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CN109679342B - Flame-retardant cyanate hot pressing plate - Google Patents

Flame-retardant cyanate hot pressing plate Download PDF

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CN109679342B
CN109679342B CN201811595579.5A CN201811595579A CN109679342B CN 109679342 B CN109679342 B CN 109679342B CN 201811595579 A CN201811595579 A CN 201811595579A CN 109679342 B CN109679342 B CN 109679342B
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flame
retardant
aramid fiber
cyanate
stirring
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CN109679342A (en
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梁国正
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Suzhou University
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Suzhou University
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
    • 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
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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    • 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
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

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  • Engineering & Computer Science (AREA)
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  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
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  • Fireproofing Substances (AREA)

Abstract

The patent relates to a flame-retardant cyanate hot pressboard, which is prepared by adding flame-retardant aramid fiber into cyanate prepolymer solution, stirring, pouring into a mold, hot-pressing, and naturally cooling to prepare the flame-retardant cyanate hot pressboard; the length of the flame-retardant aramid fiber is 2.5-3 mm; the using amount of the flame-retardant aramid fiber is 14-15% of the mass of the cyanate ester prepolymer solution. The modified cyanate ester plate obtained by the invention has better flame retardant property and impact strength, and simultaneously improves the ultraviolet aging resistance compared with a pure cyanate ester system.

Description

Flame-retardant cyanate hot pressing plate
Technical Field
The invention relates to a high-performance resin composite modification technology, in particular to a flame-retardant cyanate ester hot pressing plate.
Background
The CE is a thermosetting resin with application potential and development prospect, and can be widely applied to high-tech fields such as high-frequency PCBs, aerospace structural materials, radomes and the like, and the development obstacle of the CE is insufficient in toughness and flame retardant property. In addition, in recent years, in order to improve the ultraviolet resistance of resin, ultraviolet screening agents are introduced, wherein organic ultraviolet screening agents have the problems of poor heat resistance and oxidation resistance, and inorganic ultraviolet screening agents have the problems of high catalytic activity, limited binding force with organic matters and falling off in the using process, so that the service reliability is influenced. The inventor aims to develop a novel aramid fiber with surface activity and ultraviolet resistance, which has a good ultraviolet resistance effect, but does not relate to flame retardant property and is not used for research on resin matrix composite materials.
Disclosure of Invention
The invention aims to research and develop a novel inorganic ultraviolet modifier on the premise of keeping the original thermal property and electrical property of cyanate not to be reduced, and an inorganic coating with strong bonding force is formed on the surface of aramid fiber by a novel preparation method and then used for cyanate modification, thereby endowing the modified cyanate plate with ultraviolet resistance and flame retardance.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the preparation method of the flame-retardant cyanate hot pressboard comprises the steps of adding flame-retardant aramid fibers into a cyanate prepolymer solution, stirring, pouring into a mold, hot-pressing, and naturally cooling to prepare the flame-retardant cyanate hot pressboard; the length of the flame-retardant aramid fiber is 2.5-3 mm; the using amount of the flame-retardant aramid fiber is 14-15% of the mass of the cyanate ester prepolymer solution.
The preparation method of the flame-retardant cyanate hot pressboard comprises the following steps of adding flame-retardant aramid fiber into cyanate prepolymer melt, stirring, pouring into a mold, hot-pressing, and naturally cooling to prepare the flame-retardant cyanate hot pressboard; the length of the flame-retardant aramid fiber is 2.5-3 mm; the using amount of the flame-retardant aramid fiber is 14-15% of the mass of the cyanate ester prepolymer solution.
The invention also discloses a prepolymer for the flame-retardant cyanate ester hot pressboard, and the preparation method of the prepolymer for the flame-retardant cyanate ester hot pressboard comprises the following steps of adding the flame-retardant aramid fiber into the cyanate ester prepolymer melt, stirring, pouring into a mold, and naturally cooling to prepare the prepolymer for the flame-retardant cyanate ester hot pressboard; the length of the flame-retardant aramid fiber is 2.5-3 mm; the using amount of the flame-retardant aramid fiber is 14-15% of the mass of the cyanate ester prepolymer solution.
