CN110079091A - A kind of preparation method of resistance to ablation composite insulation material - Google Patents
A kind of preparation method of resistance to ablation composite insulation material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of composite insulation material of resistance to ablation, belong to heat-insulating material technical field.The present invention is using phenyl siloxane rubber as substrate, prepare the composite insulation material of resistance to ablation, silastic polymer has excellent resistance to height, low temperature properties, flexibility, electrical insulating property and chemical stability, suitable large volume phenyl group is introduced on the side chain of polysiloxanes, destroy the regularity of dimethylsiloxane polymer chain structure, it can reduce the crystallization temperature of polymer, change intermolecular active force, improve the heat resistance and elasticity of silicon rubber, since phenyl has certain capture ability to free radical, the active force between strand can be increased, the mechanical property of phenyl siloxane rubber is improved with the increase of phenyl content, the processing performance of phenyl siloxane rubber is good, since the regularity of phenyl chain link is low, phenyl being evenly distributed in segment, the regularity of strand can be effectively reduced, so that processing performance makes moderate progress, material is improved to exist Elasticity under hot environment.
Description
Technical field
The present invention relates to a kind of preparation methods of composite insulation material of resistance to ablation, belong to heat-insulating material technical field.
Background technique
Resistance to ablative insulative material is mainly made of basis material, supporting material and the filler of resistance to ablation, has high-intensitive, high temperature
The characteristics of inoxidizability, in high temperature and pressure, its physical property and chemical property are all comparatively stable, are generally applied
In exceedingly odious working environments such as hypersonic vehicle, atmosphere loading and rocket propulsion systems.Master in heat-insulating material
Mian part is divided into basis material, and structure has significant impact to the ablation resistance of material.The addition of supporting material can improve resistance to burning
The mechanical properties such as tensile strength, the flexural strength of corrosion material, and the compatibility of supporting material and basis material also can be to material
Mechanical property have an important influence on.Resistance to ablation inorganic filler generally has high-melting-point, high resistivity and low thermal coefficient of expansion etc.
Feature, the addition for the filler of resistance to ablation can make what material was capable of the long period under the ablation of thermal-flame to keep its own machine
Tool performance.
It is respectively hard heat-insulating material and soft heat-insulating material that heat-insulating material, which can be divided into two major classes type,.Hard heat-insulating material
Basis material is usually rigid carbon or resin material, and the basis material of soft heat-insulating material is then using flexible rubber elasticity
Body.
Ablation resistant material can be divided into subliming type, fusing type and carbonization type three categories type by ablative mechanism.Typical subliming type
Ablation resistant material has graphite and carbon-carbon composite etc., and resistance to ablative mechanism is the carbon meeting under the action of thermal-flame of ablation
It distils, a large amount of heat is simultaneously absorbed, and due to carbon material radiation coefficient with higher, so the resistance to burning of subliming type
Corrosion material possesses good Burning corrosion resistance energy.It is the glass of silica that common fusing type ablation resistant material, which for example has main component,
Glass and quartz-like material, silica has very high viscosity under hot environment, and the liquid film that will form melting have it is fine
The ability washed away of resistance high-speed flow, and Aerodynamic Heating can be absorbed in ablation process and then generate fusing and evaporation.It is common
Fiber-like reinforced resin profile material belong to carbonization type ablation resistant material, with resin have resistance to ablation, high-carbon content, high fixing carbon
The advantages that with good processing performance, so generally using it as basis material.
According to the difference of its basis material, the heat insulation composite material of resistance to ablation can be broadly divided into: the ceramic base heat insulating material of resistance to ablation
Material, the resistance to ablative insulative material of Metal Substrate, the resistance to ablative insulative material of C/C base, the resistance to ablative insulative material of resin base and rubber-based are resistance to
Five seed type such as ablative insulative material.And wherein the density of the resistance to ablative insulative material of Metal Substrate is larger, and under hot environment its
Mechanical property is lower, the excessive payload that aircraft can be significantly reduced using this kind of material, therefore the resistance to ablation of Metal Substrate is exhausted
The defect of hot material limits it in the application of space industry.
The resin base heat insulation composite material of resistance to ablation is using organic polymer as matrix, by the way that the reinforcing materials such as fiber are added
And a kind of novel fire resistant material made from resistance to ablation inorganic filler.Wherein poly- aryl ethane polymer matrix composites, phenolic aldehyde
Polymer matrix composites and epoxy resin-base composite material etc. have certain representativeness in each application field most study, it
Have the characteristics that high fixing carbon, low thermal conductivity.
C/C based composites are to use carbon cloth or carbon fiber as composite material prepared by increasing body using carbon as basis material.
