CN110003421A - A kind of ultralow temperature toughening material and modified cyanic acid ester resin and its preparation method and application - Google Patents
A kind of ultralow temperature toughening material and modified cyanic acid ester resin and its preparation method and application Download PDFInfo
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- CN110003421A CN110003421A CN201910323748.8A CN201910323748A CN110003421A CN 110003421 A CN110003421 A CN 110003421A CN 201910323748 A CN201910323748 A CN 201910323748A CN 110003421 A CN110003421 A CN 110003421A
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- ester resin
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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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
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention provides a kind of ultralow temperature toughening material and modified cyanic acid ester resins and its preparation method and application, belong to field of new materials.Ultralow temperature toughening material provided by the invention, is prepared by the component comprising following mass fraction: polyurethane elastomer, 0.1~0.5 part of promotor, 0.01~0.10 part of dispersing agent, 50~120 parts of solvents and 1000~2000 parts of water of 10~90 parts of poly phenol oxygen resinoids, 1~10 part of end seal isocyanate group.Ultralow temperature toughening material provided by the invention has core-shell structure, shell is with low-temperature flexibility poly phenol oxygen resinoid, kernel is the single blocked polyurethane elastomer of activity, ultralow temperature toughening material has ultralow-temperature flexibility high, the good characteristic of cold cycling stability can satisfy the actual requirement that extreme environment uses.
Description
Technical field
The invention belongs to field of new materials more particularly to a kind of ultralow temperature toughening material and modified cyanic acid ester resin and its systems
Preparation Method and application.
Background technique
Deep-space spacecraft be execute deep space explore task important carrier, need extreme deep space environment (- 196 DEG C~
200 DEG C of alternating hot and colds, cosmic ray radiation, high vacuum degree etc.) in stable operation.Generally in order to improve thrust ratio, spacecraft
Most of load-carrying members are all made of polymer matrix composites design, such as truss, special cabin exterior panel and propellant receptacle box enclosure
Deng, it plays maintenance and protects the important function of spacecraft function operation, and the base resin material in these composite materials is long
Phase is exposed in space environment.The stability (mainly mechanical strength and anti-flammability) of resin performance in deep space environment is to determine
Can deep-space spacecraft complete the key factor that deep space explores task.Space industry composite element mostly uses epoxy resin to make
For basis material, with excellent in mechanical performance, the advantages that good manufacturability, anti-space radiation is functional, but its temperature tolerance
It is poor with anti-flammability, have been unable to meet the application demand of deep-space spacecraft.
In recent years, cyanate ester resin (CE) is because its solidfied material is with unique triazine ring-ether structure, to have good
Temperature tolerance (260 DEG C of Tg >), anti-flammability and mechanical strength, and the craftsmanship of its own is suitable with epoxy resin, and be used for
In the design of material of Aeronautics and Astronautics advanced configuration part.Thus, cyanate ester resin has as resin for the latent of extreme environment
Matter, but its ultralow-temperature flexibility in extreme environment is still insufficient, affects the alternating hot and cold performance (- 196 DEG C~200 of material
DEG C), cause the application effect in space flight extreme environment to be deteriorated.
Summary of the invention
In consideration of it, the purpose of the present invention is to provide a kind of ultralow temperature toughening material and modified cyanic acid ester resin and its preparations
Methods and applications.Modified cyanic acid ester resin provided by the invention is high with ultralow-temperature flexibility, the good characteristic of cold cycling stability,
It can satisfy the actual requirement that extreme environment uses.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of ultralow temperature toughening materials, are prepared by the component comprising following mass fraction: 10~
90 parts of poly phenol oxygen resinoids, the polyurethane elastomer of 1~10 part of end seal isocyanate group, 0.1~0.5 part of promotor, 0.01~
0.10 part of dispersing agent, 50~120 parts of solvents and 1000~2000 parts of water.
Preferably, the structural formula of the poly phenol oxygen resinoid is as shown in formula 1~6:
N=50~100 in formula 1~6.
Preferably, the end seal isocyanate based polyurethane thermoplastic elastomer (TPE) is by the component system comprising following mass fraction
Standby to obtain: 95~100 number simple function terminal isocyanate group base polyurethane prepolymer for use as, 1~5 part of sealer and 500~1000 parts are molten
Agent.
Preferably, the structural formula of the simple function terminal isocyanate group base polyurethane prepolymer for use as is as shown in Equation 7:
N=5~10 in formula 7；
In formula 7 R include formula 1.~it is one of 6. or a variety of:
R in formula 71Including one of I~H of formula or a variety of:
X=20~100 in formula I~V；
R in formula 72Including one of formula a~f or a variety of:
The present invention also provides the preparation methods of ultralow temperature toughening material described in above-mentioned technical proposal comprising the steps of:
By water, dispersing agent, focus ratio, end seal isocyanate based polyurethane thermoplastic elastomer (TPE), promotor and solvent
It after mixing, is heated in protective atmosphere, carries out suspension home position polymerization reaction, obtain ultralow temperature toughening material.
Preferably, the temperature of the suspension home position polymerization reaction is 90~95 DEG C, and the time is 5h~8h.
The present invention also provides a kind of modified cyanic acid ester resins, are prepared by the component comprising following mass fraction:
1~70 part of cyanate ester resin, 1~20 part of epoxy resin, 1~10 part of bimaleimide resin, 1~20 part it is above-mentioned
Ultralow temperature toughening material described in technical solution, 1~5 portion of reactive diluent, 0.1~1 part of interface modifier and 0.01~0.05
Part deaeration agent.
The present invention also provides the preparation methods of the modified cyanic acid ester resin described in above-mentioned technical proposal, include following step
It is rapid:
It is heated after cyanate ester resin, epoxy resin, bimaleimide resin and reactive diluent are mixed, adds institute
Ultralow temperature toughening material and interface modifier are stated, is heated in protective atmosphere, is cooled down after carrying out bulk prepolymerization reaction, is added de-
After infusion, modified cyanic acid ester resin is obtained.
Preferably, the temperature of the bulk prepolymerization reaction is 125~145 DEG C, and the time is 1h~4h.
The present invention also provides modified cyanic acid ester trees made from modified cyanic acid ester resin described above or above-mentioned preparation method
Application of the rouge in aerospace component and electronic circuit board preparation field.
