CN111825696B - Benzoxazole ion compound, PBO fiber emulsion sizing agent containing benzoxazole ion compound and preparation method of PBO fiber emulsion sizing agent - Google Patents

Benzoxazole ion compound, PBO fiber emulsion sizing agent containing benzoxazole ion compound and preparation method of PBO fiber emulsion sizing agent Download PDF

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CN111825696B
CN111825696B CN201910311610.6A CN201910311610A CN111825696B CN 111825696 B CN111825696 B CN 111825696B CN 201910311610 A CN201910311610 A CN 201910311610A CN 111825696 B CN111825696 B CN 111825696B
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sizing agent
benzoxazole
organic resin
resin
compound
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CN111825696A (en
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吴绍华
李春成
肖耀南
张博
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D263/57—Aryl or substituted aryl radicals
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

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Abstract

Benzoxazole ionic compound shown as formula X, sizing agent containing the compound, and preparation method and application thereof. The benzoxazole ion compound shown in the formula X has a chemical structure similar to that of PBO fiber, is beneficial to improving the compatibility of the sizing agent and the PBO fiber, and has a simple preparation process and easy operation. The sizing agent overcomes the problems that the existing sizing agent has poor compatibility with PBO fibers, a large amount of flammable and explosive organic solvent is required for the sizing agent, and a nano reinforcement in the sizing agent is difficult to effectively cover the surface of the fibers. The sizing agent takes water as a solvent, is green and efficient, is simple to prepare, is environment-friendly, can keep the original tensile strength of the PBO fiber, and can obviously improve the IFSS of the composite material.
Figure DDA0002031698780000011

Description

Benzoxazole ion compound, PBO fiber emulsion sizing agent containing benzoxazole ion compound and preparation method of PBO fiber emulsion sizing agent
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a benzoxazole ion compound, a PBO fiber emulsion sizing agent containing the benzoxazole ion compound and a preparation method of the PBO fiber emulsion sizing agent.
Background
PBO (poly (phenylene benzobisoxazole)) is a rigid rod-shaped liquid crystal polymer with full aromatic heterocyclic rings, PBO fibers prepared by a dry-jet wet spinning process have ultrahigh strength, modulus, heat resistance and flame retardance, are known as super fibers in the 21 st century, and have wide application prospects in the advanced fields of aerospace, national defense and military industry, rail transit, high-temperature production, new energy and the like.
The molecular structure of PBO fibers is shown below:
Figure BDA0002031698760000011
however, the rigid structure makes the surface of the PBO fiber very smooth, and the lack of active groups makes the surface of the PBO fiber to be extremely chemically inert, which results in that the PBO fiber is difficult to be infiltrated by the matrix resin, and the interface bonding strength of the PBO fiber and the matrix resin is low, thus severely limiting the application of the PBO fiber in composite materials.
In recent years, much research has been conducted around surface modification of PBO fibers, and various modification methods have been developed, mainly including: plasma/irradiation treatment, coupling agent treatment, copolymerization modification, oxidation etching, chemical grafting and the like. Although the method can improve the interface performance of the PBO fiber composite material to a certain extent, the mechanical property of the fiber body is generally sacrificed. Meanwhile, the problems of complicated processing steps, long reaction time and the like make it difficult to carry out large-scale continuous surface treatment.
The sizing treatment is a common surface treatment technology in the carbon fiber industry, and has the advantages of mild conditions, no damage to fibers, simple operation, easy integration with a spinning production line to realize continuous treatment and the like. However, the application of sizing treatment to PBO fiber surface modification has been very rare at home and abroad. Specifically, PBO fibers are alternately impregnated with titanium dioxide (TiO) by Song dynasty, etc2) The ethanol solution (0.1-1 wt%) and the tetrahydrofuran solution (1 wt%) of polyhedral oligomeric silsesquioxane (POSS) are added to obtain the POSS/TiO coated surface2The interface shear strength (IFSS) of the coated PBO fiber and the composite material thereof is improved by 30 percent (Chinese patent document CN 102634976A; Bo Song2)nMulti-coatings based on PBO fiber surface for improvement of UV resistance, fibers and Polymers,2013,14(3), 375-381); qian et al used TiO2 ethanol solution (0.7 wt%) to treat PBO fiber to increase IFSS of its composite material by 60% (Jun Qianobisoxazole fiber/epoxy resin composite by n～TiO2Journal of Applied Polymer Science,2013,127(4): 2990-2995); liurong Biao et al uses phosphated castor oil modified epoxy resin, and prepares the mixture into 10 wt% ethanol solution to perform surface treatment on PBO fiber, so as to improve the IFSS of the composite material by 155% (p-phenylene benzobisoxazole) fiber/epoxy resin composite vitamin a novel surface coating agent, Polymer Composites,2016,37(4): 1198-1205).
However, the sizing agent and the PBO fiber have different chemical structures, so that the compatibility between the two is poor, and the sizing agent is difficult to uniformly disperse on the surface of the fiber. Moreover, the content of the organic solvent in the sizing agent is up to more than 90 wt%, and the sizing process has the risks of flammability and explosiveness, causes great pollution to the environment and does not accord with the development concept of green chemistry. In addition, nanoreinforcements in the sizing agent, e.g. spherical TiO2And cage-like POSS do not achieve effective coverage of the fiber surface.
Disclosure of Invention
In order to solve the above technical problems, the present invention first provides a benzoxazole ionic compound represented by the following formula X,
Figure BDA0002031698760000021
wherein n is an integer of 3-6, and A is selected from the following groups:
Figure BDA0002031698760000031
Figure BDA0002031698760000032
m is selected from H or alkali metal ions; ar is selected from
Figure BDA0002031698760000033
R、R1、R2Identical or different, independently of one another, from H, OH, NH2Halogen, halogen、C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkyl group; m is an integer of 1-4;
Figure BDA0002031698760000034
indicates the attachment site.