The invention researches the effect of adding flame-retardant aramid fiber on improving flame-retardant performance and impact strength based on pure cyanate, and the embodiment shows that the impact strength and oxygen index of cyanate can be improved by adopting a certain amount of flame-retardant aramid fiber, inorganic particles on the surface of the flame-retardant aramid fiber play a role in promoting the curing of cyanate, and a modified cyanate system can be cured well without adding a catalyst.
In the invention, the preparation method of the flame-retardant aramid fiber comprises the following steps:
(1) dissolving cerium salt and inorganic base in water, stirring for 20-45 min, then adding hydrogen peroxide to obtain a suspension, adjusting the pH of the suspension to 10-14, reacting for 10-20 h at 20-50 ℃, washing with water, filtering, drying, and calcining for 1-3 h at 500-800 ℃ to obtain nano cerium oxide; dispersing the nano cerium oxide, the boron source and the nitrogen-containing compound in a mixed solution consisting of ethanol and water, ultrasonically stirring for 0.5-1.5 h, then carrying out rotary steaming and drying, then dispersing in a cobalt nitrate aqueous solution, ultrasonically stirring for 0.5-1 h, and carrying out rotary steaming and drying to obtain a solid; calcining the solid for 13-15 h at 850-950 ℃ in the atmosphere of nitrogen source gas, and then crushing to obtain nano particles;
(2) adding the nano particles into a hydrogen peroxide solution, magnetically stirring for 0.5-1 h, adding a sulfuric acid solution, and continuously magnetically stirring for 0.5 h; then filtering to obtain a filter cake, washing the filter cake with water, and drying to obtain modified particles;
(3) adding the modified particles and dopamine hydrochloride into a buffer solution with the pH value of 8.3-8.8, and stirring at room temperature for 2-3 hours; then adding a curcumin ethanol solution, and continuously stirring for 1-2 h; then filtering, washing and drying to obtain organic modified particles;
(4) immersing silicon methoxylated aramid fiber in an aqueous solution containing trimethylsilanol, and oscillating for 0.5-1 h; then immersing the particles into an aqueous solution containing organic matter modified particles, and carrying out oscillation reaction for 2-3 h at the temperature of 70-80 ℃; and after the reaction is finished, washing and drying to obtain the flame-retardant aramid fiber.
In the invention, the silicon methoxylated aramid fiber is the prior art and is described in the invention application 2018104223562; the aramid fiber is para-aramid fiber or meta-aramid fiber. In the present invention, the silicon methoxylated aramid fiber may be prepared by, by mass,
(1) sequentially immersing aramid fibers in acetone, petroleum ether and deionized water, respectively staying for 2-4 h, then washing and drying to obtain the aramid fibers with clean surfaces;
(2) soaking 1 part of aramid fiber with clean surface into an alcohol solution of alkali metal hydroxide with the mass concentration of 5.0-15.0 wt%, and carrying out oscillation reaction for 4-8 h at the temperature of 50-80 ℃; after the reaction is finished, washing and drying to obtain the aramid fiber with amino and carboxyl on the surface;
(3) and (3) under an inert gas atmosphere, soaking 1 part of the aramid fiber with amino and carboxyl on the surface obtained in the step (2) into 150-350 parts of organic solvent containing 100-200 parts of gamma-glycidyl ether oxypropyl trimethoxy silane, and reacting at 50-100 ℃ for 10-18 h to obtain the silicon methoxylated aramid fiber.
In the invention, the inorganic alkali is sodium hydroxide or potassium hydroxide; the cerium salt is one or any combination of cerium nitrate and cerium chloride; the boron source is one of boric acid and metaboric acid; the nitrogen-containing compound is one of urea, trichlorocyanamide and ammonium bromide; the buffer solution is one of Tris-HCl and disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution; the nitrogen source gas is one of nitrogen and ammonia.