There are many C/C base heat insulation composite material of resistance to ablation feature: (1) composite density is smaller, with the ceramic material of same volume and general
Alloy material compare, there are many light weight of C/C based composites, and the carbon element content of product is very high, can reach 99% with
On；(2) when carbon fiber occur in the composite in the same direction be orientated when, C/C based composites show good mechanical property and
Higher flexibility；(3) high temperature resistant ablation property is excellent, moreover it is possible to which in ablation, heat is taken away in distillation；(4) 1000 DEG C with
On hot environment in it is different from metal material, can also continue to keep excellent crocking resistance, will not occur at 2000 DEG C
Fusing.Since C/C based composites have excellent heat resistance, rub resistance, fracture toughness, the work of high load capacity can satisfy
It is required that so being widely used in the civilian industries such as aerospace field.
The resistance to ablative insulative material of resin base and carbon/carbon-based resistance to ablative insulative material belong to the resistance to ablative insulative material of hard, by
Heat can thermally expand, and the brittleness of these hard materials is bigger, and brittle fracture can occur for when high temperature fracture, accelerate fire
The heat transmitting of flame.And rubber matrix resistance to ablation insulation layer material belongs to flexible material, possesses good high temperature resistant and good flexible
The advantages of property.
Silicon rubber is a kind of very important synthesis specific rubber, is connected based on Si-O-Si chain, is connected on the silicon atoms
Machine group can be used as side chain, such as can connect phenyl, vinyl and methyl etc..Silicon rubber is nontoxic and has very high bullet
Property and corrosion resistance.According to curing temperature and mode difference, silicon rubber can be broadly divided into heat vulcanized silicone rubber and room temperature vulcanization
Silicon rubber two major classes type.
Due to the difference of side-chain radical in heat vulcanized silicone rubber, the property that silicon rubber shows also can be different.It is common
Raw rubber include dimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methyl phenyl vinyl silicone rubber (PVMQ) and
Four class of fluorine silicone rubber (FVMQ).
With the continuous development of science and technology, in order to meet the high temperature ablation environment needs that more rocket engine is increasingly harsher,
The silicon rubber base heat-insulating material for developing higher performance will face a very big challenge, heat-insulating material for investigation of materials personnel
Research key be exactly the ablation resistance for improving material.It has been investigated that the rubber of two or more different cultivars is mixed
Refining forms rubber blend, while having both the excellent properties of a variety of rubber, on the one hand can possess the heat-resisting of silicon rubber itself, resistance to
On the other hand ageing properties also overcome some disadvantages such as its mechanical strength is low.
Summary of the invention
The technical problems to be solved by the invention: it can be thermally expanded for existing heat-insulating material is heated, high temperature Shi Huifa
Raw brittle fracture and the low problem of charring rate, provide a kind of preparation method of composite insulation material of resistance to ablation.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) polyurethane-modified polysulfone resin, silicon carbide, polyimides are placed on three-roll grinder, are turned with 100~150r/min
Fast 1~2h of grinding distribution, resulting dispersion；
(2) dispersion, hydrogenated nitrile-butadiene rubber particle, dibutyl tin dilaurate, ethyl orthosilicate are added in phenyl siloxane rubber,
It is poured into mold after stirring 30~40min under room temperature with 200~300r/min revolving speed, vacuum defoamation, 70~72h of room temperature curing,
Obtain solidfied material；
(3) solidfied material is placed on vulcanizing press, vulcanizes 20~30min under conditions of 140~150 DEG C, it is multiple to obtain resistance to ablation
Close heat-insulating material.
The phenyl siloxane rubber, hydrogenated nitrile-butadiene rubber particle, polyurethane-modified polysulfone resin, silicon carbide, polyimides,
Dibutyl tin dilaurate, ethyl orthosilicate parts by weight be 100~120 parts of phenyl siloxane rubbers, 50~60 parts of hydrogenated butyronitrile rubbers
Glue particle, 25~30 parts of polyurethane-modified polysulfone resins, 10~12 parts of silicon carbide, 10~12 parts of polyimides, 1~3 part of two fourth
Base tin dilaurate tin, 3~5 parts of ethyl orthosilicates.
Grinding condition described in step (1) be in, 0.02~0.25mm of back roller gap, in, preliminary roller gap 0.01~
0.25mm, 30~50 DEG C of temperature.
The specific preparation step of polyurethane-modified polysulfone resin described in step (1) are as follows:
(1) it by diphenol propane, 4,4 '-dichloro diphenyl sulfones, Anhydrous potassium carbonate and is added in dimethyl acetamide, is passed through nitrogen guarantor
Shield stirs 20~30min under 40~50 DEG C of water bath condition with 200~240r/min revolving speed, obtains mixed solution；
(2) toluene is added in mixed solution, is stirred to react 1 under conditions of 150~190 DEG C with 300~360r/min revolving speed
~4h, obtains polymer solution；
(3) by polypropylene glycol, toluene di-isocyanate(TDI) adding into acetone, it is passed through nitrogen protection, in 60~70 DEG C of water bath condition
Under 2~3h is stirred to react with 200~240r/min revolving speed, keep the temperature, obtain reaction system；
(4) 2,2- dihydromethyl propionic acid is added in reaction system, it is anti-with the stirring of 300~320r/min revolving speed at 60~70 DEG C
1~2h is answered, polyurethane prepolymer is obtained；
(5) polymer solution, polyurethane prepolymer are added in dimethyl acetamide, with 240~280r/min revolving speed under room temperature
20~40min is stirred, polymer solution is obtained；
(6) dibutyl tin dilaurate is added in polymer solution, with 320~340r/ under 70~90 DEG C of water bath condition
Min revolving speed is stirred to react 2~4h, obtain mixture；
(7) mixture being filtered, solid is placed in 60~80 lower dry 1~2h, then is placed in extracting 20 in Soxhlet extractor~for 24 hours,
It is dried in vacuo 8-10h, obtains polyurethane-modified polysulfone resin.