According to an embodiment of the invention, wherein n is selected from 3, 4 or 5; m is selected from H or Na; r, R1、R2Identical or different, independently of one another, from H, OH, C1-3Alkyl radical, C1-3Alkoxy or halo C1-3An alkyl group; m is selected from 1,2, 3 or 4.
According to a preferred embodiment of the present invention, the benzoxazole ion compound represented by formula X is selected from the group consisting of compounds represented by the following formulas (I) to (III),
Figure BDA0002031698760000035
wherein Ar is selected from
Figure BDA0002031698760000041
R is selected from H or OH.
As an example, the benzoxazole ionic compound represented by formula X is selected from at least one of the following compounds:
Figure BDA0002031698760000042
Figure BDA0002031698760000051
the invention also provides a preparation method of the benzoxazole ionic compound shown as the formula X, which comprises the following steps:
the compound X-1 reacts with the compound X-2 to obtain a benzoxazole ionic compound shown in the formula X,
Figure BDA0002031698760000052
wherein A, M, n has the definitions as described above;
when M is selected from alkali metal ions, the process further comprises reacting X with an alkali metal hydroxide to give a salt thereof.
According to an embodiment of the present invention, in the above step, the reaction is carried out under an inert gas, for example, under a nitrogen atmosphere.
According to the embodiment of the invention, in the above steps, the reaction temperature is 40-160 ℃; the reaction time is 1-24 hours.
According to an embodiment of the present invention, in the above step, the alkali metal hydroxide is selected from sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.
According to an embodiment of the present invention, in the above step, the molar ratio of the compound represented by the formula X-3 to the alkali metal hydroxide is 1:2 to 4.
By way of example, the benzoxazole ionic compound represented by formula X is prepared as follows:
dissolving benzoxazole diamine shown in formulas (IV) to (VI) in a reaction solvent, and adding 1, 3-propane sultone, wherein the molar ratio of the benzoxazole diamine shown in formulas (IV) to (VI) to the 1, 3-propane sultone is 1: 1-4, N2Raising the temperature of the system to 50-150 ℃ under protection, stirring and reacting for 1-12 h, pouring reactants into acetone for precipitation, carrying out suction filtration, washing a filter cake with acetone, drying, adding a crude product into an alkali metal hydroxide aqueous solution for reaction, wherein the molar ratio of the crude product to the alkali metal hydroxide is 1:2, carrying out rotary evaporation to remove water, and further drying to obtain a benzoxazole ionic compound shown in the formula X;
Figure BDA0002031698760000061
wherein Ar is selected from
Figure BDA0002031698760000071
R is selected from H or OH.
According to an embodiment of the present invention, the preparation method of the benzoxazole ionic compound represented by the formula X further comprises a synthesis of a benzoxazole diamine compound represented by X-1, specifically, comprises the following steps:
step (s 1'), adding a compound A, a compound B and stannous chloride into polyphosphoric acid, wherein the molar ratio of the compound A to the compound B to the stannous chloride is 1: 2-2.5: 0.1-0.3, and the content of phosphorus pentoxide in the polyphosphoric acid is 80-85 wt%; n is a radical of2Slowly heating to 100-140 ℃ under protection, stirring, heating to 150-200 ℃, and continuously stirring for reaction for 1-15 hours to obtain a wine red transparent solution; pouring the solution into water for precipitation, performing suction filtration, repeatedly washing a filter cake with water until the pH value of the filtrate is close to 6-8, and drying to obtain a crude product; recrystallizing the crude product to obtain benzoxazole diamine shown as X-1;
when the reactant a in the step (s1 ') is any one of 4, 6-diaminoresorcinol dihydrochloride, 3' -dihydroxybenzidine and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the reactant B is p-aminobenzoic acid or 4-aminosalicylic acid, the finally obtained benzoxazole ionic compound has a chemical structure shown in formula (I); when the reactant A is 2, 4-diaminophenol dihydrochloride and the reactant B is p-aminobenzoic acid or 4-aminosalicylic acid, the finally obtained benzoxazole ion compound has a chemical structure shown as a formula (II); when the reactant A is 2, 4-diaminophenol dihydrochloride and the reactant B is terephthalic acid or 2, 5-dihydroxyterephthalic acid, the finally obtained benzoxazole ionic compound has a chemical structure shown in a formula (III).
According to an embodiment of the present invention, the solvent used for the recrystallization in the above step (s 1') is any one of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, or a mixture thereof with water in any ratio.
According to an embodiment of the present invention, the solvent used in the reaction in the above step (s1) is one, two or more of N, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
The invention also provides application of the benzoxazole ion compound shown in the formula X in preparation of a sizing agent.
As an example, the benzoxazole ionic compound represented by the formula X may be applied to a sizing treatment of PBO fibers.
The invention also provides a sizing agent, which is characterized by comprising a mixed system consisting of organic resin, an emulsifier, a lubricant, a benzoxazole ionic compound shown as the formula X and water, wherein the content of the emulsifier is 1-20 wt% of the organic resin; the content of the lubricant is 0.3-5 wt% of the organic resin; the content of the benzoxazole ionic compound shown in the formula X is 0.5-60 wt% of the organic resin; the solid content of the sizing agent is 0.05-8 wt%;
the organic resin is at least one of epoxy resin, cyanate resin, bismaleimide resin, polyimide resin and polyurethane;
the emulsifier is nonionic surfactant;
the lubricant is at least one of polyoxyethylene ether, butyl stearate, higher fatty amine, higher fatty alcohol and higher fatty ester.
According to the embodiment of the invention, the sizing agent further comprises graphene, wherein the graphene is graphene oxide with polar groups on the surface prepared by a Hummers method, or graphene without any groups on the surface after reduction, and the average number of layers of the graphene is 1-10.
According to the embodiment of the invention, when the sizing agent further comprises graphene, the content of the graphene is 0.5-60 wt% of the organic resin.
According to an embodiment of the present invention, the sizing agent optionally includes an organic solvent selected from at least one of ketone solvents, ether solvents, haloalkane solvents, and nitrogen-containing organic solvents.