In the invention, the mass ratio of the nano cerium oxide to the boron source to the nitrogen-containing compound to the cobalt nitrate is 100 to (30-50) to (60-120) to (10-13); the mass ratio of the nano particles to the hydrogen peroxide solution to the sulfuric acid solution is 100 to (60-70) to (5-7); the mass ratio of the modified particles to the dopamine hydrochloride to the curcumin is 100 to (30-50) to (10-12); the mass ratio of the silicon methoxylated aramid fiber to the organic matter modified particles to the trimethylsilanol is 1: 2-9: 0.3-0.35; the mass ratio of the cerium salt to the inorganic base is 100: 20-50.
In the invention, cyanate is heated at 110-115 ℃ for 0.5-1 hour to obtain cyanate prepolymer solution; the stirring is mechanical stirring for 3-3.5 hours at 145-150 ℃. The hot pressing process is 0.5MPa/110 ℃/0.5 hour +0.5MPa/130 ℃/1.5 hour +1MPa/160 ℃/2 hour +1MPa/200 ℃/2 hour. Stirring at a higher temperature to ensure that the viscosity of the cyanate ester is very low, which is beneficial to the dispersion and contact of aramid fibers, and simultaneously, the temperature gives a certain reaction degree to the cyanate ester, which is considered to improve the resin fluidity during hot pressing and avoid excessive glue flowing; during hot pressing, the whole system is slowly heated at a lower temperature, so that uneven reaction caused by uneven heating of the periphery and the middle of the die is avoided, a well-cured plate can be obtained through subsequent step curing, and the die is an existing conventional product.
According to the invention, after the nano cerium oxide, the boron source and the nitrogen-containing compound are mixed and adsorbed and react, cobalt nitrate is added, the disadvantages of wrapping boron nitride are reduced, cobalt is adsorbed on the surface of the nano cerium oxide, and according to element analysis, the cobalt ions contained in the nano particles can be found; the presence of cobalt is believed to improve the reactivity of the nanoparticles, particularly the reactivity with aramid interfaces, which is beneficial to the attachment of the nanoparticles to the aramid surfaces and also plays a certain role in curing cyanate ester, thereby improving the flame retardancy.
In the present invention, the mass concentrations of the hydrogen peroxide solution and the sulfuric acid solution are 30% and 98%, respectively. The invention discloses the surface treatment of the nano particles for the first time, which can form unevenness on the surfaces of the nano particles, which is caused by oxidation etching, and can also increase the surface active groups of the nano particles, such as hydroxyl; this is advantageous for improving the reactivity and interfacial action of the nanoparticles. According to the invention, a small amount of curcumin is adopted to be combined to react successively, so that the influence on the reaction of dopamine hydrochloride on the surface of the modified particle is small, and the curcumin can react on the surface of the particle, so that the improvement on the interfacial effect of the particle and the aramid fiber is facilitated.
In the invention, the addition of trimethylsilanol can be compatible with silicon methoxyl on the surface of aramid fiber on one hand, and can react with curcumin and dopamine to a certain extent on the other hand, and more importantly, can be cooperated with boron nitride to improve the flame retardant property; as can be seen from the examples, the addition of trimethylsilanol is advantageous for flame retardancy.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, on the basis that the polydopamine is modified to ensure that the inorganic nanoparticles are connected with the aramid fiber surface by chemical bonds, the nanoparticles are treated by hydrogen peroxide and sulfuric acid solution to obtain modified particles with improved surface structures and activities, so that the reactivity of the nanoparticles is further improved.
2. The inorganic nano modifier provided by the invention keeps the high ultraviolet absorptivity of the polydopamine modified turbostratic boron nitride coated cerium oxide, and the addition of cobalt improves the adhesive force of the nanoparticles, can improve the dispersibility of the nanoparticles in cyanate ester, and is beneficial to flame retardance.
3. According to the invention, the flame retardant effect is obviously improved on the surface of aramid fiber with good flame retardancy by virtue of the nanometer particles, the interface action of the nanometer particles and the aramid fiber and the synergistic action of silanol, and the influence on the ultraviolet resistance is very small.
4. In a pure cyanate system, a cyanate plate with good curing can be obtained by the effect of aramid fiber surface nano particles without adding an organic tin catalyst, and the flame retardant property and the mechanical property of the system are actually improved compared with the plate added with the catalyst.