The diphenol propane, 4,4 '-dichloro diphenyl sulfones, Anhydrous potassium carbonate, dimethyl acetamide, toluene, poly- the third two
Alcohol, toluene di-isocyanate(TDI), 2,2- dihydromethyl propionic acid, acetone, dimethyl acetamide, the parts by weight of dibutyl tin dilaurate
For 50~60 parts of diphenol propanes, 25~30 part 4,4 '-dichloro diphenyl sulfones, 6~8 parts of Anhydrous potassium carbonates, 100~120 parts of diformazans
Yl acetamide, 40~50 parts of toluene, 50~60 parts of polypropylene glycols, 25~30 parts of toluene di-isocyanate(TDI)s, 10~12 parts of 2,2- bis-
Hydroxymethyl propionic acid, 100~120 parts of acetone, 200~240 parts of dimethyl acetamides, 6~8 parts of dibutyl tin dilaurates.
The rate that is passed through of the nitrogen is 30~40mL/min.
The specific preparation step of phenyl siloxane rubber described in step (2) are as follows:
(1) octaphenylcyclotetrasiloxane is added in octamethylcy-clotetrasiloxane, nitrogen protection is passed through, in 80~90 DEG C of water-bath
Under the conditions of with 200~300r/min revolving speed 5~6h of heating stirring, be cooled to 40~60 DEG C and keep the temperature, obtain reaction solution；
(2) potassium hydroxide is added in reaction solution, it is anti-with the stirring of 240~280r/min revolving speed under 90~95 DEG C of water bath condition
3~5h is answered, keeps the temperature, obtains mixed reaction solution；
(3) hexamethyldisiloxane is added in mixed reaction solution, with 300~320r/min under 90~95 DEG C of water bath condition
Revolving speed is stirred to react 30~40min, then heats 10~20min under conditions of being placed in 170~180 DEG C, obtains reaction mechanism liquid；
(4) reaction mechanism liquid is set into vacuum decompression 20~30min of degassing, obtains phenyl siloxane rubber.
The methyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane, potassium hydroxide, hexamethyldisiloxane parts by weight
For 80~100 parts of octamethylcy-clotetrasiloxanes, 50~60 parts of octaphenylcyclotetrasiloxanes, 0.5~1.5 part of potassium hydroxide, 1~3
Part hexamethyldisiloxane.
The rate that is passed through of nitrogen described in step (1) is 20~40mL/min.
The condition of decompression degassing described in step (1) is 3~5KPa of pressure.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention prepares the composite insulation material of resistance to ablation, silastic polymer is by Si-O key using phenyl siloxane rubber as substrate
The helicoidal structure macromolecule that is linked to be of alternating, bond energy is bigger than the bond energy of common high polymer C-C and C-O key, with excellent resistance to
High and low warm nature, flexibility, electrical insulating property and chemical stability introduce suitable large volume phenyl on the side chain of polysiloxanes
Group, destroys the regularity of dimethylsiloxane polymer chain structure, can reduce the crystallization temperature of polymer, changes and divides
Active force between son improves the heat resistance and elasticity of silicon rubber, since phenyl has certain capture ability, Ke Yizeng to free radical
The mechanical property of active force between bonus point subchain, phenyl siloxane rubber is improved with the increase of phenyl content, phenyl siloxane rubber
Processing performance is good, and since the regularity of phenyl chain link is low, the rule of strand can be effectively reduced in phenyl being evenly distributed in segment
It is elastic in a high temperauture environment to improve material so that processing performance makes moderate progress for whole property；
(2) present invention prepares the composite insulation material of resistance to ablation, polysulfones is one kind by different by adding polyurethane-modified polysulfone resin
The linear polymer that trimethylene base, ehter bond and sulfuryl connect, ehter bond compared with the flexibility that can increase polysulfones strand,
Thermal stability can be improved, the phenyl at ehter bond both ends can effectively enhance the toughness of polymer around its inward turning, on two penylene sulfuryls
Oxygen atom is symmetrical, and polarity is smaller, and the sulphur atom on main chain is in its highest oxidation state, furthermore sulfuryl and two adjacent phenyl ring groups
At the diphenyl sulphone (DPS) structure of height conjugation, which has the trend for attracting electronics from adjacent phenyl rings, to enable these phenyl ring
Electron number it is insufficient, the high resonant structure of diphenylene sulfone group also provides thermal stability, this high resonance also enables it have height
Strength chemical key, the stability of this substance in an oxidizing environment make it have powerful resistance and lose electronics and become oxide
Trend, entire diphenylene sulfone group just have inherent intrinsic oxidation resistance, therefore, a large amount of incident heats or electricity
It can be dissipated from radiation, without causing chain rupture or crosslinking, improve polymerizable molecular thermal stability, oxidation resistance, poly- ammonia
Ester can be reacted with polysulfones generates the bigger copolymer of molecular weight, and-the NCO of base polyurethane prepolymer for use as is in polyurethane segment end, has
Very strong reactivity polymerize with the polysulfones of-OH sealing end, so that the elasticity of material is effectively improved, when reducing material at high temperature
The phenomenon that brittle fracture；
