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CN109679342A - Fire-retardant cyanate heating platen - Google Patents

Fire-retardant cyanate heating platen Download PDF

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Publication number
CN109679342A
CN109679342A CN201811595579.5A CN201811595579A CN109679342A CN 109679342 A CN109679342 A CN 109679342A CN 201811595579 A CN201811595579 A CN 201811595579A CN 109679342 A CN109679342 A CN 109679342A
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fire
cyanate
retardant
aramid fiber
heating platen
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CN201811595579.5A
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CN109679342B (en
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梁国正
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Suzhou University
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • 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
    • D06M11/32—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
    • 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
    • D06M11/32—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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

This patent is related to a kind of fire-retardant cyanate heating platen, and preparation method is that fire-retardant aramid fiber is added in cyanate prepolymer melt, pours into mold, then hot pressing, natural cooling after stirring, prepares fire-retardant cyanate heating platen；The length of the fire-retardant aramid fiber is 2.5~3 millimeters；The dosage of the fire-retardant aramid fiber is the 14~15% of cyanate prepolymer melt quality.The modified cyanic acid ester plate that the present invention obtains has preferable flame retardant property and impact strength, while purer cyanate system improves anti-ultraviolet ageing performance.

Description

Fire-retardant cyanate heating platen
Technical field
The present invention relates to a kind of high performance resin composite modification technologies, and in particular to a kind of fire-retardant cyanate heating platen.
Background technique
CE is a kind of thermosetting resin for relatively having application potential and development prospect, in frequency PCB, Aerospace structural material and thunder It will be more widely used up to high-tech areas such as covers, the obstacle of CE development is that toughness and flame retardant property are insufficient.Separately Outside, people are to improve resin ultra-violet resistance in recent years, introduce ultraviolet light screener, wherein there are heat resistances for organic ultraviolet screener With oxidative resistance difference problem, that there are catalytic activity is high for inorganic UV screener, with the binding force of organic matter it is limited, in use process In will appear the problem of falling off, to influence service reliability.Inventor seminar has developed one kind and has both surface-active and resistance to UV protection novel aramid fiber has preferable resistance to ultraviolet effect, but without reference to flame retardant property, also without being used for resin The research of based composites.
Summary of the invention
Under the premise of keeping the original hot property of cyanate and electrical property not to reduce, research and development novel inorganic is purple Outer modifying agent forms a kind of inorganic coating that binding force is strong in aramid fiber surface, is used further to cyanic acid by new preparation method It is ester modified, to assign modified cyanic acid ester plate UV resistance and anti-flammability.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is that:
Fire-retardant cyanate heating platen, preparation method are fire-retardant aramid fiber to be added in cyanate prepolymer melt, after stirring It pours into mold, then hot pressing, natural cooling, prepares fire-retardant cyanate heating platen；The length of the fire-retardant aramid fiber is 2.5 ~3 millimeters；The dosage of the fire-retardant aramid fiber is the 14~15% of cyanate prepolymer melt quality.
The preparation method of fire-retardant cyanate heating platen, includes the following steps, cyanate pre-polymerization is added in fire-retardant aramid fiber It in object melt, is poured into mold after stirring, then hot pressing, natural cooling, prepares fire-retardant cyanate heating platen；The fire-retardant aramid fiber The length of fiber is 2.5~3 millimeters；The dosage of the fire-retardant aramid fiber is the 14~15% of cyanate prepolymer melt quality.
The invention also discloses fire-retardant cyanate heating platen prepolymer, the fire-retardant cyanate heating platen prepolymer Preparation method includes the following steps, fire-retardant aramid fiber is added in cyanate prepolymer melt, is poured into mold after stirring, from It is so cooling, prepare fire-retardant cyanate heating platen prepolymer；The length of the fire-retardant aramid fiber is 2.5~3 millimeters；The resistance The dosage for firing aramid fiber is the 14~15% of cyanate prepolymer melt quality.
The present invention studies the addition of fire-retardant aramid fiber to the work for improving flame retardant property, impact strength based on pure cyanate With effect, embodiment shows that cyanate impact strength and oxygen index (OI) can be improved using a certain amount of fire-retardant aramid fiber, hinders The inorganic particulate for firing aramid fiber surface plays accelerative action in curing to cyanate, and modified cyanic acid ester system does not need addition catalyst i.e. Can preferably it solidify.