According to an embodiment of the present invention, the organic solvent is used as an aid for dispersing or forming a uniform phase of the organic resin, and may be selectively added or not added according to the properties of the organic resin.
According to an embodiment of the present invention, when the sizing agent further includes an organic solvent, the content thereof is 0.5 to 300 wt%, preferably 0.5 to 100 wt%, and further preferably 0.5 to 50 wt% of the organic resin.
As an example, the organic resin is selected from at least one of epoxy resin 601, epoxy resin 618, cyanate ester resin AroCyB-10, bismaleimide resin QY9511, polyimide resin GCPI-PAA, polyurethane WP-4 and epoxy 6101.
As an example, the emulsifier is at least one selected from the group consisting of polyoxyethylene sorbitan monooleate (Tweer81), alkylphenol polyoxyethylene (Igegal CA-630), polyoxyethylene sorbitan palmitate (Tweer40), polyoxyethylene sorbitan trioleate (Tweer85), polyoxyethylene sorbitan monooleate (Tweer80), polyoxyethylene sorbitan monostearate (Tweer21), and polyoxyethylene castor oil (Atlas 1794).
As an example, the lubricant is selected from at least one of fatty alcohol-polyoxyethylene ether 0-10, primary octadecane, butyl stearate and octadeca-9-enol.
Preferably, the water is deionized water.
Preferably, the content of the emulsifier is 1-15 wt% of the organic resin.
Preferably, the lubricant is contained in an amount of 0.5 to 3 wt%, and more preferably 0.5 to 2 wt% of the organic resin.
Preferably, the content of the graphene is 5-50 wt% of the organic resin.
Preferably, the content of the benzoxazole ionic compound represented by the formula X is 1-55 wt% of the organic resin, and more preferably 1-50 wt%.
Preferably, the organic solvent is at least one of acetone, tetrahydrofuran, chloroform, 2-butanone, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the content of the organic solvent is 1 to 250 wt% of the organic resin, and more preferably 10 to 200 wt%.
Preferably, the solid content of the sizing agent is 0.1-5 wt%.
The invention also provides a preparation method of the sizing agent, which comprises the following steps:
(1) mixing organic resin, an emulsifier, a lubricant and an optional organic solvent, adding water until the system is subjected to phase inversion, stirring, adding water for dilution, and adjusting the solid content of the system to 10-50 wt% to obtain an organic resin emulsion;
(2) adding the benzoxazole ionic compound shown as the formula X and optional graphene into an organic resin emulsion, performing ultrasonic dispersion, and adding water to further dilute the organic resin emulsion until the solid content is 0.05-8 wt%, so as to obtain the sizing agent;
wherein the content of the emulsifier is 1-20 wt% of the organic resin; the content of the lubricant is 0.3-5 wt% of the organic resin; the content of the benzoxazole ionic compound shown in the formula X is 0.5-60 wt% of the organic resin; the content of graphene is 0-60 wt% of the organic resin; the content of the organic solvent is 0-300 wt% of the organic resin;
the organic resin is at least one of epoxy resin, cyanate resin, bismaleimide resin, polyimide resin and polyurethane;
the emulsifier is nonionic surfactant;
the lubricant is at least one of polyoxyethylene ether, butyl stearate, higher fatty amine, higher fatty alcohol and higher fatty ester.
The organic solvent is selected from ketone solvent, ether solvent, halogenated alkane solvent and nitrogen-containing organic solvent.
Preferably, the sizing agent is prepared by adopting the following method:
(a1) adding organic resin, an emulsifier and a lubricant into an organic solvent, uniformly dispersing by a high-speed emulsifying machine, simultaneously dropwise adding deionized water until the system is subjected to phase inversion, continuously stirring for 0.5-1 h, adding a large amount of deionized water for dilution, and adjusting the solid content of the system to 10-50 wt% to obtain an organic resin emulsion;
(a2) adding the benzoxazole ionic compound shown in the formula X and graphene into an organic resin emulsion, uniformly dispersing by ultrasonic, and then adding water to further dilute the organic resin emulsion until the solid content is 0.1-5 wt% to obtain the sizing agent.
The invention also provides the sizing agent prepared by the method.
The invention also provides the use of a sizing as described above in the treatment of PBO fibres.
According to an embodiment of the present invention, the treatment process is performed by a dipping method, and the sizing agent is coated on the surface of the PBO fiber.
According to an embodiment of the invention, the treatment process further comprises a drying step after completion of the coating; the drying temperature is 80-120 ℃.
The invention also provides a composite material which comprises the PBO fiber and the sizing agent coated on the surface of the PBO fiber.
The invention also provides the application of the composite material in the fields of aerospace, national defense and military industry, rail transit, high-temperature production and new energy.
Advantageous effects
(1) The benzoxazole ionic compound with a novel structure is prepared and synthesized, has a chemical structure similar to that of PBO fibers, is beneficial to improving the compatibility of a sizing agent and the PBO fibers, and is simple in preparation process and easy to operate;
(2) the invention also provides a sizing agent containing benzoxazole ionic compound and having excellent performance, and solves the problems that the existing sizing agent has poor compatibility with PBO fibers, the sizing agent needs a large amount of flammable and explosive organic solvent, and the nano reinforcement in the sizing agent is difficult to effectively cover the fiber surface. The sizing agent takes water as a solvent, is green and efficient, is simple to prepare, and is environment-friendly, and the sizing agent not only can keep the original tensile strength of PBO fibers, but also can obviously improve the IFSS of the composite material;
(3) when the sizing agent provided by the invention further comprises graphene, the nano reinforcement graphene in the sizing agent can be effectively coated on the surface of the fiber to form a compact film, so that the interface performance of the PBO fiber treated by the sizing agent and the matrix resin is obviously improved. The functional PBO fiber sizing agent can optimize the interface performance and the macroscopic performance of the PBO fiber reinforced composite material, and has important significance for promoting the application of the functional PBO fiber sizing agent in high and new technical fields of aerospace, defense industry and the like.
Definition and description of terms
Unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.
The term "halogen" refers to fluorine, chlorine, bromine or iodine.
