,2-propanediol, dimethyl sulfoxide.

[0030] Further, in some embodiments of the present application, the mass ratio of the perylene derivative and the nitrogen-containing compound is 1:(1-10).

[0031] The concentration of the perylene derivative in the first solvent is 0.01-0.1 g / mL; and the concentration of the nitrogen-containing compound in the first solvent is 0.02-0.2 g / mL.

[0032] In a fourth aspect, the present application also provides a use of the perylene-based nitrogen-containing organic derivative of the first aspect, or the perylene-based nitrogen-containing organic nanosheet of the second aspect, or the perylene-based nitrogen-containing organic nanosheet prepared by the preparation method of the third aspect, in the modification of resin, organic photocatalyst, organic semiconductor, and optoelectronics.

[0033] In a fifth aspect, the present application also provides a modified resin, wherein the modified resin is a resin modified by a perylene-based nitrogen-containing organic nanosheet; and the perylene-based nitrogen-containing organic nanosheet is a nanosheet formed by a perylene derivative and a nitrogen-containing compound, or the perylene-based nitrogen-containing organic nanosheet of the second aspect, or the perylene-based nitrogen-containing organic nanosheet prepared by the preparation method of the third aspect.

[0034] Further, in some embodiments of the present application, the bismaleimide resin is a resin formed by a bismaleimide monomer, and the bismaleimide monomer is at least one selected from the following formulae:

[0035]

[0036] In a sixth aspect, the present application also provides a preparation method of the modified resin of the fourth aspect, characterized in that, the method comprises:

[0037] providing a perylene-based nitrogen-containing organic nanosheet and a bismaleimide resin;

[0038] The perylene-based nitrogen-containing organic nanosheets and bismaleimide resin were mixed using a grinding process to obtain a blend;

[0039] The blend was cured using a gradient curing process and then cooled to obtain a modified resin.

[0040] Furthermore, in some embodiments of this application, the gradient curing process includes: curing at 100℃~130℃ for 1~3h, curing at 160℃~180℃ for 2~4h, and curing at 200℃~260℃ for 2~6h.

[0041] Furthermore, in some embodiments of this application, the mass ratio of the perylene-based nitrogen-containing organic nanosheets, the diamine, and the bismaleimide is (0.001–0.005):1.

[0042] Furthermore, in some embodiments of this application, a diamine is added to the blend, wherein the amount of the diamine added is 0.1 wt% to 0.5 wt% of the total mass of the perylene-based nitrogen-containing organic nanosheets, the diamine, and the bismaleimide.

[0043] In a seventh aspect, this application also provides a composite material, comprising the modified resin prepared by the method described in the fourth aspect or the modified resin described in the fifth aspect.

[0044] Eighthly, this application also provides the application of perylene derivatives, nitrogen-containing compounds, or perylene-based nitrogen-containing organic nanosheets prepared by the preparation method of perylene-based nitrogen-containing organic nanosheets described in the second aspect or the third aspect, or modified resins prepared by the preparation method of modified resins described in the fifth aspect or the sixth aspect, in the field of aerospace materials.

[0045] This application provides a perylene-based nitrogen-containing organic derivative, which is a compound with perylene and imide groups formed by a perylene derivative and a nitrogen-containing organic compound. Due to the large π-π conjugation of its benzene ring and the p-π conjugation linked to the benzene ring, this compound has extremely high planarity and a very high degree of intramolecular electronic conjugation. It has good photothermal stability, excellent photoelectric properties, strong electron affinity, and a high molar absorptivity. It can be used to modify the mechanical properties of bismaleimide resin and improve the chemical stability, solvent resistance, and oxidation resistance of bismaleimide resin.

[0046] This application also provides a perylene-based nitrogen-containing organic nanosheet, which is a crystalline nanosheet with an ultra-stable rigid conjugated planar structure formed from a perylene-based nitrogen-containing organic derivative. It has high rigidity and is easy to manufacture.