The present invention provides a kind of ultralow temperature toughening materials, are prepared by the component comprising following mass fraction: 10~
90 parts of poly phenol oxygen resinoids, the polyurethane elastomer of 1~10 part of end seal isocyanate group, 0.1~0.5 part of promotor, 0.01~
0.10 part of dispersing agent, 50~120 parts of solvents and 1000~2000 parts of water.Ultralow temperature toughening material provided by the invention has nucleocapsid
Structure, shell are with low-temperature flexibility poly phenol oxygen resinoid, and kernel is the single blocked polyurethane elastomer of activity, poly phenol oxygen resinoid
The generation of suspension home position polymerization reaction occurs with the continuous phase in the polyurethane elastomer molecule of end seal isocyanate group to be effectively bonded,
Composite toughening microcell is generated after hardening, the toughened ability of original poly phenol oxygen resinoid is greatly improved, while not influencing
Its high temp glass temperature (- 196 DEG C~200 DEG C), ultralow temperature toughening material can effectively dispersion generate concentrated stress, keep away
Exempt from material and cracked.And solves the storage period of existing polyurethane elastomer influence cyanate ester resin, easily from resinite
It is precipitated in system and the technical problem of toughening failure, obtains performed polymer with cyanate ester resin melt blending, system viscosity is without change within 30 days
Change.Embodiment the result shows that, had both using the modified cyanic acid ester resin that ultralow temperature toughening material provided by the invention is prepared-
196 DEG C of toughness (> 20KJ/m2) and Toughness, glass transition temperature be more than 200 DEG C, by 40 cold cyclings (- 196 DEG C~
200 DEG C) have no crackle, while anti-flammability is UL94V0, (24 DEG C) of storage period are greater than 20 days.
And the viscosity of modified cyanic acid ester resin provided by the invention can be adjusted according to actual needs, it can be generally applicable
In the aerospace component of resistance to extreme environment preparation field and electronic circuit board preparation field.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the infrared spectrum for the ultralow temperature toughening material that embodiment 1 is prepared；
Fig. 2 is the transmission electron microscope picture for the ultralow temperature toughening material that embodiment 1 is prepared；
Fig. 3 is the infrared spectrum for the modified cyanic acid ester resin that embodiment 1 is prepared；
Fig. 4 is the ultralow temperature toughening material and the miscible microscopic appearance figure of cyanate ester resin that embodiment 1 is prepared, wherein
(a) it is ultralow temperature toughening material and the miscible microscopic appearance figure before curing of cyanate ester resin, (b) is ultralow temperature toughening material and cyanogen
Microscopic appearance figure after the miscible solidification of acid ester resin；
Fig. 5 is the modified cyanic acid ester resin that embodiment 1 is prepared and the high performance engineering plastics that comparative example is prepared
Modified cyanate ester resin (- 196 DEG C~200 DEG C) sample after cold cycling destroys shape appearance figure, wherein (a) is the system of embodiment 1
Standby obtained modified cyanic acid ester resin (- 196 DEG C~200 DEG C) sample after cold cycling destroys shape appearance figure, (b) is comparative example system
The modified cyanate ester resin of standby obtained HIGH-PERFORMANCE ENGINEERING PLASTICS POLYSULFONE (- 196 DEG C~200 DEG C) sample after cold cycling destroys
Shape appearance figure.
Specific embodiment
The present invention provides a kind of ultralow temperature toughening materials, are prepared by the component comprising following mass fraction: 10~
90 parts of poly phenol oxygen resinoids, the polyurethane elastomer of 1~10 part of end seal isocyanate group, 0.1~0.5 part of promotor, 0.01~
0.10 part of dispersing agent, 50~120 parts of solvents and 1000~2000 parts of water.
The present invention provides a kind of ultralow temperature toughening material, the ultralow temperature toughening material includes 10~90 parts of mass fractions
Poly phenol oxygen resinoid, further preferably 30~70 parts, more preferably 40~50 parts.In the present invention, the poly phenol oxygen class
The number-average molecular weight of resin is preferably 30000~400000, and further preferably 100000~350000, more preferably 300000
~330000；The structural formula of the poly phenol oxygen resinoid is preferably as shown in formula 1~6:
N is preferably 50~100 in formula 1~6.The present invention does not have special limit to the specific source of the poly phenol oxygen resinoid
It is fixed, using made from this field conventional commercial product or conventional technical means in the art.
On the basis of the mass fraction of the poly phenol oxygen resinoid, the ultralow temperature toughening material includes 0.1~0.5 part of matter
Measure the promotor of number, further preferably 0.2~0.4 part, more preferably 0.25~0.3 part.In the present invention, the promotion
Agent preferably includes one of organic transistion metal compound, glyoxaline compound, carbamide derivative and organic phosphine compound
Or it is a variety of, the organo-transition metal compound more preferably includes dibutyl tin dilaurate, n-BuLi, two cyclopentadienyl of acetyl group
Iron, ferric acetyl acetonade or acetylacetone cobalt；The glyoxaline compound more preferably includes methylimidazole, dimethyl tetraethyl
Imidazoles, 1 phenyl, 2 methylimidazole, 1- 1-cyanoethyl-2-methylimidazole or 2 methylimidazole azine complex compounds；The carbamide derivative is more
Preferably include 1,3 dimethyl ureas, 3- (the chloro- 4- aminomethyl phenyl of 3-) -1,1- dimethyl urea or 3- (3,4- dichlorophenyl) -1,1- bis-
Methylurea etc.；Organic phosphine compound more preferably includes triphenylphosphine, triphenyl acylphosphine oxide or triethyl phosphine and three
Methylphosphine.The present invention does not have special restriction to the specific source of the promotor, using this field conventional commercial product.
On the basis of the mass fraction of the poly phenol oxygen resinoid, the ultralow temperature toughening material includes 0.01~0.10 part
The dispersing agent of mass fraction, further preferably 0.02~0.07 part, more preferably 0.03~0.05 part.In the present invention, institute
It states dispersing agent and preferably includes polyvinyl alcohol, calcium carbonate, magnesium carbonate, barium sulfate, lauryl sodium sulfate, cetyl trimethyl bromine
Change one of ammonium and hexadecanol or a variety of.The present invention does not have special restriction to the specific source of the dispersing agent, using this
Field conventional commercial product.
On the basis of the mass fraction of the poly phenol oxygen resinoid, the ultralow temperature toughening material includes 50~120 parts of matter
Measure the solvent of number, further preferably 60~110 parts, more preferably 70~100 parts.In the present invention, the solvent is preferred
Including butanone, toluene, N, one of N-dimethylformamide, tetrahydrofuran and dioxane or a variety of.The present invention is to described molten
The specific source of agent does not have special restriction, using this field conventional commercial product.
On the basis of the mass fraction of the poly phenol oxygen resinoid, the ultralow temperature toughening material includes 1000~2000 parts
The water of mass fraction.In the present invention, the water is preferably distilled water.
On the basis of the mass fraction of the poly phenol oxygen resinoid, the ultralow temperature toughening material includes 1~10 part of quality
The polyurethane elastomer of the end seal isocyanate group of number, further preferably 2~9 parts, more preferably 5~7 parts.In the present invention
In, the polyurethane elastomer of the end seal isocyanate group is preferably prepared by the component comprising following mass fraction: 95~
100 number simple function terminal isocyanate group base polyurethane prepolymer for use as, 1~5 part of sealer and 500~1000 parts of solvents.
In the present invention, the structural formula of the simple function terminal isocyanate group base polyurethane prepolymer for use as is preferably as shown in Equation 7:
N is preferably 5~10 in formula 7；
In formula 7 R preferably include formula 1.~it is one of 6. or a variety of:
R in formula 71Preferably include one of formula I~V or a variety of:
X in Formulas I~V is preferably 20~100；
R in formula 72Preferably include one of formula a~f or a variety of:
The present invention does not have special restriction to the specific source of the simple function terminal isocyanate group base polyurethane prepolymer for use as, adopts
Made from this field conventional commercial product or conventional technical means in the art.