The term "C1-6Alkyl is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 6 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a1, 2-dimethylpropyl group, a neopentyl group, a1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a2, 2-dimethylbutyl group, a1, 1-dimethylbutyl group, a2, 3-dimethylbutyl group, a1, 3-dimethylbutyl group or a1, 2-dimethylbutyl group, or the like, or isomers thereof.
The term "C1-6Alkoxy "denotes-O-C1-6Alkyl structure wherein C1-6Alkyl groups have the definitions as described above.
The term "halo C1-6Alkyl "represents C1-6A structure formed by substituting at least one H in the alkyl group by halogen, wherein C1-6Alkyl groups have the definitions as described above. Said halo C1-6Alkyl is, for example, trifluoromethyl.
Drawings
FIG. 1 is a drawing showing benzoxazole diamine IV-ad obtained in step (1) of example 61H NMR spectrum (deuterated reagent is DMSO-d)6)；
FIG. 2 shows benzoxazole ionic compounds I-ad obtained in step (2) of example 61H NMR spectrum (deuterated reagent is DMSO-d)6And D2Mixed solvent of O).
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
(1) 0.1mol of 4, 6-diaminoresorcinol dihydrochloride, 0.2mol of 4-aminosalicylic acid and 0.01mol of stannous chloride were added to 480g of polyphosphoric acid (80 wt% phosphorus pentoxide), N2Slowly heating to 120 ℃ under protection, stirring for 1h, then heating to 150 ℃, and continuously stirring for reaction for 15h to obtain a wine red transparent solution. And pouring the solution into water for precipitation, performing suction filtration, repeatedly washing a filter cake by using deionized water until the pH value of the filtrate is close to 7.4, and drying to obtain a crude product. And recrystallizing the crude product by using N, N-dimethylformamide to obtain the high-purity benzoxazole diamine IV-ae.
(2) Dissolving 0.1mol of IV-ae in N-methylpyrrolidone, adding 0.1mol of 1, 3-propane sultone, N2And under protection, raising the temperature of the system to 50 ℃, stirring and reacting for 12h, pouring reactants into acetone for precipitation, carrying out suction filtration, washing a filter cake for 3 times by using acetone, drying, adding a crude product into 0.2L of sodium hydroxide aqueous solution (1mol/L) for reaction, carrying out rotary evaporation to remove water, and further drying to obtain the benzoxazole ionic compound I-ae.
(3) Directly mixing 1 kg of epoxy resin (brand 601), 0.01 kg of polyoxyethylene sorbitan monooleate (Tweer81) and 0.005 kg of fatty alcohol-polyoxyethylene ether (0-10), uniformly dispersing by using a high-speed emulsifying machine, simultaneously dropwise adding deionized water until the system undergoes phase inversion, continuously stirring for 0.5h, adding a large amount of deionized water for dilution, and adjusting the solid content of the system to 10 wt% to obtain the organic resin emulsion.
(4) Adding 0.5 kg of I-ae into the organic resin emulsion, uniformly dispersing by ultrasonic, and then adding water to further dilute the organic resin emulsion until the solid content is 0.1 wt% so as to obtain the sizing agent modified by the benzoxazole ionic compound.
Coating the prepared sizing agent on the surface of the PBO fiber by a dipping method for 10s, then drying at 100 ℃ for 0.5h to remove the solvent, and placing the sample in N2The atmosphere desiccator was ready for use.
According to ASTM-D3379 Standard "tensile Strength and Young's modulus test method for high modulus monofilament Material", a microcomputer controlled electronic tensile tester was used to test the tensile Strength of the monofilament of PBO fiber before and after the sizing agent treatment, and the test results are shown in Table 1.
The sizing agent-treated PBO fibers obtained in the present example, the organic resin emulsion-treated PBO fibers obtained in step (3) of the present example, and IFSS between the untreated PBO fibers and the matrix resin were tested by a composite interface performance evaluation apparatus (HM-410, manufactured by Toho industries, Japan) and the results are shown in Table 2.
The matrix resin is a mixture of epoxy resin (the mark 601) and 4,4 '-methylene-bis (2-ethyl) aniline curing agent, wherein the mass ratio of the epoxy resin (the mark 601) to the 4,4' -methylene-bis (2-ethyl) aniline curing agent is 100: 13.
Example 2
(1) 0.1mol of 3,3' -dihydroxybenzidine, 0.25mol of p-aminobenzoic acid and 0.03mol of stannous chloride were added to 480g of polyphosphoric acid (85% by weight of phosphorus pentoxide), N2Slowly heating to 120 ℃ under protection, stirring for 2h, then heating to 200 ℃, and continuously stirring for reaction for 5h to obtain a wine red transparent solution. And pouring the solution into water for precipitation, performing suction filtration, repeatedly washing a filter cake by using deionized water until the pH value of the filtrate is close to 7.4, and drying to obtain a crude product. And recrystallizing the crude product by using N-methylpyrrolidone to obtain high-purity benzoxazole diamine IV-bd.
(2) Dissolving 0.1mol of IV-bd in N, N-dimethylacetamide, and adding 0.4mol of 1, 3-propane sultone, N2Heating the system to 150 ℃ under protection, stirring and reacting for 3h, pouring the reactant into acetone for precipitation, filtering and filteringAnd washing the filter cake with acetone for 3 times, drying, adding the crude product into 0.2L of sodium hydroxide aqueous solution (1mol/L) for reaction, removing water by rotary evaporation, and further drying to obtain the benzoxazole ionic compound I-bd.
(3) Adding 1 kg of epoxy resin (trade marks 601 and 618, mass ratio 50:50), 0.15 kg of alkylphenol polyoxyethylene ether (Igegal CA-630) and 0.02 kg of higher fatty amine (octadecylamine) into 0.2 kg of acetone, uniformly dispersing by a high-speed emulsifying machine, simultaneously dropwise adding deionized water until phase inversion occurs in the system, continuously stirring for 1h, adding a large amount of deionized water for dilution, and adjusting the solid content of the system to 50 wt% to obtain the organic resin emulsion.