Detailed Description
Reference 2018104223562:
(1) 1g of aramid fiber (Kevlar-49, diameter 12 μm, density 1.45 g/m)3Manufactured by dupont, usa) were sequentially immersed in acetone at 70 ℃, petroleum ether at 75 ℃ and deionized water at 115 ℃ for 3 hours, respectively; then taking out the fiber, and drying in a vacuum oven at 80 ℃ to obtain clean aramid fiber, which is marked as KF;
(2) dissolving 10.5g of sodium hydroxide in 120mL of ethanol to prepare an ethanol solution A of the sodium hydroxide; immersing the clean aramid fiber KF obtained in the step (1) in the solution A, carrying out oscillation reaction for 5h at 65 ℃, and washing and drying after the reaction is finished to obtain the aramid fiber with amino and carboxyl on the surface;
(3) adding 0.25g of aramid fiber with amino and carboxyl on the surface and 30mL of gamma-glycidoxypropyltrimethoxysilane into 70mL of ethanol, and reacting at 70 ℃ for 12h in a nitrogen atmosphere; and after the reaction is finished, taking out the fiber to obtain the aramid fiber with silicon methoxyl on the surface.
Example 1
(1) Dissolving 12.32g of cerium chloride and 6g of sodium hydroxide in an aqueous solution, and stirring for 35min to obtain a suspension A; adding hydrogen peroxide, adjusting the pH value of the suspension A to 12 by using sodium hydroxide, reacting for 12 hours at 40 ℃, filtering, washing and drying; calcining the mixture in a muffle furnace at 700 ℃ for 2h to obtain the nano-particlesCerium oxide CeO2(ii) a Putting 3g of nano cerium oxide, 1.2g of boric acid and 2.1g of urea into a mixed solution of 400mL of ethanol and 200mL of water, and performing ultrasonic dispersion for 1 h; performing rotary evaporation and drying to obtain a dried substance, then dispersing the dried substance in 100 mL of cobalt nitrate aqueous solution (3.6 mg/mL), performing ultrasonic stirring for 50 minutes, and performing rotary evaporation and drying to obtain a solid substance; calcining the solid for 15 hours at 950 ℃ in a nitrogen atmosphere; after the reaction is finished, washing, drying and crushing to obtain nano particles with the particle size of less than 100nm, wherein the nano particles contain cobalt element through elemental analysis;
(2) adding 5g of nano particles into 3g of hydrogen peroxide solution (30 wt%), magnetically stirring for 0.5h, adding 0.3 g of sulfuric acid solution (98 wt%), and continuously magnetically stirring for 0.5 h; then filtering to obtain a filter cake, washing the filter cake with water, and drying to obtain modified particles; the scanning electron microscope shows that the surface of the modified particle is coarser than that of the nano particle, and the modified particle has tiny unevenness; the modified particles are added into water in the same way, and the number of bubbles generated by the modified particles is slightly more than that of the nano particles;
(3) preparing a Tris-HCl buffer solution with the concentration of 10mM, and adjusting the pH value of the buffer solution to 8.5 by using sodium hydroxide to obtain a buffer solution B; adding the modified particles and dopamine hydrochloride into the buffer solution B according to the mass ratio of the modified particles to the dopamine hydrochloride of 5:1.6, stirring for 2 hours at room temperature, then adding a curcumin ethanol solution, and continuing stirring for 2 hours; after the reaction is finished, filtering, washing and drying to obtain organic modified particles, wherein the mass ratio of the modified particles to the curcumin is 10: 1.2;
(4) immersing 0.2g of silicon methoxylated aramid fiber in an aqueous solution containing 0.06g of trimethylsilanol, and oscillating for 0.5 h; after the reaction is finished, taking out the fiber, dispersing the fiber and 1g of organic matter modified particles in an aqueous solution, and oscillating for 2.5 hours at the temperature of 80 ℃; and (4) taking out the fiber after the reaction is finished, washing and drying to obtain the flame-retardant aramid fiber.