On the basis of the mass fraction of the simple function terminal isocyanate group base polyurethane prepolymer for use as, the end seal isocyanates
The polyurethane elastomer of base preferably comprises the sealer of 1~5 number, and the sealer preferably includes phenol, parachlorophenol, acetyl
One of aniline, ethylene glycol monoethyl ether, acetoxime and caprolactam are a variety of.Specific source of the present invention to the sealer
There is no special restriction, using this field conventional commercial product.
On the basis of the mass fraction of the simple function terminal isocyanate group base polyurethane prepolymer for use as, the end seal isocyanates
The polyurethane elastomer of base preferably comprises the solvent of 500~1000 numbers, and the solvent is preferably consistent with above scheme, not herein
It repeats one by one.
The present invention also provides the preparation methods of ultralow temperature toughening material described in above-mentioned technical proposal comprising the steps of:
By water, dispersing agent, focus ratio, end seal isocyanate based polyurethane thermoplastic elastomer (TPE), promotor and solvent
It after mixing, is heated in protective atmosphere, carries out suspension home position polymerization reaction, obtain ultralow temperature toughening material.
After the present invention preferably mixes simple function terminal isocyanate group base polyurethane prepolymer for use as and solvent, add in protective atmosphere
Sealer is added in heat, carries out closing end group reaction, obtains end seal isocyanate based polyurethane thermoplastic elastomer (TPE).The present invention couple
The mixed concrete operations do not have special restriction, specific as stirred using this field routine hybrid mode.The present invention
There is no special restriction to the velocity and time of the stirring, can satisfy dissolution.
The present invention preferably successively removes water monofunctional isocyanates based polyurethanes performed polymer, sealer and solvent respectively
It is mixed with after vacuum drying processing.The present invention does not have special limit to the concrete operations of the water removal and vacuum drying processing
It is fixed, using this field routine operation.
The solvent is preferably divided into A group and B group by the present invention.In the present invention, the poly- ammonia of monofunctional isocyanates base
Ester performed polymer is preferably dissolved in A group solvent, the quality point of the A group solvent and monofunctional isocyanates based polyurethanes performed polymer
Number is than being preferably 2~5:1；The sealer is preferably dissolved in B group solvent, the mass fraction of the B group solvent and sealer
Than being preferably 10~20:1.
In the present invention, the temperature of the heating is preferably 50~100 DEG C, and further preferably 60~90 DEG C, more preferably
It is 70~75 DEG C, until the heating rate of the temperature of the heating is preferably 0.3~1.5 DEG C/min, further preferably 0.8~1
℃/min.In the present invention, the protective atmosphere is preferably nitrogen.
In the present invention, the adding manner of the sealer is preferably added dropwise, and the rate of the dropwise addition is preferably 0.02~
0.2mL/s, further preferably 0.03~0.15mL/s, more preferably 0.05~0.1mL/s.
In the present invention, closing end group reaction preferably occur in system viscosity it is constant after, stop reaction, the reaction
Temperature be preferably 50~100 DEG C, it is described closing end group reaction time be preferably 3h~5h.In the present invention, the system
Viscosity preferably pass through the monitoring of online viscosity monitoring probe.
After reaction, the product for closing end group reaction is preferably vacuum-treated to perseverance the closing end group by the present invention
After weight, end seal isocyanate based polyurethane thermoplastic elastomer (TPE) is obtained.
After obtaining end seal isocyanate based polyurethane thermoplastic elastomer (TPE), the present invention by water, dispersing agent, focus ratio,
After the end seal isocyanate based polyurethane thermoplastic elastomer (TPE), promotor and solvent mixing, heats, carry out in protective atmosphere
Suspension home position polymerization reaction obtains ultralow temperature toughening material.
The present invention is preferably by water, dispersing agent, focus ratio, end seal isocyanate based polyurethane thermoplastic elastomer (TPE),
Protective atmosphere is passed through after a part of promotor and solvent mixing.In the present invention, the focus ratio is preferably added in three times
In mixed solution.The present invention does not have special restriction to the mixed concrete operations, equal using this field routine hybrid mode
Can, specific as stirred, in the present invention, the rate of the stirring is preferably 3000~5000r/min.
In the present invention, the suspension home position polymerization reaction carries out preferably in closed reactor；The suspension is poly- in situ
The temperature for closing reaction is preferably 90~95 DEG C, until the heating rate of the suspension home position polymerization reaction temperature is preferably 0.3~1.5
DEG C/min, further preferably 0.8~1 DEG C/min.In the present invention, it is excellent after the suspension home position polymerization reaction carries out 3~5h
Choosing fills into remaining promotor, the reaction was continued 2~3h.In the present invention, the matter of first part's promotor and remaining promotor
Amount is than being preferably 1:1.
After the suspension home position polymerization reaction, the present invention preferably to the product of the suspension home position polymerization reaction successively
It carries out obtaining ultralow temperature toughening material except solvent, water washing, vacuum drying and ultrasonic disperse.In the present invention, the ultralow temperature
Toughening material is preferably pale translucent particle, and the partial size of the ultralow temperature toughening material is preferably 0.05~2mm, further
Preferably 0.08~0.15mm, more preferably 0.10~0.12mm.The present invention to it is described except solvent, water washing, vacuum drying and
The concrete operations of ultrasonic disperse do not have special restriction, using this field routine operation.
The present invention also provides a kind of modified cyanic acid ester resins, are prepared by the component comprising following mass fraction:
1~70 part of cyanate ester resin, 1~20 part of epoxy resin, 1~10 part of bimaleimide resin, 1~20 part it is above-mentioned
Ultralow temperature toughening material described in technical solution, 1~5 portion of reactive diluent, 0.1~1 part of interface modifier and 0.01~0.05
Part deaeration agent.
In the present invention, the modified cyanic acid ester resin includes the cyanate ester resin of 1~70 part of mass fraction, further excellent
It is selected as 10~70 parts, more preferably 50~70 parts.In the present invention, the cyanate ester resin preferably includes bisphenol A cyanate ester
Resin, bis-phenol M cyanate ester resin, one of bisphenol E-type cyanate resin and dicyclopentadiene type ethylene rhodanate resin or more
Kind.The present invention does not have special restriction to the specific source of the cyanate ester resin, using this field conventional commercial product.
On the basis of the mass fraction of the cyanate ester resin, the modified cyanic acid ester resin includes 1~20 part of mass parts
Several epoxy resin, further preferably 5~20 parts, more preferably 10~20 parts.In the present invention, the epoxy resin is preferred
Including one of bisphenol A type epoxy resin, E-51, E-44, E-54 and bisphenol f type epoxy resin or a variety of.The present invention is to institute
The specific source for stating epoxy resin does not have special restriction, using this field conventional commercial product.