(3) present invention prepares the composite insulation material of resistance to ablation, hydrogenated butyronitrile rubber by addition hydrogenated nitrile-butadiene rubber and polyimides
Glue is made of acrylonitrile group, carbon-to-carbon saturation singly-bound and a small amount of carbon-to-carbon double bond, and the carbon-to-carbon singly-bound of saturation assigns hydrogenation fourth
For nitrile polymer with excellent elasticity, heat resistance, resistance to ag(e)ing, ozone resistance, acrylonitrile group provides good oil resistivity, resistance to
Special fuel and high intensity, hydrogenated nitrile-butadiene rubber be added can effectively supporting material mechanical strength and heat resistance, improve material
The carbon forming rate of material contains phenyl ring and imide ring structure on polyimide molecule main chain, since electronic polarization and crystallinity cause
Polyimides causes polyimide molecule chain tightly packed there are very strong molecule inter-chain action, can effectively improve the tight of material
Close property, improves the charring rate of material.
Specific embodiment
According to parts by weight, 80~100 parts of octamethylcy-clotetrasiloxanes, 50~60 parts of four silicon oxygen of octaphenyl ring are weighed respectively
Four silicon of prestox ring is added in octaphenylcyclotetrasiloxane by alkane, 0.5~1.5 part of potassium hydroxide, 1~3 part of hexamethyldisiloxane
In oxygen alkane, nitrogen protection is passed through with the air velocity of 20~40mL/min, under 80~90 DEG C of water bath condition with 200~
300r/min revolving speed 5~6h of heating stirring, is cooled to 40~60 DEG C and keeps the temperature, obtain reaction solution, reaction solution is added in potassium hydroxide
In, 3~5h is stirred to react with 240~280r/min revolving speed under 90~95 DEG C of water bath condition, keeps the temperature, obtains mixed reaction solution,
Hexamethyldisiloxane is added in mixed reaction solution, is stirred under 90~95 DEG C of water bath condition with 300~320r/min revolving speed
30~40min of reaction is mixed, then heats 10~20min under conditions of being placed in 170~180 DEG C, reaction mechanism liquid is obtained, by reaction mechanism
Liquid is placed in vacuum decompression 20~30min of degassing under conditions of 3~5KPa, obtains phenyl siloxane rubber, then according to parts by weight, claim respectively
Measure 50~60 parts of diphenol propanes, 25~30 part 4,4 '-dichloro diphenyl sulfones, 6~8 parts of Anhydrous potassium carbonates, 100~120 parts of diformazans
Yl acetamide, 40~50 parts of toluene, 50~60 parts of polypropylene glycols, 25~30 parts of toluene di-isocyanate(TDI)s, 10~12 parts of 2,2- bis-
Hydroxymethyl propionic acid, 100~120 parts of acetone, 200~240 parts of dimethyl acetamides, 6~8 parts of dibutyl tin dilaurates, by two
Phenolic group propane, 4,4 '-dichloro diphenyl sulfones, Anhydrous potassium carbonate and be added dimethyl acetamide in, with the air-flow of 30~40mL/min
Speed is passed through nitrogen protection, stirs 20~30min under 40~50 DEG C of water bath condition with 200~240r/min revolving speed, obtains mixed
Solution is closed, toluene is added in mixed solution, is stirred to react 1 under conditions of 150~190 DEG C with 300~360r/min revolving speed
~4h, obtains polymer solution, by polypropylene glycol, toluene di-isocyanate(TDI) adding into acetone, with the gas velocity of 30~40mL/min
Degree is passed through nitrogen protection, is stirred to react 2~3h under 60~70 DEG C of water bath condition with 200~240r/min revolving speed, keeps the temperature, obtains
2,2- dihydromethyl propionic acid is added in reaction system reaction system, with the stirring of 300~320r/min revolving speed at 60~70 DEG C
React 1~2h, obtain polyurethane prepolymer, by polymer solution, polyurethane prepolymer be added dimethyl acetamide in, under room temperature with
240~280r/min revolving speed stirs 20~40min, obtains polymer solution, polymer solution is added in dibutyl tin dilaurate
In, 2~4h is stirred to react with 320~340r/min revolving speed under 70~90 DEG C of water bath condition, obtains mixture, by mixture mistake
Filter, solid are placed at 60~80 DEG C dry 1~2h, then are placed in extracting 20 in Soxhlet extractor~for 24 hours, are dried in vacuo 8~10h,
Polyurethane-modified polysulfone resin is obtained, then according to parts by weight, weighs 100~120 parts of phenyl siloxane rubbers, 50~60 parts of hydrogenations respectively
Nitrile rubber particle, 25~30 parts of polyurethane-modified polysulfone resins, 10~12 parts of silicon carbide, 10~12 parts of polyimides, 1~3
Part dibutyl tin dilaurate, 3~5 parts of ethyl orthosilicates, polyurethane-modified polysulfone resin, silicon carbide, polyimides are placed in
On three-roll grinder, in, 0.02~0.25mm of back roller gap, in, 0.01~0.25mm of preliminary roller gap, 30~50 DEG C of temperature
Under the conditions of, with 100~150r/min revolving speed 1~2h of grinding distribution, resulting dispersion, by dispersion, hydrogenated nitrile-butadiene rubber particle, two
Butyl tin dilaurate tin, ethyl orthosilicate be added phenyl siloxane rubber in, under room temperature with 200~300r/min revolving speed stirring 30~
It is poured into mold after 40min, vacuum defoamation, 70~72h of room temperature curing obtain solidfied material, solidfied material are placed on vulcanizing press,
Vulcanize 20~30min under conditions of 140~150 DEG C, obtains the composite insulation material of resistance to ablation.