[0047] This application also provides a modified resin, which is a bismaleimide resin modified with perylene-based nitrogen-containing organic nanosheets having an ultra-stable rigid conjugated planar structure. Utilizing the dicyandiamine nanosheets and hydrogen bonding effect within the perylene-based nitrogen-containing organic nanosheets, and the triazine ring structure formed under thermal action, not only is the heat resistance of the material increased, but the compatibility between the perylene-based nitrogen-containing organic nanosheets and the matrix resin (bismaleimide resin) is also improved. Compared to unmodified bismaleimide resin, this modified resin exhibits superior mechanical properties, with a flexural strength increase of 87.1% and an impact strength increase of 135.8%, thus solving the problem of significant brittleness and poor fracture toughness exhibited in cured bismaleimide resins.

[0048] This application also provides a method for preparing perylene-based nitrogen-containing organic nanosheets. This method is simple to operate, has mild reaction conditions, is easy to industrialize, and has significant industrial value.

[0049] This application also provides a method for preparing a modified resin. This method is simple to operate, has mild reaction conditions, is easy to industrialize, and has significant industrial value. Attached Figure Description

[0050] Figure 1 The NMR and IR spectra of perylene-based nitrogen-containing organic nanosheets are shown in the figure. (a) is the NMR spectrum of perylene-dicyandiamine organic nanosheets (P-DCD), and (b) is the IR spectrum of the raw materials 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), dicyandiamine (DCD), and P-DCD.

[0051] Figure 2 The figures show the morphology of perylene-based nitrogen-containing organic nanosheets. In the figure, (a) is the morphology characterization image of scanning electron microscopy and (b) is the morphology characterization image of transmission electron microscopy.

[0052] Figure 3 The figures show the infrared spectra of bismaleimide resin before and after modification. The ratio in the figures is perylene-dicyandiamine organic nanosheets: diamine: N,N'-(4,4'-methylenediphenyl)bismaleimide. Among them, (a) is the infrared spectrum of bismaleimide resin before modification, and (b) is the infrared spectrum of bismaleimide resin after modification. Detailed Implementation

[0053] The present application will now be clearly and completely described with reference to the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all of them. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present application.

[0054] In a first aspect, this application provides a perylene-based nitrogen-containing organic derivative, the structural formula of which is shown in Formula I:

[0055]

[0056] The R is a substituent containing a cyano group, an amino group, or an N-containing heterocycle.

[0057] It should be noted that R is a group containing at least two nitrogen atoms, such as a group containing two cyano groups, a group containing two amino groups, or a group containing one cyano group and one amino group. R can also be a substituted or unsubstituted cyclic substituent containing two nitrogen atoms, such as a substituted or unsubstituted five-membered ring containing two nitrogen atoms, a substituted or unsubstituted five-membered ring containing three nitrogen atoms, a substituted or unsubstituted five-membered ring containing four nitrogen atoms, a substituted or unsubstituted six-membered ring containing two nitrogen atoms, a substituted or unsubstituted six-membered ring containing three nitrogen atoms, or a substituted or unsubstituted six-membered ring containing four nitrogen atoms.

[0058] In some embodiments, the structural formula of the perylene-based nitrogen-containing organic derivative is:

[0059]

[0060]

[0061] Secondly, this application also provides a perylene-based nitrogen-containing organic nanosheet composed of the compound described in the first aspect. In this application, the perylene-based nitrogen-containing organic nanosheet is a nanosheet-like condensate formed by the condensation of perylene-based nitrogen-containing organic derivatives. Depending on its degree of aggregation, the surface area of ​​the nanosheet varies, exhibiting the characteristics of a two-dimensional material. Those skilled in the art can control its degree of aggregation as needed, such as by controlling reaction parameters; therefore, in this application, the degree of aggregation is not limited. It should be noted that in this application, the perylene-based nitrogen-containing organic nanosheet is a nanosheet-like product with a planar or near-planar surface. The nanosheet-like structure is formed by the highly planarity and extremely high degree of intramolecular electronic conjugation resulting from the large π-π conjugation of the benzene ring and the p-π conjugation linked to the benzene ring, characteristic of perylene-based nitrogen-containing organic derivatives. It is precisely for this reason that the perylene-based nitrogen-containing organic nanosheet provided in this application has high rigidity; it is a rigid, highly stable crystalline nanosheet with a conjugated planar structure.