In the present invention, the preparation method of the fire-retardant aramid fiber includes the following steps:
(1) cerium salt and inorganic base are dissolved in water, stir 20~45min, hydrogen peroxide is then added, obtains suspension, adjusted 10~20h is reacted after the pH to 10~14 of suspension at 20 DEG C~50 DEG C, using washing, filtering, it is dry after, 500~ 1~3h is calcined at 800 DEG C, obtains nano-cerium oxide；The nano-cerium oxide, boron source and nitrogenous compound are dispersed in by ethyl alcohol In the mixed solution of water composition, 0.5~1.5h is stirred by ultrasonic, using revolving, it is dry after be redispersed in cobalt nitrate aqueous solution In, 0.5~1h is stirred by ultrasonic, using rotating, be dried to obtain solids；The solids is under nitrogen source gas atmosphere, in 850 DEG C~950 DEG C at calcine 13~15h, then crush obtain nanoparticle；
(2) nanoparticle is added in hydrogen peroxide solution, 0.5~1h of magnetic agitation, adds sulfuric acid solution, continue magnetic agitation 0.5h；Then filter cake is obtained by filtration, then by filter cake washing, drying, obtains modified particle；
(3) modified particle and Dopamine hydrochloride are added in the buffer that pH is 8.3~8.8,2~3h is stirred at room temperature； Then curcumin ethanol solution is added, continues 1~2h of stirring；Then it is filtered, washed, dries, obtain organics modifications grain Son；
(4) silicon methoxylation aramid fiber is immersed in the aqueous solution containing trimethyl silanol, vibrates 0.5~1h；Then it soaks Enter in the aqueous solution containing organics modifications particle, 2~3h of oscillating reactions at 70 DEG C~80 DEG C；After reaction by washing It washs, dry, obtain fire-retardant aramid fiber.
In the present invention, silicon methoxylation aramid fiber is the prior art, is recorded in 2018104223562 patent applications； The aramid fiber is para-aramid fiber, meta-aramid fibers.In the present invention, the preparation method of silicon methoxylation aramid fiber Can be as follows, by mass,
(1) aramid fiber successively submerges in acetone, petroleum ether, deionized water, stops 2h~4h respectively, then washs, dry, Obtain the aramid fiber of clean surface；
(2) aramid fiber of 1 part of clean surface is immersed to the alcohol for the alkali metal hydroxide that mass concentration is 5.0~15.0wt% In solution, under conditions of temperature is 50 DEG C~80 DEG C, 4~8h of oscillating reactions；After reaction, it washes, dry to get table is arrived Face has the aramid fiber of amino and carboxyl；
(3) under atmosphere of inert gases, the surface that 1 part of step (2) obtains is contained with the immersion of the aramid fiber of amino and carboxyl In 100~200 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes, 150~350 parts of organic solvents, temperature be 50~ 10~18h is reacted under the conditions of 100 DEG C, obtains silicon methoxylation aramid fiber.
In the present invention, the inorganic base is sodium hydroxide or potassium hydroxide；The cerium salt is cerous nitrate, in cerium chloride A kind of or their any combination；The boron source is one of boric acid, metaboric acid；The nitrogenous compound is urea, three One of chlorocyanamide, ammonium bromide；The buffer is Tris-HCl, one in disodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution Kind；The nitrogen source gas is one of nitrogen, ammonia.
In the present invention, nano-cerium oxide, boron source, nitrogenous compound, cobalt nitrate mass ratio be 100: (30~50): (60 ~120): (10~13)；Nanoparticle, hydrogen peroxide solution, sulfuric acid solution mass ratio be 100: (60~70): (5~7)；Change Property particle, Dopamine hydrochloride, curcumin mass ratio be 100: (30~50): (10~12)；Silicon methoxylation aramid fiber has Machine object modified particle, trimethyl silanol mass ratio be 1: (2~9): (0.3~0.35)；The mass ratio of cerium salt and inorganic base is 100: (20~50).