Embodiment 1
According to parts by weight, 80 parts of octamethylcy-clotetrasiloxanes, 50 parts of octaphenylcyclotetrasiloxanes, 0.5 part of hydrogen-oxygen are weighed respectively
Change potassium, 1 part of hexamethyldisiloxane, octaphenylcyclotetrasiloxane is added in octamethylcy-clotetrasiloxane, with 20mL/min's
Air velocity is passed through nitrogen protection, with 200r/min revolving speed heating stirring 5h under 80 DEG C of water bath condition, is cooled to 40 DEG C simultaneously
Heat preservation, obtains reaction solution, and potassium hydroxide is added in reaction solution, is stirred to react under 90 DEG C of water bath condition with 240r/min revolving speed
3h, heat preservation, obtain mixed reaction solution, by hexamethyldisiloxane be added mixed reaction solution in, under 90 DEG C of water bath condition with
300r/min revolving speed is stirred to react 30min, then heats 10min under conditions of being placed in 170 DEG C, obtains reaction mechanism liquid, will react machine
Reason liquid is placed in vacuum decompression degassing 20min under conditions of 3KPa, obtains phenyl siloxane rubber, then according to parts by weight, weigh 50 respectively
Part diphenol propane, 25 part 4,4 '-dichloro diphenyl sulfones, 6 parts of Anhydrous potassium carbonates, 100 parts of dimethyl acetamides, 40 parts of toluene, 50
Part polypropylene glycol, 25 parts of toluene di-isocyanate(TDI)s, 10 parts of 2,2- dihydromethyl propionic acids, 100 parts of acetone, 200 parts of dimethylacetamides
Amine, 6 parts of dibutyl tin dilaurates, by diphenol propane, 4,4 '-dichloro diphenyl sulfones, Anhydrous potassium carbonate and addition dimethyl second
In amide, nitrogen protection is passed through with the air velocity of 30mL/min, with the stirring of 200r/min revolving speed under 40 DEG C of water bath condition
20min obtains mixed solution, and toluene is added in mixed solution, is stirred to react under conditions of 150 DEG C with 300r/min revolving speed
1h obtains polymer solution, and polypropylene glycol, toluene di-isocyanate(TDI) adding into acetone are passed through with the air velocity of 30mL/min
Nitrogen protection is stirred to react 2h under 60 DEG C of water bath condition with 200r/min revolving speed, and heat preservation obtains reaction system, by 2,2- bis-
Hydroxymethyl propionic acid is added in reaction system, is stirred to react 1h at 60 DEG C with 300r/min revolving speed, obtains polyurethane prepolymer, will gather
Polymer solution, polyurethane prepolymer are added in dimethyl acetamide, stir 20min under room temperature with 240r/min revolving speed, must polymerize
Dibutyl tin dilaurate is added in polymer solution, is stirred under 70 DEG C of water bath condition with 320r/min revolving speed by object solution
Reaction 2h is mixed, mixture is obtained, mixture is filtered, solid is placed at 60 DEG C dry 1h, then is placed in Soxhlet extractor and extracts
20h is dried in vacuo 8h, obtains polyurethane-modified polysulfone resin, then according to parts by weight, weighs 100 parts of phenyl siloxane rubbers, 50 respectively
Part hydrogenated nitrile-butadiene rubber particle, 25 parts of polyurethane-modified polysulfone resins, 10 parts of silicon carbide, 10 parts of polyimides, 1 part of dibutyl two
Tin laurate, 3 parts of ethyl orthosilicates, polyurethane-modified polysulfone resin, silicon carbide, polyimides are placed on three-roll grinder,
In, the 0.02mm of back roller gap, in, preliminary roller gap 0.01mm, under conditions of 30 DEG C of temperature, with 100r/min revolving speed grinding distribution
Phenyl silicon rubber is added in dispersion, hydrogenated nitrile-butadiene rubber particle, dibutyl tin dilaurate, ethyl orthosilicate by 1h, resulting dispersion
In glue, to be poured into mold after stirring 30min under room temperature with 200r/min revolving speed, vacuum defoamation, room temperature curing 70h obtain solidfied material,
Solidfied material is placed on vulcanizing press, vulcanizes 20min under conditions of 140 DEG C, obtains the composite insulation material of resistance to ablation.