[0062] In some embodiments, the perylene-based nitrogen-containing organic nanosheets have a width of 50–100 nm and a length of 100–550 nm. It should be noted that the diameter of the nanosheets in this application is based on the diameter of the side with the largest surface area.

[0063] Thirdly, this application also provides a method for preparing perylene-based nitrogen-containing organic nanosheets, wherein the perylene-based nitrogen-containing organic nanosheets are formed by the condensation of perylene derivatives and nitrogen-containing compounds.

[0064] The perylene derivatives are 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,9-bis(9H-purin-6-yl)anthracene[2,1,9-def:6,5-10-d'e f']diisoquinoline-1,3,8,10(2H,9H)-tetraone, and 2,9-bis(4,6-diamino-1,3,5-triazin-2-yl)anthracene[2,19-def:6,5-10-d'e f']. f']diisoquinoline-1,3,8,10(2H,9H)-tetraone, 2,9-bis([1,2,4]triazolo[4,3-b][1,2,4,5]tetraazin-3-yl)anthracene[2,1,9-def:6,5,10-d'ef']diisoquinoline-1,3,8,10(2H,9H)-tetraone, 2,9-bis(5-amino-4H-1,2,3-triazol-4-yl)anthracene[2,19-def:6,5-10-d'e f']diisoquinoline-1,3,8,10(2H,9H)-tetraone, 3,3'-(1,3,8,10-tetraoxo-1,3,8,10-tetrahydroanthracene[2,1,9-d ... [ef:6,5-10-d'ef']diisoquinoline-2,9-diyl)bis(1H-pyrazol-4-carbamate), 2,9-bis(3,5-dinitro-1H-pyrazol-4-yl)anthracene[2,19-def:6,5-10-d'e f']diisoquinoline-1,3,8,10(2H,9H)-tetraone, 2,9-bis(4-methyl-1,2,5-oxadiazol-3-yl)anthracene[2,19-def:6,5-10-d'e f']diisoquinoline-1,3,8,10(2H,9H)-tetraone, 2,9-bis(4-amino-3,6-dinitropyrazolo[4,3-c]pyrazol-1(4H)-yl)anthracene[2,19-de [f:6,5-10-d'f']diisoquinoline-1,3,8,10(2H,9H)-tetraone, 2,9-bis(1-vinyl-1H-tetrazo-5-yl)anthracene[2,1,9-def:6,5-10-d”f']diisoquinoline-1,3,8,10(2H,9H)-tetraone, 4,4'-(1,3,8,10-tetraoxo-1,3,8,10-tetrahydroanthracene[2,1,9-d ef:6,5-10-d'ef']diisoquinoline-2,9-diyl)diphtherianitrile.

[0065] The nitrogen-containing compound is one or a mixture of two or more of the following: dicyandiamine, 6-methyladenosine, melamine, [1,2,4]triazolo[4,3-b][1,2,4,5]tetraazine-3-amine, tetrazolium-1,5-diamine, 3-amino-4-cyanopyrazole, 3,5-dinitro-1H-pyrazole-4-amine, 4-methyl-1,2,5-oxadiazole-3-amine, 3,6-dinitropyrazolo[4,3-c]pyrazole-1,4-diamine, 1-vinyl-1H-tetrazolium-5-amine, and 4-aminophthalonitrile;

[0066] The first solvent is selected from at least one of N,N-dimethylformamide, ethylene glycol, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylaniline, 1,2-propanediol, and dimethyl sulfoxide. It should be noted that since the first solvent needs to be removed after the synthesis of the perylene-based nitrogen-containing organic nanosheets, it is preferably an organic solvent with good volatility. Preferably, it is a mixed solvent of N,N-dimethylformamide and ethylene glycol, wherein the N,N-dimethylformamide and ethylene glycol can be mixed in any ratio, more preferably in a ratio of (1–10):(10–1).