On the basis of the mass fraction of the cyanate ester resin, the modified cyanic acid ester resin includes 1~10 part of mass parts
Several bimaleimide resins, further preferably 2~7 parts, more preferably 3~5 parts.In the present invention, the span comes
Imide resin is preferably N, N'-4,4'- diphenyl methane dimaleimide.The present invention is to the bimaleimide resin
Specific source does not have special restriction, using this field conventional commercial product.
On the basis of the mass fraction of the cyanate ester resin, the modified cyanic acid ester resin includes 1~20 part of mass parts
Ultralow temperature toughening material described in several above-mentioned technical proposals, further preferably 2~20 parts, more preferably 8~12 parts.
On the basis of the mass fraction of the cyanate ester resin, the modified cyanic acid ester resin includes 1~5 part of mass fraction
Reactive diluent, further preferably 2~5 parts, more preferably 2~4 parts.In the present invention, the reactive diluent is preferred
Including in alicyclic ring type glycidol ether, lard type glycidol ether, lard type ethylene oxidic ester and episulfide-epoxy active diluent
It is one or more；The alicyclic ring type glycidol ether is preferably hydrogenated bisphenol A diglycidyl ether, the contracting of 1,2- cyclohexanediol two
One of water glycerin ether diepoxy glycidol ether and triphenol methane triglycidyl ether are a variety of, and the lard type is shunk sweet
Oily ether is preferably 1,4-butanediol diglycidyl ether, in one glycidol ether of polyethylene glycol and glycerin triglycidyl ether
It is one or more.The lard type ethylene oxidic ester is preferably butyric acid glycidol butyl ester, tertiary carbonic acid glycidyl ester and methyl
One of glycidyl acrylate is a variety of, and the episulfide-epoxy active diluent is preferably ethylene glycol diglycidyl
Ether-ring compound.The present invention does not have special restriction to the specific source of the reactive diluent, using this field routine
Commercial product.
On the basis of the mass fraction of the cyanate ester resin, the modified cyanic acid ester resin includes 0.1~1 part of mass parts
Several interface modifiers, further preferably 0.2~0.9 part, more preferably 0.3~0.7 part.In the present invention, the interface
Modifying agent preferably includes alkaline earth oxide, 3- glycidyl ether oxypropyltrimethoxysilane, three second of 3- aminopropyl
One of oxysilane and nano silica are a variety of；The alkaline earth oxide preferably includes calcium oxide, calcium carbonate,
One of magnesia and zinc oxide are a variety of.The present invention does not have special restriction to the specific source of the interface modifier,
Using this field conventional commercial product.
On the basis of the mass fraction of the cyanate ester resin, the modified cyanic acid ester resin includes 0.01~0.05 part of matter
Measure the deaeration agent of number, further preferably 0.01~0.04 part, more preferably 0.01~0.03 part.In the present invention, described
Deaeration agent preferably includes polyethers defoaming agent, high-carbon alcohol defoaming agent, modified silicon class defoaming agent and self-emulsifying type silicone antifoam
One of agent is a variety of.The present invention does not have special restriction to the specific source of the deaeration agent, using this field routine city
Sell product.
The present invention also provides the preparation methods of the modified cyanic acid ester resin described in above-mentioned technical proposal, include following step
It is rapid:
It is heated after cyanate ester resin, epoxy resin, bimaleimide resin and reactive diluent are mixed, adds institute
Ultralow temperature toughening material and interface modifier are stated, is heated in protective atmosphere, is cooled down after carrying out bulk prepolymerization reaction, is added de-
After infusion, modified cyanic acid ester resin is obtained.
The present invention does not have special restriction to the mixed concrete mode, using this field routine hybrid mode,
It is specific such as to stir.The present invention does not have special restriction to the rate of the stirring, can satisfy by system mix to it is homogeneous i.e.
It can.The present invention preferably mixes system to after being in homogeneous, the ultralow temperature toughening material and interface modification is added, and be passed through protection
Atmosphere.
In the present invention, the temperature of the heating is preferably 100 DEG C~120 DEG C, further preferably 110 DEG C, until described
The heating rate of the temperature of heating is preferably 0.3~1.5 DEG C/min, further preferably 0.8~1 DEG C/min.
In the present invention, the temperature of the bulk prepolymerization reaction is preferably 125~145 DEG C, further preferably 130
DEG C, until the heating rate of the bulk prepolymerization reaction temperature is preferably 1~1.5 DEG C/min, further preferably 0.8~1 DEG C/
min；The time of the bulk prepolymerization reaction is preferably 1h~4h.
In the present invention, bulk prepolymerization reaction preferably occurs in after system viscosity is 100~1000cp, further
Preferably 500~900cp stops reaction.In the present invention, the viscosity of the system preferably passes through online viscosity monitoring probe prison
Control.
After reaction, the present invention cools down gained reaction system to the bulk prepolymerization, be added deaeration agent after, successively into
Row vacuum outgas and cooling, obtain modified cyanic acid ester resin.In the present invention, the temperature of the cooling is preferably 100~120
DEG C, further preferably 110 DEG C.The present invention does not have special restriction to the vacuum outgas and cooling concrete operations, uses
This field routine operation.
The present invention also provides modified cyanic acid ester trees made from modified cyanic acid ester resin described above or above-mentioned preparation method
Application of the rouge in aerospace component and electronic circuit board preparation field.
In the present invention, the application method of the modified cyanic acid ester resin, preferably comprises following steps: by the modified cyanogen
After acid ester resin and reinforcing fiber successively carry out compound, die-filling and solidification, aerospace component is obtained.In the present invention, described
Die-filling mode is preferably that solvent-free dry method winding or monofilament multi-angle are plated in automatically.The present invention does not have the mixed equipment
Special restriction, the equipment routinely mixed using this field are specific such as moulding machine.The present invention is to the die-filling equipment
There is no special restriction, it is specific such as wrapping machine or automated tape-laying machine using the conventional die-filling equipment in this field.The present invention
There is no special restriction to the mixing and die-filling concrete operations, in such a way that this field routinely mixes.
In the present invention, the application method of the modified cyanic acid ester resin, further preferably comprises the steps of:
After modified cyanic acid ester resin and enhanced fabrics are mixed, the preimpregnation of aerospace component covering preparation is obtained
Material；
After the prepreg of the aerospace component covering preparation is successively carried out die-filling and solidification, aerospace is obtained
Component.
In the present invention, the die-filling mode is preferably that solvent-free dry method winding or monofilament multi-angle are plated in automatically.This
Invention does not have special restriction to the mixed equipment, the equipment routinely mixed using this field, specific such as molding
Machine.The present invention does not have special restriction to the die-filling equipment, using the conventional die-filling equipment in this field, specifically such as
Wrapping machine or automated tape-laying machine.The present invention does not have special restriction to the mixing and die-filling concrete operations, using this field
The mode routinely mixed.
In the present invention, the cured temperature is preferably 130~230 DEG C；The cured time is preferably 2~4h.