(4) Adding 0.01 kg of I-bd and 0.5 kg of graphene into the organic resin emulsion, uniformly dispersing by ultrasonic, and then adding water to further dilute the organic resin emulsion until the solid content is 5 wt% to obtain the benzoxazole ionic compound and the graphene modified sizing agent.
The tensile strength of the PBO fibers before and after the sizing agent treatment was measured for the monofilament under the same test conditions as in example 1, and the results are shown in Table 1. The sizing agent-treated PBO fibers prepared in this example, the organic resin emulsion-treated PBO fibers prepared in step (3) of this example, and IFSS between the untreated PBO fibers and the matrix resin were tested under the same test conditions as in example 1, and the results are shown in table 2.
The matrix resin is a mixture of epoxy resin (the mark 601), epoxy resin (the mark 618) and 4,4 '-methylene-bis (2-ethyl) aniline curing agent, wherein the mass ratio of the epoxy resin (the mark 601), the epoxy resin (the mark 618) and the 4,4' -methylene-bis (2-ethyl) aniline curing agent is 50:50: 23.
Example 3
(1) 0.1mol of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 0.23mol of p-aminobenzoic acid and 0.02mol of stannous chloride were added to 480g of polyphosphoric acid (83 wt% phosphorus pentoxide), N2Slowly raising the temperature to 120 ℃ under protection, stirring for 1.5h, then raising the temperature to 180 ℃, and continuously stirring and reacting for 10h to obtain a wine red transparent solution. Pouring the solution into water for precipitation, performing suction filtration, and repeatedly washing a filter cake with deionized water until filtrateThe pH is close to 7.4, and the crude product is obtained after drying. And recrystallizing the crude product by using N-methylpyrrolidone to obtain the high-purity benzoxazole diamine IV-cd.
(2) Dissolving 0.1mol of IV-cd in dimethyl sulfoxide, adding 0.25mol of 1, 3-propane sultone, N2Raising the temperature of the system to 100 ℃ under protection, stirring and reacting for 7h, pouring reactants into acetone for precipitation, carrying out suction filtration, washing a filter cake for 3 times by using acetone, drying, adding a crude product into 0.2L of sodium hydroxide aqueous solution (1mol/L) for reaction, carrying out rotary evaporation to remove water, and further drying to obtain the benzoxazole ionic compound I-cd.
(3) Adding 1 kg of cyanate ester resin (the trademark AroCyB-10), 0.08 kg of polyoxyethylene sorbitan palmitate (Tweer40) and 0.01 kg of butyl stearate into 1 kg of tetrahydrofuran, uniformly dispersing by using a high-speed emulsifying machine, simultaneously dropwise adding deionized water until the system is subjected to phase inversion, continuously stirring for 0.5h, adding a large amount of deionized water for dilution, and adjusting the solid content of the system to 30 wt% to obtain the organic resin emulsion.
(4) Adding 0.25 kg of I-cd and 0.25 kg of graphene into the organic resin emulsion, uniformly dispersing by ultrasonic, and then adding water to further dilute the organic resin emulsion until the solid content is 2.5 wt% to obtain the benzoxazole ionic compound and the graphene modified sizing agent.
The tensile strength of the PBO fibers before and after the sizing agent treatment was measured for the monofilament under the same test conditions as in example 1, and the results are shown in Table 1. The sizing agent-treated PBO fibers prepared in this example, the organic resin emulsion-treated PBO fibers prepared in step (3) of this example, and IFSS between the untreated PBO fibers and the matrix resin were tested under the same test conditions as in example 1, and the results are shown in table 2.
The matrix resin is a mixture of cyanate ester resin (the trademark AroCyB-10) and epoxy resin (the trademark 618), wherein the mass ratio of the cyanate ester resin (the trademark AroCyB-10) to the epoxy resin (the trademark 618) is 19: 1.
Example 4
(1) 0.1mol of 2, 4-diaminophenol dihydrochloride, 0.21mol of p-aminobenzoic acid and 0.02mol of stannous chloride were added to 480g of polyatomic alcoholIn polyphosphoric acid (84 wt% phosphorus pentoxide), N2Slowly heating to 120 ℃ under protection, stirring for 2h, then heating to 150 ℃, reacting for 6h, heating to 200 ℃, and reacting for 4h to obtain wine red transparent solution. And pouring the solution into water for precipitation, performing suction filtration, repeatedly washing a filter cake by using deionized water until the pH value of the filtrate is close to 7.4, and drying to obtain a crude product. And recrystallizing the crude product by using N, N-dimethylformamide/water to obtain the high-purity benzoxazole diamine V-d.
(2) 0.1mol of V-d is dissolved in N, N-dimethylacetamide, 0.2mol of 1, 3-propane sultone, N is added2And under protection, raising the temperature of the system to 100 ℃, stirring and reacting for 6h, pouring reactants into acetone for precipitation, carrying out suction filtration, washing a filter cake for 3 times by using acetone, drying, adding a crude product into 0.2L of sodium hydroxide aqueous solution (1mol/L) for reaction, carrying out rotary evaporation to remove water, and further drying to obtain benzoxazole ionic compounds II-d.
(3) Adding 1 kg of bismaleimide resin (No. QY9511), 0.06 kg of polyoxyethylene sorbitan trioleate (Tweer85) and 0.01 kg of higher fatty alcohol (octadec-9-enol) into 2 kg of N-methyl pyrrolidone, uniformly dispersing by a high-speed emulsifying machine, simultaneously dropwise adding deionized water until the system is subjected to phase inversion, continuously stirring for 1h, adding a large amount of deionized water for dilution, and adjusting the solid content of the system to 25 wt% to obtain the organic resin emulsion.
(4) Adding 0.25 kg of I-cd and 0.35 kg of graphene into the organic resin emulsion, uniformly dispersing by ultrasonic, and then adding water to further dilute the organic resin emulsion until the solid content is 2.5 wt% to obtain the benzoxazole ionic compound and the graphene modified sizing agent.