(5) Heating bisphenol A cyanate at 115 ℃ for 0.5 hour to obtain cyanate prepolymer melt; intercepting flame-retardant aramid fibers with the length of 2.5-3 mm, adding the flame-retardant aramid fibers into the cyanate ester prepolymer solution, mechanically stirring the mixture at 150 ℃ for 3 hours, pouring the mixture into a conventional mold, naturally cooling the mixture, and breaking the mixture to prepare a prepolymer for the flame-retardant cyanate ester hot pressing plate; the using amount of the flame-retardant aramid fiber is 15% of the mass of the cyanate ester prepolymer melt.
Preparing the flame-retardant cyanate hot-pressing board by hot-pressing and naturally cooling the prepolymer for the flame-retardant cyanate hot-pressing board; the hot pressing process is 0.5MPa/110 ℃/0.5 hour +0.5MPa/130 ℃/1.5 hour +1MPa/160 ℃/2 hour +1MPa/200 ℃/2 hour.
Performance testing
The flame-retardant cyanate ester hot pressboard is exposed to a QUV/spray type ultraviolet light accelerated aging tester (U.S. Q-Lab company) for 168h of UV irradiation (the radiation illumination is 1.55W/m)2And the test temperature is 60 ℃), and the flame-retardant cyanate hot-pressing board subjected to 168-hour irradiation is obtained.
The impact strength of the flame-retardant cyanate ester hot-pressing plate before and after ultraviolet irradiation is 16.68KJ/m2、13.84KJ/m2And the reduction is 17.03%; the oxygen index before and after irradiation was 31, 29. Five positions (middle and four corners) of one epoxy modified cyanate ester composite board are sintered at 950 ℃ in the same size, the difference of the residual substance mass is less than 1%, and the filler is uniformly dispersed.
The obtained CE cured resin and composite material have excellent performance by using organic tin compound as catalyst for curing reaction of cyanate ester resin, the cyanate ester resin has good solubility and technological properties and can meet various processing requirements including prepreg, resin transfer molding, winding, pultrusion, pressure molding, compression molding and the like, and the cured cyanate ester resin has the characteristics of low dielectric constant, extremely small dielectric loss, high glass transition temperature, low shrinkage, low moisture absorption rate, excellent mechanical property, excellent adhesive property and the like. According to the invention, the nano particles with high binding force are prepared on the surface of the aramid fiber, a catalyst is not needed, cyanate ester can be effectively cured by heating, particularly, the interface reactivity of each component is good in the presence of the aramid fiber with the nano particles on the surface, and the impact strength and the flame retardant property are further improved from the test result.
Comparative example
Heating bisphenol A cyanate at 115 deg.C for 0.5 hr, mechanically stirring at 150 deg.C for 3 hr, adding conventional organic tin compound as catalyst, and stirring 2Pouring the mixture into a conventional die after minutes, naturally cooling the mixture and then breaking the mixture to prepare a prepolymer for a cyanate hot-pressing plate; preparing the cyanate hot pressing board by hot pressing and natural cooling the prepolymer for the cyanate hot pressing board; the hot pressing process is 0.5MPa/110 ℃/0.5 hour +0.5MPa/130 ℃/1.5 hour +0.5MPa/160 ℃/2 hour +1MPa/200 ℃/2 hour. The impact strength of the cyanate ester hot pressing plate before and after ultraviolet irradiation is 11.69KJ/m2、6.32KJ/m245.94% drop; the pre-irradiation oxygen index was 24.
Comparative examples were obtained by substituting the conditions in Table 1 and performing the performance tests in accordance with the examples, see Table 1, wherein "-" indicates no test.
TABLE 1 preparation conditions and test results
Figure 507366DEST_PATH_IMAGE002
The unique structure of the cyanate ester determines the properties, including excellent dielectric property, high heat resistance, good comprehensive mechanical property, good dimensional stability, extremely low water absorption rate and the like, but the flame retardance and the impact strength are poor, the modified cyanate ester is used as a composite material, the combustion mechanism is complex, and the process influence factors are many, the invention seems to be an effective method for improving the flame retardance from the interface action of the modified particles and aramid fibers/resin and the synergistic action of the property of the modified particles and the property combination elements, and further research is needed for the thermal property and the electrical property; the invention not only solves the problems of poor ultraviolet resistance and the like of cyanate ester resin, but also mainly improves the flame retardant property of cyanate ester, so that the aramid fiber modified cyanate ester can play an important role in the military or civil field as a typical representative of high-performance resin materials.