[0067] In some embodiments, the method for preparing perylene-based nitrogen-containing organic nanosheets includes:

[0068] Provides perylene derivatives, nitrogen-containing compounds, and a first solvent;

[0069] The perylene derivative, nitrogen-containing compound, and first solvent are mixed and subjected to a solvothermal reaction at 180–220°C for 40–80 h.

[0070] After the solvothermal reaction is completed, the first solvent is removed, and the mixture is freeze-dried to obtain perylene-based nitrogen-containing organic nanosheets.

[0071] The preferred method for removing the first solvent is a low-temperature removal method, that is, removal below the reaction temperature at which the perylene derivative and nitrogen-containing compound undergo condensation reaction, such as removal at a temperature below -60°C using freeze drying, water washing, or vacuum evaporation processes, in order to avoid agglomeration or condensation changes of the perylene-based nitrogen-containing organic nanosheets.

[0072] In some embodiments, the mass ratio of the perylene derivative to the nitrogen-containing compound is 1:(1-10); preferably 1:(1-5); more preferably 1:(2-4).

[0073] The concentration of the perylene derivative in the first solvent is 0.01–0.1 g / mL, preferably 0.02–0.06 g / mL; more preferably 0.025–0.05 g / mL; the concentration of the nitrogen-containing compound in the first solvent is 0.02–0.2 g / mL, preferably 0.04–0.12 g / mL; more preferably 0.05–0.1 g / mL.

[0074] Preferably, the mass ratio of the perylene derivative to the nitrogen-containing compound is 1:2 to obtain perylene-based nitrogen-containing organic nanosheets for the reinforcement and modification of bismaleimide resin.

[0075] Fourthly, this application also provides the application of the perylene-based nitrogen-containing organic derivatives described in the first aspect, or the perylene-based nitrogen-containing organic nanosheets described in the second aspect, or the perylene-based nitrogen-containing organic nanosheets prepared by the preparation method described in the third aspect, in the fields of modified resins, organic photocatalysts, organic semiconductors, and optoelectronics.

[0076] Fifthly, this application also provides a modified resin, wherein the modified resin is a resin obtained by modifying bismaleimide resin with perylene-based nitrogen-containing organic nanosheets; wherein the perylene-based nitrogen-containing organic nanosheets are perylene derivatives, nanosheets formed from nitrogen-containing compounds, or perylene-based nitrogen-containing organic nanosheets as described in the second aspect, or perylene-based nitrogen-containing organic nanosheets prepared by the preparation method described in the third aspect.

[0077] It should be noted that the modified resin in this application is a blend resin formed by bismaleimide resin as the matrix resin and perylene-based nitrogen-containing organic nanosheets, wherein the end maleimide of the bismaleimide resin and the end nitrogen-rich molecules of the perylene-based nitrogen-containing organic nanosheets are connected by carbon-nitrogen bonds.

[0078] In some embodiments, the bismaleimide resin is a resin formed from bismaleimide monomers, wherein the bismaleimide monomers are selected from at least one of the following formulas:

[0079]

[0080]

[0081] Sixthly, this application also provides a method for preparing the modified resin described in the fifth aspect, characterized in that it includes:

[0082] We provide perylene-based nitrogen-containing organic nanosheets and bismaleimide resins;

[0083] The perylene-based nitrogen-containing organic nanosheets and bismaleimide resin were mixed using a grinding process to obtain a blend;

[0084] The blend was cured using a gradient curing process and then cooled to obtain a modified resin.

[0085] The mass ratio of the perylene-based nitrogen-containing organic nanosheets to bismaleimide is (0.001–0.005):1.

[0086] In some embodiments, the gradient curing process includes: curing at 100℃~130℃ for 1~3h, curing at 160℃~180℃ for 2~4h, and curing at 200℃~260℃ for 2~6h.