The tensile strength of the PBO fibers before and after the sizing agent treatment was measured for the monofilament under the same test conditions as in example 1, and the results are shown in Table 1. The sizing agent-treated PBO fibers prepared in this example, the organic resin emulsion-treated PBO fibers prepared in step (3) of this example, and IFSS between the untreated PBO fibers and the matrix resin were tested under the same test conditions as in example 1, and the results are shown in table 2.
The matrix resin is bismaleimide resin (the trademark QY 9511).
Example 5
(1) 0.1mol of 2, 4-diaminophenol dihydrochloride, 0.22mol of terephthalic acid and 0.025mol of stannous chloride were added to 480g of polyphosphoric acid (82 wt% phosphorus pentoxide), N2Slowly heating to 120 ℃ under protection, stirring for 1.5h, then heating to 160 ℃, reacting for 4h, heating to 180 ℃, and reacting for 6h to obtain wine red transparent solution. And pouring the solution into water for precipitation, performing suction filtration, repeatedly washing a filter cake by using deionized water until the pH value of the filtrate is close to 7.4, and drying to obtain a crude product. And recrystallizing the crude product by using N-methylpyrrolidone to obtain high-purity benzoxazole diamine VI-d.
(2) 0.1mol of VI-d is dissolved in N, N-dimethylformamide, 0.3mol of 1, 3-propane sultone, N is added2And raising the temperature of the system to 120 ℃ under protection, stirring and reacting for 5h, pouring reactants into acetone for precipitation, carrying out suction filtration, washing a filter cake for 3 times by using acetone, drying, adding a crude product into 0.2L of sodium hydroxide aqueous solution (1mol/L) for reaction, carrying out rotary evaporation to remove water, and further drying to obtain benzoxazole ionic compounds III-d.
(3) 1 kg of polyimide resin (the trademark is GCPI-PAA), 0.04 kg of polyoxyethylene sorbitan monooleate (Tweer80), 0.02 kg of polyoxyethylene sorbitan tristearate (Tweer65), 0.02 kg of polyoxyethylene castor oil (Atlas1794) and 0.008 kg of higher aliphatic alcohol (octadeca-9-enol) are added into 1.2 kg of N, N-dimethylacetamide, the mixture is uniformly dispersed by a high-speed emulsifying machine, deionized water is dripped at the same time until the system is subjected to phase inversion, a large amount of deionized water is added for dilution after continuous stirring for 0.5h, and the solid content of the system is adjusted to 40 wt%, so that the organic resin emulsion is obtained.
(4) Adding 0.1 kg of III-d and 0.1 kg of graphene into the organic resin emulsion, uniformly dispersing by ultrasonic, and then adding water to further dilute the organic resin emulsion until the solid content is 1 wt% so as to obtain the benzoxazole ionic compound and the graphene modified sizing agent.
The tensile strength of the PBO fibers before and after the sizing agent treatment was measured for the monofilament under the same test conditions as in example 1, and the results are shown in Table 1. The sizing agent-treated PBO fibers prepared in this example, the organic resin emulsion-treated PBO fibers prepared in step (3) of this example, and IFSS between the untreated PBO fibers and the matrix resin were tested under the same test conditions as in example 1, and the results are shown in table 2.
The matrix resin is polyimide resin (GCPI-PAA).
Example 6
(1) 0.1mol of 4, 6-diaminoresorcinol dihydrochloride, 0.24mol of p-aminobenzoic acid and 0.012mol of stannous chloride were added to 480g of polyphosphoric acid (81 wt% phosphorus pentoxide), N2Slowly heating to 120 ℃ under protection, stirring for 2h, then heating to 190 ℃, and reacting for 7h to obtain wine red transparent solution. And pouring the solution into water for precipitation, performing suction filtration, repeatedly washing a filter cake by using deionized water until the pH value of the filtrate is close to 7.4, and drying to obtain a crude product. The crude product was recrystallized using N-methylpyrrolidone to give high purity benzoxazole diamine IV-ad with nuclear magnetic characterization data shown in figure 1.
(2) Dissolving 0.1mol of IV-ad in dimethyl sulfoxide, adding 0.4mol of 1, 3-propane sultone, N2And under protection, raising the temperature of the system to 130 ℃, stirring and reacting for 4h, pouring reactants into acetone for precipitation, carrying out suction filtration, washing a filter cake for 3 times by using acetone, drying, adding a crude product into 0.2L of sodium hydroxide aqueous solution (1mol/L) for reaction, carrying out rotary evaporation to remove water, and further drying to obtain a benzoxazole ionic compound I-ad, wherein nuclear magnetic characterization data of the benzoxazole ionic compound I-ad are shown in figure 2.
(3) Adding 1 kg of polyurethane (brand WP-4), 0.11 kg of polyoxyethylene sorbitan monostearate (Tweer21) and 0.016 kg of fatty alcohol-polyoxyethylene ether (0-10) into 0.9 kg of trichloromethane, uniformly dispersing by using a high-speed emulsifying machine, simultaneously dropwise adding deionized water until the system undergoes phase inversion, continuously stirring for 0.8h, adding a large amount of deionized water for dilution, and adjusting the solid content of the system to 15 wt% to obtain the organic resin emulsion.
(4) Adding 0.3 kg of I-ad and 0.25 kg of graphene into the organic resin emulsion, uniformly dispersing by ultrasonic, and then adding water to further dilute the organic resin emulsion until the solid content is 3.5 wt% to obtain the benzoxazole ionic compound and the graphene modified sizing agent.
The tensile strength of the PBO fibers before and after the sizing agent treatment was measured for the monofilament under the same test conditions as in example 1, and the results are shown in Table 1. The sizing agent-treated PBO fibers prepared in this example, the organic resin emulsion-treated PBO fibers prepared in step (3) of this example, and IFSS between the untreated PBO fibers and the matrix resin were tested under the same test conditions as in example 1, and the results are shown in table 2.
The matrix resin is polyurethane (brand WP-4).