In the present invention, cyanate is heated 0.5~1 hour in 110~115 DEG C, obtains cyanate prepolymer melt；Stirring For in 145~150 DEG C mechanical stirring 3~3.5 hours.The technique of hot pressing is 0.5MPa/110 DEG C/0.5 hour+0.5MPa/130 DEG C /+1MPa/200 DEG C/2 hours+1MPa/160 DEG C/2 hours 1.5 hours.Stirring is so that cyanate viscosity is non-at relatively high temperatures It is often low, conducive to the dispersion of aramid fiber with contact, while this temperature gives cyanate certain extent of reaction, is believed to change Resin Flow when kind hot pressing, avoids excessive gummosis；When hot pressing, make whole system heating slow under lower temperature Slowly, mold surrounding is avoided to react uneven with caused by intermediate uneven heating, subsequent staged curing available solidification is good Plate, mold are existing conventional products.
The present invention adds cobalt nitrate after reacting after nano-cerium oxide, boron source and nitrogenous compound mixing and absorption, reduces To the unfavorable of boron nitride package, while in nano-cerium oxide adsorption cobalt, according to elemental analysis, it can be found that nanoparticle contains Cobalt ions；The presence of cobalt is believed to improve nanoparticle reactivity especially with aramid fiber interfacial reaction performance, this is to nanoparticle Attachment of the son on aramid fiber surface is advantageous, also plays a role to cyanate solidification, to be improved effect to anti-flammability, other cobalt The performance that nanoparticle Yu aramid fiber cyanate interface conjugate may be improved, to improving, interface anti-flammability is advantageous.
In the present invention, hydrogen peroxide solution, sulfuric acid solution mass concentration be respectively 30%, 98%.The present invention is first public right The surface treatment of nanoparticle can form injustice in nanoparticle surface, it should can also be increased and receive caused by oxide etch Rice corpuscles surface active groups such as hydroxyl；It is advantageous with interface interaction to the reactivity for improving nanoparticle in this way.The present invention adopts Reaction of the successively reaction on Dopamine hydrochloride on modified particle surface is combined to influence with a small amount of curcumin small, while curcumin can To be reacted to particle surface, this is advantageous to raising particle and aramid fiber interfacial effect, can be seen that curcumin from embodiment comparison Addition improves particle in the binding force on aramid fiber surface, it is believed that nanoparticle is avoided to fall off, collect in stirring, hot pressing It is poly-.
In the present invention, the addition of trimethyl silanol on the one hand can be compatible with the silicon methoxyl group on aramid fiber surface, on the other hand Can occur with curcumin, dopamine it is certain react, more important is, can act synergistically with boron nitride, improve anti-flammability Energy；From embodiment as can be seen that the addition of trimethyl silanol is to fire-retardant advantageous.
Compared with prior art, the beneficial effect that the present invention obtains is:
1, the present invention is led on the basis of poly-dopamine modified lithium makes inorganic nano-particle and aramid fiber surface with chemistry key connection It crosses hydrogen peroxide, the modified particle that sulfuric acid solution nanoparticle obtains surface texture and activity improves, further improves and receive The reactivity of rice corpuscles.
2, poly-dopamine modified lithium unrest layer boron nitride coating cerium oxide tool is maintained for inorganic nanometer modified dose provided by the invention There is high ultraviolet absorbability, and by the addition of cobalt, the adhesive force of nanoparticle is promoted, nanoparticle can be improved and exist Dispersibility in cyanate, thus to fire-retardant advantageous.
3, the present invention fire-retardant good aramid fiber surface itself by nanoparticle, nanoparticle and aramid fiber interface interaction with And the synergistic effect of silanol, flame retardant effect is significantly improved, and influence on UV resistance very small.
It 4,, can it is not necessary that organotin catalysts are added by the effect of aramid fiber nano surface particle in pure cyanate system To obtain solidifying good cyanate plate, the plate with addition catalyst can be seen that from mechanical property and flame retardant property It compares, the present invention improves fire-retardant, the mechanical property of system really.