Below with reference to embodiment to ultralow temperature toughening material provided by the invention and modified cyanic acid ester resin and its preparation side
Method and application are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
1) 100 parts of simple function terminal isocyanate group base polyurethane prepolymer for use as (structural formula is as shown in Equation 8) are weighed by mass fraction,
1.0 parts of antifebrins, 520 parts of butanone are carried out except water process, vacuum drying, for use.Butanone is divided into A, B group, A group is 500 parts
Butanone, B group are 20 parts of butanone.
2) the monofunctional isocyanates based polyurethanes performed polymer handled well in step 1) and A group butanone are added to and are assembled
Reaction vessel in stirring and dissolving, lead to nitrogen, be warming up to 75 DEG C, heating rate is 1.0 DEG C/min, and dropwise addition is dissolved in B group butanone
In antifebrin, drop rate 0.1mL/s stirs into homogeneous phase transparent, reacts 3h, stops logical nitrogen, stop reaction (if
There are also remaining-NCO group be appropriately extended the reaction time), vacuum post-processing remove solvent, until constant weight, obtains transparent rubber shape
Elastic solid (Hookean body), obtained product are end seal isocyanate based polyurethane thermoplastic elastomer (TPE)s, which is sealed for use.
3) the poly- ammonia of end seal isocyanate group of 90 parts of focus ratio, the preparation of 10 parts of step 2) is weighed by mass fraction
Ester thermoplastic elastomer (TPE), 0.2 part of dibutyl tin dilaurate (mass fractions is waited to be divided to two parts), 0.07 part of polyvinyl alcohol, magnesium carbonate
With cetyl ammonium bromide mixture (2:1:1), 120 parts of dioxane and butanone mixture (2:1) and 1000 parts of distilled water, gather
The structural formula of phenoxy resin is as shown in Equation 9.
4) in the reaction vessel, load weighted distilled water, polyvinyl alcohol, magnesium carbonate and cetyl ammonium bromide are mixed first
Object is closed, is stirred evenly, then the end seal isocyanide of the focus ratio for weighing and being uniformly mixed in advance, step 2) preparation is added in three times
The mixed liquor of perester radical polyurethane termoplastic elastomer, dioxane and butanone mixture and 0.1 part of dibutyl tin dilaurate
Body leads to nitrogen, and high-speed stirred forms microlayer model and is mixed into homogeneously, sealed reaction vessel, high-speed stirred, and revolving speed 3000r/min rises
For temperature to 95 DEG C, heating rate is 1.0 DEG C/min, maintains reaction 3h, adds 0.1 part of dibutyl tin dilaurate, continues to anti-
2h, end of reaction are answered, cooling post-processes and removes solvent, vacuum drying, and ultrasonic disperse obtains partial size in the light white of 0.05mm~2mm
Color translucent particle, product are ultralow temperature toughening materials.
5) 70 parts of bisphenol A cyanate ester resins, 10 parts of epoxy resin E-51,5 parts of N, N'-4 are weighed by mass fraction,
4'- diphenyl methane dimaleimide resin, the ultralow temperature toughening material of 15 parts of steps 4) preparation, 2 parts of 1,4-butanediol two contract
Water glycerin ether, 0.2 part of 3- glycidyl ether oxypropyltrimethoxysilane and 0.01 part of polyethers defoaming agent 6800.
6) in reaction vessel, load weighted bisphenol A cyanate ester resin, epoxy resin E-51, N, N'-4,4'- bis- is added
Phenylmethane bimaleimide resin and 1,4-butanediol diglycidyl ether, are warming up to 110 DEG C, and heating rate is 0.8 DEG C/
Min stirs system to be mixed in the ultralow temperature toughening material and 3- glycidol ether that load weighted step 4) preparation homogeneously, is added
Oxygroup propyl trimethoxy silicane leads to nitrogen, is warming up to 140 DEG C, and heating rate is 0.8 DEG C/min, and stirring maintains reaction 3h, body
It is viscosity control between 500 ± 10cp, stops reaction, be cooled to 120 DEG C, load weighted polyethers defoaming agent 6800 is added,
Room temperature is down in vacuum outgas, is sealed to get the translucent modified cyanic acid ester resin of brown homogenous is arrived.
Modified cyanic acid ester resin is solidified under the process conditions of 177 DEG C/4h, GB/ is pressed in mechanical strength test
T2567-2008 " casting resin method for testing performance " relevant regulations execute, respectively tensile strength, modulus and impact strength ,-
Test keeps the temperature external member using liquid nitrogen under the conditions of 196 DEG C.Cold cycling performance measures as follows: specimen size isSample is placed in 50 DEG C of drying boxes before experiment, constant temperature 30min then takes out, put rapidly
Enter in the insulating utensils equipped with liquid nitrogen, keep the temperature 10min, taking-up is put into 200 DEG C of insulating box inside holding 10min, and cold-hot recycles 40 times
Crack density (the root/cm of specimen surface is measured afterwards2)；Base resin material storage stability is executed by GB/T7123-2002；Base
Body resin material anti-flammability is executed by " U.S.'s fire proofing standard " ANSI/UL-94-1985 related content；Glass transition temperature is adopted
With DMA method.The all-round property testing result of modified cyanic acid ester resin is referring to table 1.
The modified cyanic acid ester resin all-round property testing result that 1 embodiment 1 of table is prepared
| Project | Performance |
| 24 DEG C of tensile strengths, MPa | 69 |
| 24 DEG C of stretch moduluses, GPa | 3.3 |
| - 196 DEG C of tensile strengths, MPa | 74 |
| - 196 DEG C of stretch moduluses, GPa | 5.2 |
| 24 DEG C of impact strengths, KJ/m2 | 21.7 |
| - 196 DEG C of impact strengths, KJ/m2 | 20.1 |
| - 196 DEG C~200 DEG C cyclical stabilities | 40 times, flawless |
| Glass transition temperature, DEG C | 223 |
| Anti-flammability | UL94V0 |
| Viscosity (24 DEG C), cp | 108000 |
| Storage period, d | 20 |
| Viscosity (24 DEG C) after storage 30 days, cp | 109500 |
Fig. 1 is the infrared spectrum for the ultralow temperature toughening material that embodiment 1 is prepared, when a starts in figure for synthetic reaction
The FTIR spectrogram of reactant, b are the ultralow temperature toughening material FTIR spectrogram being prepared.As seen from Figure 1, reaction front and back
3400cm-1Locate hydroxyl absorption peak to weaken, 2270cm-1Place-NCO group disappears, carbamate characteristic peak 1672cm-1Intensity increases
By force, illustrate the polyurethane elastomer in microlayer model, deblocking forms isocyanate-reactive end group under reaction, in reaction process
The phenolic hydroxyl group of middle consumption focus ratio forms effective bonding.
Fig. 2 is transmission electron microscope (TEM) figure for the ultralow temperature toughening material that embodiment 1 is prepared, can be obvious from figure
Find out that ultralow temperature toughening material has core-shell structure.