Example 7
(1) 0.1mol of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 0.21mol of 4-aminosalicylic acid and 0.01mol of stannous chloride were added to 480g of polyphosphoric acid (80 wt% phosphorus pentoxide), N2Slowly raising the temperature to 120 ℃ under protection, stirring for 1h, then raising the temperature to 160 ℃, and reacting for 13h to obtain wine red transparent solution. And pouring the solution into water for precipitation, performing suction filtration, repeatedly washing a filter cake by using deionized water until the pH value of the filtrate is close to 7.4, and drying to obtain a crude product. And recrystallizing the crude product by using N, N-dimethylacetamide/water to obtain the high-purity benzoxazole diamine IV-ce.
(2) Dissolving 0.1mol of IV-ce in N, N-dimethylformamide, and adding 0.15mol of 1, 3-propane sultone, N2And raising the temperature of the system to 70 ℃ under protection, stirring and reacting for 10h, pouring reactants into acetone for precipitation, carrying out suction filtration, washing a filter cake for 3 times by using acetone, drying, adding a crude product into 0.2L of sodium hydroxide aqueous solution (1mol/L) for reaction, carrying out rotary evaporation to remove water, and further drying to obtain the benzoxazole ionic compound I-ce.
(3) Adding 0.5 kg of epoxy resin (No. 6101), 0.3 kg of cyanate ester resin (No. AroCyB-10), 0.2 kg of bismaleimide resin (No. QY9511), 0.03 kg of polyoxyethylene sorbitan monooleate (Tween 81) and 0.006 kg of higher aliphatic alcohol (octadeca-9-enol) into 1.3 kg of N, N-dimethylformamide, uniformly dispersing by a high-speed emulsifying machine, simultaneously dripping deionized water until the system is subjected to phase inversion, continuously stirring for 1h, adding a large amount of deionized water for dilution, adjusting the solid content of the system to 50 wt%, and obtaining the organic resin emulsion.
(4) Adding 0.1 kg of I-ce into the organic resin emulsion, uniformly dispersing by ultrasonic, and then adding water to further dilute the organic resin emulsion until the solid content is 5 wt% to obtain the sizing agent modified by the benzoxazole ionic compound.
The tensile strength of the PBO fibers before and after the sizing agent treatment was measured for the monofilament under the same test conditions as in example 1, and the results are shown in Table 1. The sizing agent-treated PBO fibers prepared in this example, the organic resin emulsion-treated PBO fibers prepared in step (3) of this example, and IFSS between the untreated PBO fibers and the matrix resin were tested under the same test conditions as in example 1, and the results are shown in table 2.
The base resin is a mixture of epoxy resin (No. 6101), cyanate resin (No. AroCyB-10) and bismaleimide resin (No. QY9511), wherein the mass ratio of the epoxy resin (No. 6101), the cyanate resin (No. AroCyB-10) and the bismaleimide resin (No. QY9511) is 5:3: 2.
Example 8
(1) 0.1mol of 2, 4-diaminophenol dihydrochloride, 0.21mol of 2, 5-dihydroxyterephthalic acid and 0.02mol of stannous chloride were added to 480g of polyphosphoric acid (84 wt% phosphorus pentoxide), N2Slowly heating to 120 ℃ under protection, stirring for 2h, then heating to 150 ℃, reacting for 5h, heating to 200 ℃, and reacting for 5h to obtain wine red transparent solution. And pouring the solution into water for precipitation, performing suction filtration, repeatedly washing a filter cake by using deionized water until the pH value of the filtrate is close to 7.4, and drying to obtain a crude product. And recrystallizing the crude product by using N, N-dimethylacetamide/water to obtain high-purity benzoxazole diamine VI-e.
(2) 0.1mol of VI-e is dissolved in N, N-dimethylacetamide, 0.2mol of 1, 3-propane sultone, N is added2And under protection, raising the temperature of the system to 100 ℃, stirring and reacting for 6h, pouring reactants into acetone for precipitation, carrying out suction filtration, washing a filter cake for 3 times by using acetone, drying, adding a crude product into 0.2L of sodium hydroxide aqueous solution (1mol/L) for reaction, carrying out rotary evaporation to remove water, and further drying to obtain the benzoxazole ionic compound III-e.
(3) Adding 0.3 kg of epoxy resin (brand 618), 0.7 kg of polyurethane (brand WP-4), 0.08 kg of polyoxyethylene sorbitan trioleate (Tweer85) and 0.01 kg of butyl stearate into 0.6 kg of tetrahydrofuran, uniformly dispersing by a high-speed emulsifying machine, simultaneously dropwise adding deionized water until the system is subjected to phase inversion, continuously stirring for 1h, adding a large amount of deionized water for dilution, and adjusting the solid content of the system to 25 wt% to obtain the organic resin emulsion.
(4) Adding 0.05 kg of III-e, 0.05 kg of I-cd and 0.4 kg of graphene into the organic resin emulsion, uniformly dispersing by ultrasonic, and then adding water to further dilute the organic resin emulsion until the solid content is 2.5 wt% so as to obtain the benzoxazole ionic compound and the graphene modified sizing agent.
The tensile strength of the PBO fibers before and after the sizing agent treatment was measured for the monofilament under the same test conditions as in example 1, and the results are shown in Table 1. The sizing agent-treated PBO fibers prepared in this example, the organic resin emulsion-treated PBO fibers prepared in step (3) of this example, and IFSS between the untreated PBO fibers and the matrix resin were tested under the same test conditions as in example 1, and the results are shown in table 2.
The matrix resin is a mixture of epoxy resin (the brand 618) and polyurethane (the brand WP-4), wherein the mass ratio of the epoxy resin (the brand 618) to the polyurethane (the brand WP-4) is 3: 7.