[0087] In some embodiments, the blend further contains a diamine, the amount of which is 0.1 wt% to 0.5 wt% of the total mass of the perylene-based nitrogen-containing organic nanosheets, the diamine, and the bismaleimide, preferably 0.1 wt% to 0.35 wt%, and more preferably 0.15 wt% to 0.25 wt%. This can improve the flexural strength and flexural modulus of the modified bismaleimide resin, and simultaneously improve its impact strength.

[0088] The mass ratio of the perylene-based nitrogen-containing organic nanosheets to the bismaleimide resin is (0.001-0.005):1, preferably (0.001-0.0035):1, and more preferably (0.002-0.0035):1.

[0089] It should be noted that gradient curing of the perylene-based nitrogen-containing organic nanosheets, bismaleimide resin, and diamine results in superior curing performance. This is because gradual temperature increases allow for a more even and complete curing reaction. The curing temperature determines the reactivity between the resin and the curing agent. Low-temperature, stepped curing of the resin, with its slow reaction, promotes the formation of a uniform cured network structure, resulting in low internal stress and good resin performance. High-temperature curing ensures complete curing, improving the mechanical properties and heat resistance of the matrix.

[0090] Furthermore, the grinding process parameters can be set using a 125mL ball mill with grinding balls of 10mm in diameter, and the quantity can be adjusted according to production volume.

[0091] In a seventh aspect, this application also provides a composite material, comprising the modified resin prepared by the method described in the fifth aspect or the modified resin described in the sixth aspect.

[0092] Eighthly, this application also provides the application of perylene derivatives, nitrogen-containing compounds, or perylene-based nitrogen-containing organic nanosheets prepared by the preparation method of perylene-based nitrogen-containing organic nanosheets described in the second aspect or the third aspect, or modified resins prepared by the preparation method of modified resins described in the fifth aspect or the sixth aspect, in the field of aerospace materials.

[0093] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0094] The perylene derivatives used in the following specific embodiments are all self-made;

[0095] The nitrogen-containing organic compounds used in the following specific embodiments were all purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0096] The solvents used in the following specific examples were purchased from Chengdu Kelon Chemical Co., Ltd.

[0097] The diamine used in the following specific examples was purchased from Adamas Reagents Ltd.;

[0098] The bismaleimide resin used in the following specific embodiments was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0099] Example 1

[0100] S1: Preparation of perylene-based nitrogen-containing organic nanosheets

[0101] 2 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 4 g of dicyandiamine (DCD) were added to 40 mL of N,N-dimethylformamide and 40 mL of ethylene glycol. After thorough mixing, the mixture was solvothermically reacted at 200 °C for 60 h. After the reaction was completed, the mixture was successively washed with large amounts of ethanol, dichloromethane, acetone, DMF, and deionized water. The resulting nanosheets were freeze-dried at -60 °C to obtain perylene-dicyandiamine organic nanosheets (P-DCD) with an ultrastable rigid conjugated planar structure, as shown in the figure. Figure 2 As shown in the characterization.

[0102] S2: Preparation of modified resin

[0103] The organic nanosheets of diamine, perylene-dicyandiamine, and N,N'-(4,4'-methylenediphenyl)bismaleimide were cured at a ratio of 0.001:0.001:1. First, the three were blended together, then injected into a mold, and cured according to the following process flow: 100℃ / 1h, 180℃ / 3h, 200℃ / 2h, 260℃ / 2h. The final modified resin 1 was obtained.

[0104] The monomer structure of the obtained P-DCD is as follows:

[0105]

[0106] Example 2

[0107] This application provides a method for preparing a modified resin, which specifically includes the following steps:

[0108] S1: Preparation of perylene-based nitrogen-containing organic nanosheets

[0109] 2 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 4 g of dicyandiamine (DCD) were added to 40 mL of N,N-dimethylformamide and 40 mL of ethylene glycol. After mixing thoroughly, the mixture was allowed to react thermally at 200 °C for 60 h. After the reaction was completed, the mixture was washed sequentially with large amounts of ethanol, dichloromethane, acetone, DMF, and deionized water. Finally, the mixture was freeze-dried at -60 °C to obtain perylene-dicyandiamine organic nanosheets (P-DCD) with an ultrastable rigid conjugated planar structure.