Fig. 3 is the infrared spectrum for the modified cyanic acid ester resin that embodiment 1 is prepared, and a is in 177 DEG C/4h condition in figure
The FTIR spectrogram of modified cyanic acid ester resin after lower solidification, b are uncured modified cyanic acid ester resin FTIR spectrogram.It can by Fig. 3
To find out, reaction front and back 3400cm-1Hydroxyl absorption peak slightly weakens, 2270cm-1Place's-OCN monomer absorption peak group disappears,
1520cm-1Place's triazine ring absorption peak increased significantly, in addition, 910cm-1He epoxide group absorption peak disappears, 679cm-1Locate C=C double bond
Flexural vibrations peak obviously weakens.The above results illustrate in modified cyanic acid ester resin, cyanate, epoxy resin, toughening material and double
Horse resin is respectively formed effective bonding reaction, it was demonstrated that preparation method provided by the invention is reasonable, can get expected technical effect.
It is analyzed in conjunction with the data of table 1, the modified cyanic acid ester resin that embodiment 1 is prepared is shown preferably at low temperature
The ability of anti-load, excellent heat stability, 30 days system viscosities can satisfy space flight actual demand, anti-flammability without significant change
Reach UL94V0 rank, craftsmanship and storage period meet practical application.
Embodiment 2
1) 100 parts of simple function terminal isocyanate group base polyurethane prepolymer for use as (structural formula such as 10 institute of formula is weighed by mass fraction
Show), 1.0 parts of antifebrins, 520 parts of butanone are carried out except water process, vacuum drying, for use.Butanone is divided into A, B group, A group is
500 parts of butanone, B group are 20 parts of butanone.
2) the monofunctional isocyanates based polyurethanes performed polymer handled well in step 1) and A group butanone are added to and are assembled
Reaction vessel in stirring and dissolving, lead to nitrogen, be warming up to 70 DEG C, heating rate is 1.0 DEG C/min, and dropwise addition is dissolved in B group butanone
In antifebrin, drop rate 0.05mL/s stirs into homogeneous phase transparent, reacts 5h, stop logical nitrogen, stop reaction (such as
Fruit also remaining-the NCO group proper extension reaction time), solvent is removed in vacuum post-processing, until constant weight, obtains transparent rubber
Shape elastic solid (Hookean body), obtained product are end seal isocyanate based polyurethane thermoplastic elastomer (TPE)s, which is sealed for use.
3) the poly- ammonia of end seal isocyanate group of 90 parts of focus ratio, the preparation of 10 parts of step 2) is weighed by mass fraction
Ester thermoplastic elastomer (TPE), 0.2 part of dibutyl tin dilaurate (mass fractions is waited to be divided to two parts), 0.07 part of polyvinyl alcohol, magnesium carbonate
With cetyl ammonium bromide mixture (2:1:1), 120 parts of dioxane and butanone mixture (2:1) and 1000 parts of distilled water, gather
The structural formula of phenoxy resin is as shown in Equation 11.
4) in the reaction vessel, load weighted distilled water, polyvinyl alcohol, magnesium carbonate and cetyl ammonium bromide are mixed first
Object is closed, is stirred evenly, then the end seal isocyanide of the focus ratio for weighing and being uniformly mixed in advance, step 2) preparation is added in three times
The mixed liquor of perester radical polyurethane termoplastic elastomer, dioxane and butanone mixture and 0.1 part of dibutyl tin dilaurate
Body leads to nitrogen, and high-speed stirred forms microlayer model and is mixed into homogeneously, sealed reaction vessel, high-speed stirred, and revolving speed 3000r/min rises
For temperature to 95 DEG C, heating rate is 1.0 DEG C/min, maintains reaction 3h, adds 0.1 part of dibutyl tin dilaurate, continues to anti-
2h, end of reaction are answered, cooling post-processes and removes solvent, vacuum drying, and ultrasonic disperse obtains partial size in the light white of 0.05mm~2mm
Color translucent particle, product are ultralow temperature toughening materials.
5) 70 parts of bisphenol A cyanate ester resins, 10 parts of epoxy resin E-51,5 parts of N, N'-4 are weighed by mass fraction,
4'- diphenyl methane dimaleimide resin, the ultralow temperature toughening material of 15 parts of steps 4) preparation, 2 parts of 1,4-butanediol two contract
Water glycerin ether, 0.2 part of 3- glycidyl ether oxypropyltrimethoxysilane and 0.01 part of polyethers defoaming agent 6800.
6) in reaction vessel, load weighted bisphenol A cyanate ester resin, epoxy resin E-51, N, N'-4,4'- bis- is added
Phenylmethane bimaleimide resin and 1,4-butanediol diglycidyl ether, are warming up to 110 DEG C, and heating rate is 0.8 DEG C/
Min stirs system to be mixed in the ultralow temperature toughening material and 3- glycidol ether that load weighted step 4) preparation homogeneously, is added
Oxygroup propyl trimethoxy silicane leads to nitrogen, is warming up to 140 DEG C, and heating rate is 0.8 DEG C/min, and stirring maintains reaction 3h, body
It is viscosity control between 500 ± 10cp, stops reaction, be cooled to 120 DEG C, load weighted polyethers defoaming agent 6800 is added,
Room temperature is down in vacuum outgas, is sealed to get the translucent modified cyanic acid ester resin of brown homogenous is arrived.
Modified cyanic acid ester resin is solidified under the process conditions of 177 DEG C/4h, GB/ is pressed in mechanical strength test
T2567-2008 " casting resin method for testing performance " relevant regulations execute, respectively tensile strength, modulus and impact strength ,-
Test keeps the temperature external member using liquid nitrogen under the conditions of 196 DEG C.Cold cycling performance measures as follows: specimen size be φ 35mm ×
5mm.Sample is placed in 50 DEG C of drying boxes before experiment, constant temperature 30min then takes out, and puts it into rapidly equipped with liquid nitrogen
In insulating utensils, 10min is kept the temperature, taking-up is put into 200 DEG C of insulating box inside holding 10min, and cold-hot measures sample table after recycling 40 times
Crack density (the root/cm in face2)；Base resin material storage stability is executed by GB/T7123-2002；Base resin material resistance
Combustion property is executed by " U.S.'s fire proofing standard " ANSI/UL-94-1985 related content；Glass transition temperature uses DMA method.It is modified
The all-round property testing result of cyanate ester resin is referring to table 2.
The modified cyanic acid ester resin all-round property testing result that 2 embodiment 2 of table is prepared
The ultralow temperature toughening material that embodiment 2 is prepared uses single benzene ring structure, and heat resistance is slightly below embodiment 1
In there is the ultralow temperature toughening materials of double benzene ring structures, cause the glass transition temperature of the modified cyanic acid ester ester basis material of preparation to be omited
There is reduction, but the modulus from resin-based materials, low-temperature impact toughness, anti-flammability and craftsmanship etc. are considered, test number
Variation is little, and high/low temperature cyclical stability improves, and therefore, is prepared using the ultralow temperature toughening material of single benzene ring structure
The comprehensive performance of modified cyanic acid ester resin sill can satisfy extreme environment requirement.