Table 1: tensile strength of PBO fibers before and after sizing treatment
Figure BDA0002031698760000211
Table 2: interfacial shear strength of PBO fiber composites
Figure BDA0002031698760000212
As can be seen from table 1, there was no significant change in tensile strength of the PBO fibers before and after the sizing treatment. As can be seen from Table 2, compared with the untreated PBO fiber composite material, the IFSS of the PBO fiber composite material treated by the organic resin emulsion is improved by 15-35%, and the IFSS of the PBO fiber composite material treated by the sizing agent is improved by 50-90%. This is due to: the sizing agent prepared by the embodiment has mild treatment conditions and no negative effect on the body performance of the PBO fiber, thereby maintaining the original tensile strength of the PBO fiber; moreover, the wetting property of the matrix resin to the PBO fiber is improved by the organic resin coating, so that the IFSS of the composite material is improved; in addition, the benzoxazole ion compound improves the compatibility of the sizing agent and the PBO fiber, and obviously improves the interaction force of the sizing agent and the PBO fiber. When graphene is contained in the sizing agent, the surface activity of the PBO fibers is also improved by introducing the graphene, so that the IFSS of the composite material is further improved.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (15)

1. A benzoxazole ionic compound represented by the following formula X,
Figure 578771DEST_PATH_IMAGE001
wherein n is an integer of 3-6, and A is selected from the following groups:
Figure 517909DEST_PATH_IMAGE002
、
Figure 434918DEST_PATH_IMAGE003
、
Figure 572638DEST_PATH_IMAGE004
m is selected from alkali metal ions; ar is selected from
Figure 34844DEST_PATH_IMAGE005
R is selected from H, OH and halogen; r1、R2Identical or different, independently of one another, from H, halogen, C1-6Alkyl radical, C1-6Alkoxy or halo C1-6An alkyl group; m is an integer of 1-4;
Figure 258015DEST_PATH_IMAGE006
indicates the attachment site.
2. The compound of claim 1, wherein n is selected from 3, 4 or 5; m is selected from Na; r is selected from H, OH and halogen; r1、R2Same or different, independently from each other selected from H, C1-3Alkyl radical, C1-3Alkoxy or halo C1-3An alkyl group; m is selected from 1,2, 3 or 4.
3. The compound according to claim 1 or 2, wherein the benzoxazole ion compound is selected from the group consisting of compounds represented by the following formulas (I) - (III),
Figure 713135DEST_PATH_IMAGE007
wherein Ar is selected from
Figure 970941DEST_PATH_IMAGE008
；
R is selected from H or OH.
4. The compound of claim 3, wherein the benzoxazole ionic compound is at least one compound selected from the group consisting of:
Figure 72890DEST_PATH_IMAGE009
Figure 32624DEST_PATH_IMAGE010
Figure 511010DEST_PATH_IMAGE011
。
5. a process for the preparation of a benzoxazole ionic compound according to any one of claims 1-4, characterized in that it comprises the following steps:
reacting a compound X-1 with a compound X-2 to obtain a compound shown as a formula X-3, reacting the compound shown as the formula X-3 with an alkali metal hydroxide to obtain a benzoxazole ionic compound shown as the formula X,
Figure 623323DEST_PATH_IMAGE012
wherein A, n has the definition set forth in claim 1.
6. A sizing agent is characterized in that the sizing agent is a mixed system consisting of organic resin, an emulsifier, a lubricant, the benzoxazole ionic compound according to any one of claims 1 to 4 and water, wherein the content of the emulsifier is 1-20 wt% of the organic resin; the content of the lubricant is 0.3-5 wt% of the organic resin; the content of the compound is 0.5-60 wt% of the organic resin; the solid content of the sizing agent is 0.05-8 wt%;
the organic resin is at least one of epoxy resin, cyanate resin, bismaleimide resin, polyimide resin and polyurethane;
the emulsifier is nonionic surfactant;
the lubricant is at least one of polyoxyethylene ether, higher fatty amine, higher fatty alcohol and higher fatty ester.
7. The sizing agent according to claim 6, wherein the lubricant is butyl stearate.
8. The sizing agent according to claim 6, further comprising graphene, wherein the graphene is graphene oxide prepared by a Hummers method and having polar groups on the surface, or graphene having no groups on the surface after reduction.
9. The sizing agent according to claim 8, wherein when graphene is further included in the sizing agent, the content of graphene is 0.5-60 wt% of the organic resin.
10. The sizing agent according to claim 6, wherein the sizing agent optionally comprises an organic solvent selected from at least one of ketone solvents, ether solvents, halogenated alkane solvents, and nitrogen-containing organic solvents.
11. The sizing agent according to claim 10, wherein when the sizing agent further comprises an organic solvent, the content of the organic solvent is 0.5 to 300 wt% of the organic resin.
12. The method for preparing the sizing agent according to claim 6, comprising:
(1) mixing organic resin, an emulsifier, a lubricant and an optional organic solvent, adding water until the system is subjected to phase inversion, stirring, adding water for dilution, and adjusting the solid content of the system to 10-50 wt% to obtain an organic resin emulsion;
(2) adding the benzoxazole ionic compound and optionally graphene according to any one of claims 1 to 4 into an organic resin emulsion, and adding water to further dilute the organic resin emulsion to a solid content of 0.05 to 8 wt% through ultrasonic dispersion to obtain the sizing agent;
wherein the content of the emulsifier is 1-20 wt% of the organic resin; the content of the lubricant is 0.3-5 wt% of the organic resin; the content of the benzoxazole ionic compound is 0.5-60 wt% of the organic resin; the content of graphene is 0-60 wt% of the organic resin; the content of the organic solvent is 0-300 wt% of the organic resin;
the organic resin is at least one of epoxy resin, cyanate resin, bismaleimide resin, polyimide resin and polyurethane;
the emulsifier is nonionic surfactant;
the lubricant is at least one of polyoxyethylene ether, higher fatty amine, higher fatty alcohol and higher fatty ester.
13. The method of claim 12, wherein the lubricant is butyl stearate.
14. Use of the sizing of claim 6 in the treatment of PBO fibers.
15. The composite material is characterized by comprising PBO fibers and a sizing agent coated on the surfaces of the PBO fibers; the sizing agent is selected from the sizing agents of claim 6.
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