[0110] S2: Preparation of modified resin

[0111] Perylene-dicyandiamine organic nanosheets, a diamine, and N,N'-(4,4'-methylenediphenyl)bismaleimide were cured at a ratio of 0.001:0.0015:1. First, the two were blended together, then injected into a mold, and cured according to the following process: 100℃ / 1h, 180℃ / 3h, 200℃ / 2h, 260℃ / 2h. The final modified resin 2 was obtained.

[0112] Example 3

[0113] S1: Preparation of perylene-based nitrogen-containing organic nanosheets

[0114] 2 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 4 g of dicyandiamine (DCD) were added to 40 mL of N,N-dimethylformamide and 40 mL of ethylene glycol. After mixing thoroughly, the mixture was allowed to react thermally at 200 °C for 60 h. After the reaction was completed, the mixture was washed sequentially with large amounts of ethanol, dichloromethane, acetone, DMF, and deionized water. Finally, the mixture was freeze-dried at -60 °C to obtain perylene-dicyandiamine organic nanosheets (P-DCD) with an ultrastable rigid conjugated planar structure.

[0115] S2: Preparation of modified resin

[0116] The organic nanosheets of diamine, perylene-dicyandiamine, and N,N'-(4,4'-methylenediphenyl)bismaleimide were cured in a ratio of 0.001:0.002:1. First, the three were blended together, then injected into a mold, and cured according to the following process flow: 100℃ / 1h, 180℃ / 3h, 200℃ / 2h, 260℃ / 2h, to obtain the modified resin 3.

[0117] Example 4

[0118] S1: Preparation of perylene-based nitrogen-containing organic nanosheets

[0119] 2 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 4 g of dicyandiamine (DCD) were added to 40 mL of N,N-dimethylformamide and 40 mL of ethylene glycol. After mixing thoroughly, the mixture was allowed to react thermally at 200 °C for 60 h. After the reaction was completed, the mixture was washed sequentially with large amounts of ethanol, dichloromethane, acetone, DMF, and deionized water. Finally, the mixture was freeze-dried at -60 °C to obtain perylene-dicyandiamine organic nanosheets (P-DCD) with an ultrastable rigid conjugated planar structure.

[0120] S2: Preparation of modified resin

[0121] The organic nanosheets of diamine, perylene-dicyandiamine, and N,N'-(4,4'-methylenediphenyl)bismaleimide were cured at a ratio of 0.001:0.0025:1. First, the three were blended together, then injected into a mold, and cured according to the following process flow: 100℃ / 1h, 180℃ / 3h, 200℃ / 2h, 260℃ / 2h. The final modified resin 4 was obtained.

[0122] Example 5

[0123] S1: Preparation of perylene-based nitrogen-containing organic nanosheets

[0124] 2 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 4 g of 2,4,6-triaminotriazine were added to 40 mL of N,N-dimethylformamide and 40 mL of ethylene glycol. After mixing thoroughly, the mixture was solvothermically reacted in the solvent at 200 °C for 60 h. After the reaction was completed, the mixture was washed successively with large amounts of ethanol, dichloromethane, acetone, DMF, and deionized water. Finally, the mixture was freeze-dried at -60 °C to obtain perylene-dicyandiamine organic nanosheets (P-DCD) with an ultrastable rigid conjugated planar structure.

[0125] S2: Preparation of modified resin

[0126] The organic nanosheets of diamine, perylene-dicyandiamine, and N,N'-(4,4'-methylenediphenyl)bismaleimide were cured at a ratio of 0.001:0.003:1. First, the three were blended together, then injected into a mold, and cured according to the following process flow: 100℃ / 1h, 180℃ / 3h, 200℃ / 2h, 260℃ / 2h. The final modified resin 5 was obtained.