Embodiment 2
According to parts by weight, 90 parts of octamethylcy-clotetrasiloxanes, 55 parts of octaphenylcyclotetrasiloxanes, 1.0 parts of hydrogen-oxygens are weighed respectively
Change potassium, 2 parts of hexamethyldisiloxane, octaphenylcyclotetrasiloxane is added in octamethylcy-clotetrasiloxane, with 30mL/min's
Air velocity is passed through nitrogen protection, with 250r/min revolving speed heating stirring 5h under 85 DEG C of water bath condition, is cooled to 50 DEG C simultaneously
Heat preservation, obtains reaction solution, and potassium hydroxide is added in reaction solution, is stirred to react under 92 DEG C of water bath condition with 260r/min revolving speed
4h, heat preservation, obtain mixed reaction solution, by hexamethyldisiloxane be added mixed reaction solution in, under 92 DEG C of water bath condition with
310r/min revolving speed is stirred to react 35min, then heats 15min under conditions of being placed in 175 DEG C, obtains reaction mechanism liquid, will react machine
Reason liquid is placed in vacuum decompression degassing 25min under conditions of 4KPa, obtains phenyl siloxane rubber, then according to parts by weight, weigh 55 respectively
Part diphenol propane, 28 part 4,4 '-dichloro diphenyl sulfones, 7 parts of Anhydrous potassium carbonates, 110 parts of dimethyl acetamides, 45 parts of toluene, 55
Part polypropylene glycol, 28 parts of toluene di-isocyanate(TDI)s, 11 parts of 2,2- dihydromethyl propionic acids, 110 parts of acetone, 220 parts of dimethylacetamides
Amine, 7 parts of dibutyl tin dilaurates, by diphenol propane, 4,4 '-dichloro diphenyl sulfones, Anhydrous potassium carbonate and addition dimethyl second
In amide, nitrogen protection is passed through with the air velocity of 35mL/min, with the stirring of 220r/min revolving speed under 45 DEG C of water bath condition
25min obtains mixed solution, and toluene is added in mixed solution, is stirred to react under conditions of 170 DEG C with 330r/min revolving speed
2h obtains polymer solution, and polypropylene glycol, toluene di-isocyanate(TDI) adding into acetone are passed through with the air velocity of 35mL/min
Nitrogen protection is stirred to react 2h under 65 DEG C of water bath condition with 220r/min revolving speed, and heat preservation obtains reaction system, by 2,2- bis-
Hydroxymethyl propionic acid is added in reaction system, is stirred to react 1h at 65 DEG C with 310r/min revolving speed, obtains polyurethane prepolymer, will gather
Polymer solution, polyurethane prepolymer are added in dimethyl acetamide, stir 30min under room temperature with 260r/min revolving speed, must polymerize
Dibutyl tin dilaurate is added in polymer solution, is stirred under 80 DEG C of water bath condition with 330r/min revolving speed by object solution
Reaction 3h is mixed, mixture is obtained, mixture is filtered, solid is placed at 70 DEG C dry 1h, then is placed in Soxhlet extractor and extracts
22h is dried in vacuo 9h, obtains polyurethane-modified polysulfone resin, then according to parts by weight, weighs 110 parts of phenyl siloxane rubbers, 55 respectively
Part hydrogenated nitrile-butadiene rubber particle, 28 parts of polyurethane-modified polysulfone resins, 11 parts of silicon carbide, 11 parts of polyimides, 2 parts of dibutyl two
Tin laurate, 4 parts of ethyl orthosilicates, polyurethane-modified polysulfone resin, silicon carbide, polyimides are placed on three-roll grinder,
In, the 0.20mm of back roller gap, in, preliminary roller gap 0.20mm, under conditions of 40 DEG C of temperature, with 125r/min revolving speed grinding distribution
Phenyl silicon rubber is added in dispersion, hydrogenated nitrile-butadiene rubber particle, dibutyl tin dilaurate, ethyl orthosilicate by 1h, resulting dispersion
In glue, to be poured into mold after stirring 35min under room temperature with 250r/min revolving speed, vacuum defoamation, room temperature curing 71h obtain solidfied material,
Solidfied material is placed on vulcanizing press, vulcanizes 25min under conditions of 145 DEG C, obtains the composite insulation material of resistance to ablation.