Claims (2)

1. The preparation method of the flame-retardant cyanate hot pressboard is characterized in that the flame-retardant cyanate hot pressboard is prepared by adding flame-retardant aramid fiber into cyanate prepolymer solution, stirring the mixture, pouring the mixture into a mold, and then carrying out hot pressing and natural cooling on the mixture to prepare the flame-retardant cyanate hot pressboard; the length of the flame-retardant aramid fiber is 2.5-3 mm; the using amount of the flame-retardant aramid fiber is 14-15% of the mass of the cyanate ester prepolymer solution; heating cyanate at 110-115 ℃ for 0.5-1 hour to obtain cyanate prepolymer solution; stirring is mechanically stirring for 3-3.5 hours at 145-150 ℃; the preparation method of the flame-retardant aramid fiber comprises the following steps:
(1) dissolving cerium salt and inorganic base in water, stirring for 20-45 min, then adding hydrogen peroxide to obtain a suspension, adjusting the pH of the suspension to 10-14, reacting for 10-20 h at 20-50 ℃, washing with water, filtering, drying, and calcining for 1-3 h at 500-800 ℃ to obtain nano cerium oxide; dispersing the nano cerium oxide, the boron source and the nitrogen-containing compound in a mixed solution consisting of ethanol and water, ultrasonically stirring for 0.5-1.5 h, then carrying out rotary steaming and drying, then dispersing in a cobalt nitrate aqueous solution, ultrasonically stirring for 0.5-1 h, and carrying out rotary steaming and drying to obtain a solid; calcining the solid for 13-15 h at 850-950 ℃ in the atmosphere of nitrogen source gas, and then crushing to obtain nano particles;
(2) adding the nano particles into a hydrogen peroxide solution, magnetically stirring for 0.5-1 h, adding a sulfuric acid solution, and continuously magnetically stirring for 0.5 h; then filtering to obtain a filter cake, washing the filter cake with water, and drying to obtain modified particles;
(3) adding the modified particles and dopamine hydrochloride into a buffer solution with the pH value of 8.3-8.8, and stirring at room temperature for 2-3 hours; then adding a curcumin ethanol solution, and continuously stirring for 1-2 h; then filtering, washing and drying to obtain organic modified particles;
(4) immersing silicon methoxylated aramid fiber in an aqueous solution containing trimethylsilanol, and oscillating for 0.5-1 h; then immersing the particles into an aqueous solution containing organic matter modified particles, and carrying out oscillation reaction for 2-3 h at the temperature of 70-80 ℃; after the reaction is finished, washing and drying to obtain the flame-retardant aramid fiber;
the mass ratio of the nano cerium oxide to the boron source to the nitrogen-containing compound to the cobalt nitrate is 100 to (30-50) to (60-120) to (10-13); the mass ratio of the nano particles to the hydrogen peroxide solution to the sulfuric acid solution is 100 to (60-70) to (5-7); the mass ratio of the modified particles to the dopamine hydrochloride to the curcumin is 100 to (30-50) to (10-12); the mass ratio of the silicon methoxylated aramid fiber to the organic matter modified particles to the trimethylsilanol is 1: 2-9: 0.3-0.35; the mass ratio of the cerium salt to the inorganic base is 100: 20-50;
the hot pressing process is 0.5MPa/110 ℃/0.5 hour +0.5MPa/130 ℃/1.5 hour +1MPa/160 ℃/2 hour +1MPa/200 ℃/2 hour.
2. The flame retardant cyanate ester hot pressboard according to claim 1, wherein: the aramid fiber is para-aramid fiber or meta-aramid fiber; the inorganic alkali is sodium hydroxide or potassium hydroxide; the cerium salt is one or any combination of cerium nitrate and cerium chloride; the boron source is one of boric acid and metaboric acid; the nitrogen-containing compound is one of urea, trichlorocyanamide and ammonium bromide; the buffer solution is one of Tris-HCl and disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution; the nitrogen source gas is one of nitrogen and ammonia.
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