[0127] Example 6

[0128] S1: Preparation of perylene-based nitrogen-containing organic nanosheets

[0129] 2 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 4 g of dicyandiamine (DCD) were added to 40 mL of N,N-dimethylformamide and 40 mL of ethylene glycol. After mixing thoroughly, the mixture was allowed to react thermally at 200 °C for 60 h. After the reaction was completed, the mixture was washed sequentially with large amounts of ethanol, dichloromethane, acetone, DMF, and deionized water. Finally, the mixture was freeze-dried at -60 °C to obtain perylene-dicyandiamine organic nanosheets (P-DCD) with an ultrastable rigid conjugated planar structure.

[0130] S2: Preparation of modified resin

[0131] Perylene-dicyandiamine organic nanosheets, diamine, and N,N'-(4,4'-methylenediphenyl)bismaleimide were cured at a ratio of 0.001:0.0035:1. First, the three were blended together, then injected into a mold, and cured at 100℃ / 1h, 180℃ / 3h, 200℃ / 2h, and 260℃ / 2h according to the following process flow to obtain modified resin 6.

[0132] Comparative Example 1

[0133] Compared to Example 1, step S1 is omitted in this example. In step S2, dicyandiamide is used to replace P-DCD to modify bismaleimide. The remaining steps and components are the same as in Example 1. The final modified resin 1 has a flexural strength of 24.06 MPa and an impact strength of 2.40 kJ / m. 2 .

[0134] Comparative Example 2

[0135] Compared to Example 1, this example performs step S1, and in step S2, the diamine and P-DCD are replaced with diamine to modify bismaleimide. The remaining steps and the components used are the same as in Example 1, and the final modified resin 2 is obtained.

[0136] Comparative Example 3

[0137] Compared to Example 2, this example performs step S1, and in step S2, the diamine and P-DCD are replaced with diamine to modify bismaleimide. The remaining steps and the components used are the same as in Example 1, and the final modified resin 3 is obtained.

[0138] Comparative Example 4

[0139] Compared to Example 3, this example performs step S1, and in step S2, the diamine and P-DCD are replaced with diamine to modify bismaleimide. The remaining steps and the components used are the same as in Example 1, and the final modified resin 4 is obtained.

[0140] Comparative Example 5

[0141] Compared to Example 4, this example performs step S1, and in step S2, the diamine and P-DCD are replaced with diamine to modify bismaleimide. The remaining steps and the components used are the same as in Example 1, and the final modified resin 5 is obtained.

[0142] Comparative Example 6

[0143] Compared to Example 5, this example performs step S1, and in step S2, the diamine and P-DCD are replaced with diamine to modify bismaleimide. The remaining steps and the components used are the same as in Example 1, and the final modified resin 6 is obtained.

[0144] Comparative Example 7

[0145] Compared to Example 6, this example performs step S1, and in step S2, the diamine and P-DCD are replaced with diamine to modify bismaleimide. The remaining steps and the components used are the same as in Example 1, and the final modified resin 7 is obtained.

[0146] The nanosheets obtained in Example 1 were characterized for molecular structure and molecular weight using NMR and IR spectrophotometry. The characterization results are as follows: Figure 1 As shown.

[0147] Impact strength, flexural strength, flexural modulus and other properties were tested on the modified resins and comparative modified resins obtained in Examples 1-6, Comparative Examples 1-6 and unmodified bismaleimide resin (hereinafter referred to as unmodified resin).

[0148] Its impact strength test is consistent with GB / T 1843-2008.

[0149] Bending strength test: consistent with GB / T 9341-2008

[0150] Flexural modulus test: consistent with GB / T 9341-2008

[0151] The test results are shown in Table 1.