Specific embodiment
With reference to 2018104223562:
(1) by 1g aramid fiber (Kevlar-49,12 μm of diameter, density 1.45g/m3, DuPont Corporation's production) successively submerge Into 70 DEG C of acetone, 75 DEG C of petroleum ether and 115 DEG C of deionized water, retain 3h respectively；Fiber is then taken out, it is true at 80 DEG C It is dry in empty baking oven, clean aramid fiber is obtained, KF is denoted as；
(2) 10.5g sodium hydroxide is dissolved in 120mL ethyl alcohol, the ethanol solution A of sodium hydroxide is made；It will be obtained by step (1) Clean aramid fiber KF be immersed in above-mentioned solution A, at 65 DEG C, oscillating reactions 5h is after reaction, washing, dry, obtains The aramid fiber of amino and carboxyl is had to surface；
(3) surface 0.25g is had to aramid fiber and 30mL γ-glycidyl ether oxygen propyl trimethoxy of amino and carboxyl Silane is added in 70mL ethyl alcohol, under nitrogen atmosphere, in 70 DEG C of reaction 12h；After reaction, fiber is taken out, surface is obtained Aramid fiber with silicon methoxyl group.
Embodiment 1
(1) in aqueous solution by 12.32g cerium chloride, the dissolution of 6g sodium hydroxide, 35min is stirred, suspending liquid A is obtained；Dioxygen is added Water is filtered, washed, is dried in 40 DEG C of reaction 12h with the pH to 12 that sodium hydroxide adjusts suspending liquid A；In Muffle furnace, in 2h is calcined at 700 DEG C, obtains nano-cerium oxide CeO2；3g nano-cerium oxide, 1.2g boric acid and 2.1g urea are put into 400mL second In the mixed solution of pure and mild 200mL water, ultrasonic disperse 1h；Dried object is obtained after revolving, drying, is then dispersed in dried object In 100 milliliters of cobalt nitrate aqueous solutions (3.6mg/mL), it is stirred by ultrasonic 50 minutes, using rotating, be dried to obtain solids；It is described Solids under nitrogen atmosphere, at 950 DEG C, calcines 15h；After reaction, it washs, dry, pulverize to obtain nanoparticle, grain Diameter is less than 100nm, and elemental analysis is found out containing cobalt element；
(2) 5g nanoparticle is added in 3g hydrogen peroxide solution (30wt%), magnetic agitation 0.5h adds 0.3 sulfuric acid solution (98wt%) continues magnetic agitation 0.5h；Then filter cake is obtained by filtration, then by filter cake washing, drying, obtains modified particle；Scanning It is coarse compared with nanoparticle that Electronic Speculum can be seen that modified particle surface, is uneven there are small；Same mode is added to the water, The steam bubble that modified particle generates is slightly more compared with nanoparticle；
(3) configuration concentration is the Tris-HCl buffer solution of 10mM, and the pH to 8.5 of buffer solution is adjusted with sodium hydroxide, is obtained Buffer solution B；It is 5:1.6 by the mass ratio of modified particle and Dopamine hydrochloride, modified particle and Dopamine hydrochloride is added to In buffer solution B, at room temperature, 2h is stirred, curcumin ethanol solution is then added, continues to stir 2h；After reaction, mistake It is filter, washing, dry, obtain organics modifications particle, modified particle, curcumin mass ratio be 10: 1.2；
(4) it takes 0.2g silicon methoxylation aramid fiber to be immersed in the aqueous solution containing 0.06g trimethyl silanol, vibrates 0.5h； Fiber is taken out after reaction to disperse in aqueous solution, at 80 DEG C, to vibrate 2.5h with 1g organics modifications particle again；Reaction knot Fiber is taken out after beam, is washed, it is dry, obtain fire-retardant aramid fiber.
(5) bisphenol A cyanate is heated 0.5 hour in 115 DEG C, obtains cyanate prepolymer melt；Intercepted length is 2.5 ~3 millimeters of fire-retardant aramid fiber is added in cyanate prepolymer melt, pours into conventional mould after mechanical stirring 3 hours in 150 DEG C It in tool, is broken into pieces after natural cooling, prepares fire-retardant cyanate heating platen prepolymer；The dosage of the fire-retardant aramid fiber is cyanic acid The 15% of ester prepolymer melt quality.
Fire-retardant cyanate heating platen prepolymer prepares fire-retardant cyanate heating platen through hot pressing, natural cooling；The work of hot pressing Skill is+1MPa/160 DEG C/2 hours+0.5MPa/130 DEG C/1.5 hours 0.5MPa/110 DEG C/0.5 hour+1MPa/200 DEG C/2 small When.