Embodiment 3
1) 100 parts of simple function terminal isocyanate group base polyurethane prepolymer for use as (structural formula such as 12 institute of formula is weighed by mass fraction
Show), 1.0 parts of antifebrins, 520 parts of butanone are carried out except water process, vacuum drying, for use.Butanone is divided into A, B group, A group is
500 parts of butanone, B group are 20 parts of butanone.
2) the monofunctional isocyanates based polyurethanes performed polymer handled well in step 1) and A group butanone are added to and are assembled
Reaction vessel in stirring and dissolving, lead to nitrogen, be warming up to 75 DEG C, heating rate is 1.0 DEG C/min, and dropwise addition is dissolved in B group butanone
In antifebrin, drop rate 0.1mL/s stirs into homogeneous phase transparent, reacts 3h, stops logical nitrogen, stop reaction (if
There are also remaining-NCO group be appropriately extended the reaction time), vacuum post-processing remove solvent, until constant weight, obtains transparent rubber shape
Elastic solid (Hookean body), obtained product are end seal isocyanate based polyurethane thermoplastic elastomer (TPE)s, which is sealed for use.
3) the poly- ammonia of end seal isocyanate group of 90 parts of focus ratio, the preparation of 10 parts of step 2) is weighed by mass fraction
Ester thermoplastic elastomer (TPE), 0.2 part of dibutyl tin dilaurate (mass fractions is waited to be divided to two parts), 0.07 part of polyvinyl alcohol, magnesium carbonate
With cetyl ammonium bromide mixture (2:1:1), 120 parts of dioxane and butanone mixture (2:1) and 1000 parts of distilled water, gather
The structural formula of phenoxy resin such as formula 13.
4) in the reaction vessel, load weighted distilled water, polyvinyl alcohol, magnesium carbonate and cetyl ammonium bromide are mixed first
Object is closed, is stirred evenly, then the end seal isocyanide of the focus ratio for weighing and being uniformly mixed in advance, step 2) preparation is added in three times
The mixed liquor of perester radical polyurethane termoplastic elastomer, dioxane and butanone mixture and 0.1 part of dibutyl tin dilaurate
Body leads to nitrogen, and high-speed stirred forms microlayer model and is mixed into homogeneously, sealed reaction vessel, high-speed stirred, and revolving speed 3000r/min rises
For temperature to 95 DEG C, heating rate is 1.0 DEG C/min, maintains reaction 3h, adds 0.1 part of dibutyl tin dilaurate, continues to anti-
2h, end of reaction are answered, cooling post-processes and removes solvent, vacuum drying, and ultrasonic disperse obtains partial size in the light white of 0.05mm~2mm
Color translucent particle, product are ultralow temperature toughening materials.
5) 70 parts of bisphenol A cyanate ester resins, 10 parts of epoxy resin E-51,5 parts of N, N'-4 are weighed by mass fraction,
4'- diphenyl methane dimaleimide resin, the ultralow temperature toughening material of 20 parts of steps 4) preparation, 2 parts of 1,4-butanediol two contract
Water glycerin ether, 0.2 part of 3- glycidyl ether oxypropyltrimethoxysilane and 0.01 part of polyethers defoaming agent 6800.
6) in reaction vessel, load weighted bisphenol A cyanate ester resin, epoxy resin E-51, N, N'-4,4'- bis- is added
Phenylmethane bimaleimide resin and 1,4-butanediol diglycidyl ether, are warming up to 110 DEG C, and heating rate is 0.8 DEG C/
Min stirs system to be mixed in the ultralow temperature toughening material and 3- glycidol ether that load weighted step 4) preparation homogeneously, is added
Oxygroup propyl trimethoxy silicane leads to nitrogen, is warming up to 140 DEG C, and heating rate is 0.8 DEG C/min, and stirring maintains reaction 3h, body
It is viscosity control between 500 ± 10cp, stops reaction, be cooled to 120 DEG C, load weighted polyethers defoaming agent 6800 is added,
Room temperature is down in vacuum outgas, is sealed to get dark-brown homogeneously translucent modified cyanic acid ester resin is arrived.
Modified cyanic acid ester resin is solidified under the process conditions of 177 DEG C/4h, mechanical strength test specimens press GB/
T2567-2008 " casting resin method for testing performance " relevant regulations execute, respectively tensile strength, modulus and impact strength ,-
Test keeps the temperature external member using liquid nitrogen under the conditions of 196 DEG C.Cold cycling performance measures as follows: specimen size be φ 35mm ×
5mm.Sample is placed in 50 DEG C of drying boxes before experiment, constant temperature 30min then takes out, and puts it into rapidly equipped with liquid nitrogen
In insulating utensils, 10min is kept the temperature, taking-up is put into 200 DEG C of insulating box inside holding 10min, and cold-hot measures sample table after recycling 40 times
Crack density (the root/cm in face2)；Base resin material storage stability is executed by GB/T7123-2002；Base resin material resistance
Combustion property is executed by " U.S.'s fire proofing standard " ANSI/UL-94-1985 related content；Glass transition temperature uses DMA method.It is modified
The all-round property testing result of cyanate ester resin is referring to table 3.
The modified cyanic acid ester resin all-round property testing result that 3 embodiment 3 of table is prepared
| Project | Performance |
| 24 DEG C of tensile strengths, MPa | 77 |
| 24 DEG C of stretch moduluses, GPa | 3.2 |
| - 196 DEG C of tensile strengths, MPa | 85 |
| - 196 DEG C of stretch moduluses, GPa | 5.1 |
| 24 DEG C of impact strengths, KJ/m2 | 22.4 |
| - 196 DEG C of impact strengths, KJ/m2 | 27.7 |
| - 196 DEG C~200 DEG C cyclical stabilities | 43 times, flawless |
| Glass transition temperature, DEG C | 220 |
| Anti-flammability | UL94V0 |
| Viscosity (24 DEG C), cp | 110050 |
| Storage period, d | 20 |
| Viscosity (24 DEG C) after storage 30 days, cp | 110000 |
The content of ultralow temperature toughening material is increased in embodiment 3 to 20 parts, in contrast to the other materials in embodiment 1
Proportion it is constant.As can be seen from Table 3, the low temperature that the addition of ultralow temperature toughening material significantly improves modified cyanic acid ester resin sill is tough
Property and intensity, 40% and 15% has been respectively increased relative to embodiment 1, and glass transition temperature is not much different, high/low temperature circulation
Stability, anti-flammability and craftsmanship and embodiment one are suitable, it is seen then that compared to general commercially available toughening material, the application preparation
Ultralow temperature toughening material better effects are obtained for the low temperature toughening of cyanate thermosetting resin, meanwhile, to resinite
The heat resistance and anti-flammability of system influence smaller.
Comparative example
1) 70 parts of bisphenol A cyanate ester resins, 10 parts of epoxy resin E-51,5 parts of N, N'-4 are weighed by mass fraction,
4'- diphenyl methane dimaleimide resin, 15 parts of engineering plastics polysulfone resins (molecular weight 35000), 2 parts of 1,4-butanediol two
Glycidol ether, 0.2 part of 3- glycidyl ether oxypropyltrimethoxysilane and 0.01 part of polyethers defoaming agent 6800.