[0152] Table 1

[0153]

[0154]

[0155] As shown in Table 1, the addition of modified diamine and perylene-dicyandiamine organic nanosheets can toughen bismaleimide resin, significantly improving impact strength, flexural strength, and flexural modulus. The addition of modified diamine at amounts ranging from 0.1 wt% to 0.5 wt% yields good modification effects (when the addition amount of modified perylene-dicyandiamine organic nanosheets is 0.1 wt%). The composite material obtained by adding modified diamine to bismaleimide resin at an amount of 0.25 wt% shows the most significant improvement in mechanical properties. When modified perylene-dicyandiamine organic nanosheets are incorporated at 0.1 wt% and modified diamine at 0.25 wt%, the impact strength of the bismaleimide resin composite material is increased by 135.8% compared to the matrix, and the flexural strength and flexural modulus are increased by 87.1% and 44.6%, respectively, compared to the pure bismaleimide resin matrix.

[0156] Therefore, the modified resin provided in this application is modified with novel perylene-based nitrogen-containing organic nanosheets and supplemented with a certain amount of diamine. The mechanical properties of the resulting modified resin are significantly improved, solving the problem of obvious brittleness and poor fracture toughness of bismaleimide cured products.

[0157] The descriptions of the above embodiments 1-5 are only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

[0158] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A modified resin, characterized in that, The modified resin is a resin obtained from perylene-based nitrogen-containing organic nanosheets and diamine-modified bismaleimide resin; The perylene-based nitrogen-containing organic nanosheets are formed from compounds with one of the following structural formulas: or , The perylene-based nitrogen-containing organic nanosheets are crystalline nanosheets with a rigid conjugated planar structure; the width of the perylene-based nitrogen-containing organic nanosheets is 50~100nm and the length is 100~550nm.

2. The modified resin according to claim 1, characterized in that, The perylene-based nitrogen-containing organic nanosheets are formed by the condensation of perylene derivatives and nitrogen-containing compounds; the perylene derivative is 3,4,9,10-perylenetetracarboxylic acid dianhydride; the nitrogen-containing compound is one or more of dicyandiamine and melamine.

3. The modified resin according to claim 1, characterized in that, The preparation method of the perylene-based nitrogen-containing organic nanosheets includes the following steps: Provides perylene derivatives, nitrogen-containing compounds, and a first solvent; The perylene derivative, nitrogen-containing compound, and first solvent are mixed and subjected to a solvothermal reaction at 180-220°C for 40-80 h. After the solvothermal reaction is completed, the first solvent is removed, and the mixture is freeze-dried to obtain perylene-based nitrogen-containing organic nanosheets.

4. The modified resin according to claim 3, characterized in that, The first solvent is selected from at least one of N,N-dimethylformamide, ethylene glycol, N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylaniline, 1,2-propanediol, and dimethyl sulfoxide.

5. The modified resin according to claim 3, characterized in that, The mass ratio of the perylene derivative to the nitrogen-containing compound is 1:(1~10); The concentration of the perylene derivative in the first solvent is 0.01~0.1 g / mL; the concentration of the nitrogen-containing compound in the first solvent is 0.02~0.2 g / mL.

6. The modified resin according to claim 1, characterized in that, The bismaleimide resin is a resin formed from bismaleimide monomers, wherein the bismaleimide monomers are selected from at least one of the following formulas: 、 。 7. The method for preparing the modified resin according to any one of claims 1 to 6, characterized in that, include: We provide perylene-based nitrogen-containing organic nanosheets and bismaleimide resins; The perylene-based nitrogen-containing organic nanosheets, diamine, and bismaleimide resin were mixed using a grinding process to obtain a blend. The blend was cured using a gradient curing process and then cooled to obtain a modified resin.

8. The method for preparing the modified resin according to claim 7, characterized in that, The gradient curing process includes: curing at 100℃~130℃ for 1~3 hours, curing at 160℃~180℃ for 2~4 hours, and curing at 200℃~260℃ for 2~6 hours.

9. A composite material, characterized in that, The modified resin includes the modified resin prepared by the preparation method of the modified resin according to any one of claims 1 to 6 or the modified resin according to any one of claims 7 to 8.

10. The application of the modified resin prepared by the method of any one of claims 1 to 6 or the modified resin of any one of claims 7 and 8 in the field of aerospace materials.

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