Performance test
Fire-retardant cyanate heating platen is exposed in QUV/spray type ultraviolet light accelerated weathering accelerator (Q-Lab company, the U.S.) The UV for carrying out 168h irradiates (radiant illumination 1.55W/m2, test temperature is 60 DEG C), obtain the fire-retardant cyanic acid irradiated through 168h Ester heating platen.
Impact strength before and after fire-retardant cyanate heating platen ultraviolet irradiation is 16.68KJ/m2、13.84KJ/m2, decline 17.03%；Oxygen index (OI) after predose is 31,29.Take one block of epoxy-modified cyanate composite board, five positions (centre, four Angle) it is onesize carry out 950 DEG C of sintering, residue mass difference illustrates that filler is uniformly dispersed less than 1%.
The catalyst for using organo-tin compound to react as ethylene rhodanate resin curing, CE solidified resin obtained and composite wood Material has excellent performance, and cyanate ester resin has good dissolubility energy and processing performance, is adapted to include prepreg, tree The various processing requests such as rouge transfer modling, winding, pultrusion, pressure molding and compression molding, solidification hydrocyanic ester acid resin have low Jie Electric constant and minimum dielectric loss, high glass-transition temperature, low-shrinkage, low hydroscopicity and excellent mechanical property and The features such as adhesive property.The present invention nanoparticle high in aramid fiber surface preparation binding force, is not necessarily to catalyst, heating can make Cyanate effectively solidifies, and particularly, in the presence of surface has the aramid fiber of nanoparticle, each group interfacial reaction is good It is good, in terms of test result, further increase impact strength and flame retardant property.
Comparative example
Bisphenol A cyanate is heated 0.5 hour in 115 DEG C, conventional organotin is then added after mechanical stirring 3 hours in 150 DEG C Compound is poured into traditional dies after 2 minutes, is broken into pieces after natural cooling as catalyst, stirring, prepares cyanate heating platen use Prepolymer；Cyanate heating platen prepolymer prepares cyanate heating platen through hot pressing, natural cooling；The technique of hot pressing is It is+0.5MPa/160 DEG C/2 hours+0.5MPa/130 DEG C/1.5 hours 0.5MPa/110 DEG C/0.5 hour+1MPa/200 DEG C/2 small When.Impact strength before and after cyanate heating platen ultraviolet irradiation is 11.69KJ/m2、6.32KJ/m2, decline 45.94%；Predose Oxygen index (OI) be 24.
It is replaced according to the condition of table 1, obtains comparative example, and progress and the consistent performance test of embodiment, be shown in Table 1, Wherein "-" expression is not tested.
1 preparation condition of table and test result
These performances that the unique structure of cyanate determines include having excellent dielectric properties, high heat resistance, good comprehensive Mechanical property, preferable dimensional stability and extremely low water absorption rate etc. are closed, but anti-flammability and impact strength are poor, it is modified Cyanate is as composite material, and combustion mechanism is complicated, there are many process influence factor, the present invention from modified particle and aramid fiber/ Resin boundary surface effect and modified particle nature combination element synergistic effect, which look like improvement flame retardant property, efficacious prescriptions Method, for hot property and electrical property, it is also necessary to further research；The present invention is in addition to solving cyanate ester resin ultra-violet resistance difference etc. Problem mainly improves cyanate flame retardant property, so that aramid fiber modified cyanic acid ester is as high performance resin The Typical Representative of material is played an important role in military or civil field.

Claims (10)

1. fire-retardant cyanate heating platen, which is characterized in that the preparation method of the fire-retardant cyanate heating platen is, by fire-retardant aramid fiber Fiber is added in cyanate prepolymer melt, pours into mold, then hot pressing, natural cooling after stirring, prepares fire-retardant cyanate Heating platen；The length of the fire-retardant aramid fiber is 2.5~3 millimeters；The dosage of the fire-retardant aramid fiber is cyanate pre-polymerization The 14~15% of object melt quality.
2. fire-retardant cyanate heating platen according to claim 1, it is characterised in that: heat cyanate in 110~115 DEG C 0.5~1 hour, obtain cyanate prepolymer melt；Stirring in 145~150 DEG C mechanical stirring 3~3.5 hours.