Embodiment 3
According to parts by weight, 100 parts of octamethylcy-clotetrasiloxanes, 60 parts of octaphenylcyclotetrasiloxanes, 1.5 parts of hydrogen-oxygens are weighed respectively
Change potassium, 3 parts of hexamethyldisiloxane, octaphenylcyclotetrasiloxane is added in octamethylcy-clotetrasiloxane, with 40mL/min's
Air velocity is passed through nitrogen protection, with 300r/min revolving speed heating stirring 6h under 90 DEG C of water bath condition, is cooled to 60 DEG C simultaneously
Heat preservation, obtains reaction solution, and potassium hydroxide is added in reaction solution, is stirred to react under 95 DEG C of water bath condition with 280r/min revolving speed
5h, heat preservation, obtain mixed reaction solution, by hexamethyldisiloxane be added mixed reaction solution in, under 95 DEG C of water bath condition with
320r/min revolving speed is stirred to react 40min, then heats 20min under conditions of being placed in 180 DEG C, obtains reaction mechanism liquid, will react machine
Reason liquid is placed in vacuum decompression degassing 30min under conditions of 5KPa, obtains phenyl siloxane rubber, then according to parts by weight, weigh 60 respectively
Part diphenol propane, 30 part 4,4 '-dichloro diphenyl sulfones, 8 parts of Anhydrous potassium carbonates, 120 parts of dimethyl acetamides, 50 parts of toluene, 60
Part polypropylene glycol, 30 parts of toluene di-isocyanate(TDI)s, 12 parts of 2,2- dihydromethyl propionic acids, 120 parts of acetone, 240 parts of dimethylacetamides
Amine, 8 parts of dibutyl tin dilaurates, by diphenol propane, 4,4 '-dichloro diphenyl sulfones, Anhydrous potassium carbonate and addition dimethyl second
In amide, nitrogen protection is passed through with the air velocity of 40mL/min, with the stirring of 240r/min revolving speed under 50 DEG C of water bath condition
30min obtains mixed solution, and toluene is added in mixed solution, is stirred to react under conditions of 190 DEG C with 360r/min revolving speed
4h obtains polymer solution, and polypropylene glycol, toluene di-isocyanate(TDI) adding into acetone are passed through with the air velocity of 40mL/min
Nitrogen protection is stirred to react 3h under 70 DEG C of water bath condition with 240r/min revolving speed, and heat preservation obtains reaction system, by 2,2- bis-
Hydroxymethyl propionic acid is added in reaction system, is stirred to react 2h at 70 DEG C with 320r/min revolving speed, obtains polyurethane prepolymer, will gather
Polymer solution, polyurethane prepolymer are added in dimethyl acetamide, stir 40min under room temperature with 280r/min revolving speed, must polymerize
Dibutyl tin dilaurate is added in polymer solution, is stirred under 90 DEG C of water bath condition with 340r/min revolving speed by object solution
Reaction 4h is mixed, mixture is obtained, mixture is filtered, solid is placed at 80 DEG C dry 2h, then is placed in Soxhlet extractor and extracts
For 24 hours, be dried in vacuo 10h, obtain polyurethane-modified polysulfone resin, then according to parts by weight, respectively weigh 120 parts of phenyl siloxane rubbers,
60 parts of hydrogenated nitrile-butadiene rubber particles, 30 parts of polyurethane-modified polysulfone resins, 12 parts of silicon carbide, 12 parts of polyimides, 3 parts of dibutyl
Tin dilaurate tin, 5 parts of ethyl orthosilicates, are placed in three-roll grinder for polyurethane-modified polysulfone resin, silicon carbide, polyimides
On, in, the 0.25mm of back roller gap, in, preliminary roller gap 0.25mm, under conditions of temperature 50 C, with the grinding of 150r/min revolving speed
Disperse 2h, phenyl is added in dispersion, hydrogenated nitrile-butadiene rubber particle, dibutyl tin dilaurate, ethyl orthosilicate by resulting dispersion
In silicon rubber, poured into mold after stirring 40min under room temperature with 300r/min revolving speed, vacuum defoamation, room temperature curing 72h must consolidate
Solidfied material is placed on vulcanizing press by compound, is vulcanized 30min under conditions of 150 DEG C, is obtained the composite insulation material of resistance to ablation.
Reference examples: the composite insulation material of resistance to ablation of Dongguan company production.
The composite insulation material of resistance to ablation that embodiment and reference examples are prepared is detected, specific detection is as follows:
Tensile strength: test experiments are according to testing standard GB/T528-2009, using UTM4304 type electronic universal tester to mute
Bell-shaped sample is tested, and test loading velocity is 5mm/min, is finally characterized with the tensile strength of sample and elongation at break
The tensile property of material.
Ablation resistance: executing, ablation flame oxy-acetylene flame stream according to standard GJB323A-1996, surveys for ablation
The sample of examination is cylinder, with a thickness of 10mm, diameter 30mm.Sample is placed in the graphite card slot of ablation device, ablation
Spray tip perpendicular alignmnet sample centre and sample spacing are 10mm, nozzle diameter 2mm, oxygen flow 1512L
h-1, acetylene flow be 1116Lh-1, the control ablation time is 20s.