3) in reaction vessel, load weighted bisphenol A cyanate ester resin, epoxy resin E-51, N, N'-4,4'- bis- is added
Phenylmethane bimaleimide resin and 1,4-butanediol diglycidyl ether are warming up to 110 DEG C, stir system to be mixed in equal
Load weighted engineering plastics polysulfone resin and 3- glycidyl ether oxypropyltrimethoxysilane is added in phase, leads to nitrogen, heating
To 150 DEG C, stirring maintains reaction 3h, and system viscosity controls between 5000 ± 500cp, stops reaction, is cooled to 130 DEG C, adds
Enter load weighted polyethers defoaming agent 6800, room temperature is down in vacuum outgas, is sealed to get translucent to a kind of brown
High performance engineering plastics modified cyanic acid ester resin basis material.
High performance engineering plastics modified cyanic acid ester resin is solidified under the process conditions of 180 DEG C/4h, mechanical strength
Test is executed by GB/T2567-2008 " casting resin method for testing performance " relevant regulations, respectively tensile strength, modulus and punching
Hit intensity, test keeps the temperature external member using liquid nitrogen under the conditions of -196 DEG C.Cold cycling performance measures as follows: specimen size is
φ35mm×5mm.Sample is placed in 50 DEG C of drying boxes before experiment, constant temperature 30min then takes out, and puts it into dress rapidly
Have in the insulating utensils of liquid nitrogen, keep the temperature 10min, taking-up is put into 200 DEG C of insulating box inside holding 10min, and cold-hot is surveyed after recycling 40 times
Determine the crack density (radical/cm of specimen surface2).Glass transition temperature uses DMA method.High performance engineering plastics modified cyanic acid ester tree
The all-round property testing result of rouge is referring to table 4.
The high performance engineering plastics modified cyanic acid ester resin all-round property testing result that 4 comparative example of table is prepared
The preferable high performance engineering plastics Cyanate Ester Resin Modified of temperature tolerance, 4 He of contrast table are used in the comparative example
The number of table 1 is it has been found that high performance engineering plastics are obvious for the room temperature toughening effect of cyanate ester resin, and temperature tolerance slightly mentions
Height, but there are many low-temperature flexibility decline, cold cycling stability is bad.
Fig. 4 is the ultralow temperature toughening material and the miscible microscopic appearance figure of cyanate ester resin that embodiment 1 is prepared, wherein
(a) it is ultralow temperature toughening material and the miscible microscopic appearance figure before curing of cyanate ester resin, (b) is ultralow temperature toughening material and cyanogen
Microscopic appearance figure after the miscible solidification of acid ester resin.Find out that the ultralow temperature toughening material synthesized is mixed with cyanate hot melt by Fig. 4
Material is in liquid nitrogen temperature fracture generation riverbed shape lines and nanoscale after forming the nano-dispersion solidification of even suspension in the process
Toughening split-phase embodies preferable low-temperature flexibility.
Fig. 5 is that the cyanate ester resin that the high performance engineering plastics that comparative example is prepared are modified and embodiment 1 are prepared
Modified cyanic acid ester resin after cold cycling (- 196 DEG C~200 DEG C) sample destroy shape appearance figure, wherein (a) be embodiment 1 make
Standby obtained modified cyanic acid ester resin (- 196 DEG C~200 DEG C) sample after cold cycling destroys shape appearance figure, (b) is comparative example system
The modified cyanate ester resin of standby obtained HIGH-PERFORMANCE ENGINEERING PLASTICS POLYSULFONE (- 196 DEG C~200 DEG C) sample after cold cycling destroys
Shape appearance figure.It can be seen from Fig. 5 that being generated very after 30 circulations using the modified cyanate ester resin matrix material of high performance engineering plastics
Much crackles cause material that can not apply, and therefore, are unable to satisfy the requirement of space flight extreme environment.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of ultralow temperature toughening material, which is characterized in that be prepared by the component comprising following mass fraction: 10~90 parts
Poly phenol oxygen resinoid, the polyurethane elastomer of 1~10 part of end seal isocyanate group, 0.1~0.5 part of promotor, 0.01~0.10
Part dispersing agent, 50~120 parts of solvents and 1000~2000 parts of water.
2. ultralow temperature toughening material according to claim 1, which is characterized in that the structural formula of the poly phenol oxygen resinoid is such as
Shown in formula 1~6:
N=50~100 in formula 1~6.
3. ultralow temperature toughening material according to claim 1, which is characterized in that the end seal isocyanate based polyurethane heat
Thermoplastic elastic is prepared by the component comprising following mass fraction: 95~100 poly- ammonia of number simple function terminal isocyanate group
Ester performed polymer, 1~5 part of sealer and 500~1000 parts of solvents.
4. ultralow temperature toughening material according to claim 3, which is characterized in that the poly- ammonia of simple function terminal isocyanate group
The structural formula of ester performed polymer is as shown in Equation 7:
N=5~10 in formula 7；
In formula 7 R include formula 1.~it is one of 6. or a variety of:
R in formula 71Including one of Formulas I~V or a variety of:
X=20~100 in Formulas I~V；
R in formula 72Including one of formula a~f or a variety of:
5. the preparation method of any one of Claims 1 to 4 ultralow temperature toughening material, which is characterized in that comprise the steps of:
Water, dispersing agent, focus ratio, end seal isocyanate based polyurethane thermoplastic elastomer (TPE), promotor and solvent are mixed
Afterwards, it is heated in protective atmosphere, carries out suspension home position polymerization reaction, obtain ultralow temperature toughening material.
6. according to right want 5 described in preparation method, which is characterized in that the temperature of the suspension home position polymerization reaction be 90~95
DEG C, the time is 5h~8h.
7. a kind of modified cyanic acid ester resin, which is characterized in that be prepared by the component comprising following mass fraction:
1~70 part of cyanate ester resin, 1~20 part of epoxy resin, 1~10 part of bimaleimide resin, 1~20 part of claim
The ultralow temperature toughening that any one of any one of 1~4 ultralow temperature toughening material or claim 5~6 preparation method obtain
Material, 1~5 portion of reactive diluent, 0.1~1 part of interface modifier and 0.01~0.05 part of deaeration agent.
8. the preparation method of modified cyanic acid ester resin as claimed in claim 7, which is characterized in that comprise the steps of:
It heats, adds described super after cyanate ester resin, epoxy resin, bimaleimide resin and reactive diluent are mixed
Low temperature toughening material and interface modifier, are heated in protective atmosphere, are cooled down after carrying out bulk prepolymerization reaction, and deaeration agent is added
Afterwards, modified cyanic acid ester resin is obtained.
9. preparation method according to claim 8, which is characterized in that the temperature of bulk prepolymerization reaction is 125~
145 DEG C, the time is 1h~4h.
10. modified made from any one of modified cyanic acid ester resin described in claim 7 or claim 8~9 preparation method
Application of the cyanate ester resin in aerospace component and electronic circuit board preparation field.
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| CN110003421B (en) | 2020-11-10 |
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