3. fire-retardant cyanate heating platen according to claim 1, it is characterised in that: the preparation method of the fire-retardant aramid fiber Include the following steps:
(1) cerium salt and inorganic base are dissolved in water, stir 20~45min, hydrogen peroxide is then added, obtains suspension, adjusted 10~20h is reacted after the pH to 10~14 of suspension at 20 DEG C~50 DEG C, using washing, filtering, it is dry after, 500~ 1~3h is calcined at 800 DEG C, obtains nano-cerium oxide；The nano-cerium oxide, boron source and nitrogenous compound are dispersed in by ethyl alcohol In the mixed solution of water composition, 0.5~1.5h is stirred by ultrasonic, using revolving, it is dry after be redispersed in cobalt nitrate aqueous solution In, 0.5~1h is stirred by ultrasonic, using rotating, be dried to obtain solids；The solids is under nitrogen source gas atmosphere, in 850 DEG C~950 DEG C at calcine 13~15h, then crush obtain nanoparticle；
(2) nanoparticle is added in hydrogen peroxide solution, 0.5~1h of magnetic agitation, adds sulfuric acid solution, continue magnetic agitation 0.5h；Then filter cake is obtained by filtration, then by filter cake washing, drying, obtains modified particle；
(3) modified particle and Dopamine hydrochloride are added in the buffer that pH is 8.3~8.8,2~3h is stirred at room temperature； Then curcumin ethanol solution is added, continues 1~2h of stirring；Then it is filtered, washed, dries, obtain organics modifications grain Son；
(4) silicon methoxylation aramid fiber is immersed in the aqueous solution containing trimethyl silanol, vibrates 0.5~1h；Then it soaks Enter in the aqueous solution containing organics modifications particle, 2~3h of oscillating reactions at 70 DEG C~80 DEG C；After reaction by washing It washs, dry, obtain fire-retardant aramid fiber.
4. fire-retardant cyanate heating platen according to claim 3, it is characterised in that: the aramid fiber is that p-aramid fiber is fine Dimension, meta-aramid fibers；The inorganic base is sodium hydroxide or potassium hydroxide；The cerium salt is cerous nitrate, in cerium chloride A kind of or their any combination；The boron source is one of boric acid, metaboric acid；The nitrogenous compound is urea, three One of chlorocyanamide, ammonium bromide；The buffer is Tris-HCl, one in disodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution Kind；The nitrogen source gas is one of nitrogen, ammonia.
5. fire-retardant cyanate heating platen according to claim 3, it is characterised in that: nano-cerium oxide, boron source, nitrogenous chemical combination Object, cobalt nitrate mass ratio be 100: (30~50): (60~120): (10~13).
6. fire-retardant cyanate heating platen according to claim 3, it is characterised in that: nanoparticle, hydrogen peroxide solution, sulfuric acid are molten The mass ratio of liquid is 100: (60~70): (5~7).
7. fire-retardant cyanate heating platen according to claim 3, it is characterised in that: modified particle, Dopamine hydrochloride, curcumin Mass ratio be 100: (30~50): (10~12).
8. fire-retardant cyanate heating platen according to claim 3, it is characterised in that: silicon methoxylation aramid fiber, organic matter Modified particle, trimethyl silanol mass ratio be 1: (2~9): (0.3~0.35).
9. fire-retardant cyanate heating platen according to claim 3, it is characterised in that: the mass ratio of cerium salt and inorganic base is 100: (20~50).
10. fire-retardant cyanate heating platen according to claim 1, it is characterised in that: the technique of hot pressing be 0.5MPa/110 DEG C/ + 1MPa/200 DEG C/2 hours+1MPa/160 DEG C/2 hours+0.5MPa/130 DEG C/1.5 hours 0.5 hour.
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CN116554709A (en) * 2023-04-28 2023-08-08 安徽江淮汽车集团股份有限公司 Modified CeO 2 Filler and high-performance thermoplastic plastic containing filler and preparation method thereof

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CN116554709A (en) * 2023-04-28 2023-08-08 安徽江淮汽车集团股份有限公司 Modified CeO 2 Filler and high-performance thermoplastic plastic containing filler and preparation method thereof

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