Adiabatic exponent: according to GJB323A-1996 standard test, pass through the back end of record ablation sample in ablation process
It the temperature time used when being increased to 353K from room temperature, is calculated according to formula.
Carbon yield measurement: first by PAA resin carry out hot setting, temperature be 115 DEG C, 120 DEG C, 130 DEG C, 150 DEG C,
At 180 DEG C, 200 DEG C, 300 DEG C, each heat preservation solidification 2h.PAA resin samples (W1) after weighing the solidification of certain mass, take one
The resin weighed up is put by the crucible (W2) of constant weight wherein covers the crucible for filling PAA resin the high temperature for being put into 800 DEG C of constant temperature
In carbide furnace, it is drawn off after heated at constant temperature 1h, it is completely cool but to quality (W3) is weighed after room temperature after it, PAA is calculated by formula
The carbon yield of resin.It is measured in parallel and is averaged afterwards three times in this way.
Specific test result such as table 1.
1 performance characterization contrast table of table
As shown in Table 1, the composite insulation material of resistance to ablation prepared by the present invention have good mechanical property, ablation resistance, absolutely
Hot property and charring rate.
Claims (10)
1. a kind of preparation method for the composite insulation material of resistance to ablation, which is characterized in that specific preparation step are as follows:
(1) polyurethane-modified polysulfone resin, silicon carbide, polyimides are placed on three-roll grinder, are turned with 100~150r/min
Fast 1~2h of grinding distribution, resulting dispersion；
(2) dispersion, hydrogenated nitrile-butadiene rubber particle, dibutyl tin dilaurate, ethyl orthosilicate are added in phenyl siloxane rubber,
It is poured into mold after stirring 30~40min under room temperature with 200~300r/min revolving speed, vacuum defoamation, 70~72h of room temperature curing,
Obtain solidfied material；
(3) solidfied material is placed on vulcanizing press, vulcanizes 20~30min under conditions of 140~150 DEG C, it is multiple to obtain resistance to ablation
Close heat-insulating material.
2. a kind of preparation method of composite insulation material of resistance to ablation according to claim 1, which is characterized in that the benzene
Base silicon rubber, hydrogenated nitrile-butadiene rubber particle, polyurethane-modified polysulfone resin, silicon carbide, polyimides, dibutyl tin cinnamic acid
Tin, ethyl orthosilicate parts by weight be 100~120 parts of phenyl siloxane rubbers, 50~60 parts of hydrogenated nitrile-butadiene rubber particles, 25~30 parts
Polyurethane-modified polysulfone resin, 10~12 parts of silicon carbide, 10~12 parts of polyimides, 1~3 part of dibutyl tin dilaurate, 3~
5 parts of ethyl orthosilicates.
3. a kind of preparation method of composite insulation material of resistance to ablation according to claim 1, which is characterized in that step (1)
The grinding condition be in, 0.02~0.25mm of back roller gap, in, 0.01~0.25mm of preliminary roller gap, 30~50 DEG C of temperature.
4. a kind of preparation method of composite insulation material of resistance to ablation according to claim 1, which is characterized in that step (1)
The specific preparation step of the polyurethane-modified polysulfone resin are as follows:
(1) it by diphenol propane, 4,4 '-dichloro diphenyl sulfones, Anhydrous potassium carbonate and is added in dimethyl acetamide, is passed through nitrogen guarantor
Shield stirs 20~30min under 40~50 DEG C of water bath condition with 200~240r/min revolving speed, obtains mixed solution；
(2) toluene is added in mixed solution, is stirred to react 1 under conditions of 150~190 DEG C with 300~360r/min revolving speed
~4h, obtains polymer solution；
(3) by polypropylene glycol, toluene di-isocyanate(TDI) adding into acetone, it is passed through nitrogen protection, in 60~70 DEG C of water bath condition
Under 2~3h is stirred to react with 200~240r/min revolving speed, keep the temperature, obtain reaction system；
(4) 2,2- dihydromethyl propionic acid is added in reaction system, it is anti-with the stirring of 300~320r/min revolving speed at 60~70 DEG C
1~2h is answered, polyurethane prepolymer is obtained；
(5) polymer solution, polyurethane prepolymer are added in dimethyl acetamide, with 240~280r/min revolving speed under room temperature
20~40min is stirred, polymer solution is obtained；
(6) dibutyl tin dilaurate is added in polymer solution, with 320~340r/ under 70~90 DEG C of water bath condition
Min revolving speed is stirred to react 2~4h, obtain mixture；
(7) mixture being filtered, solid is placed in 60~80 lower dry 1~2h, then is placed in extracting 20 in Soxhlet extractor~for 24 hours,
It is dried in vacuo 8-10h, obtains polyurethane-modified polysulfone resin.
5. a kind of preparation method of composite insulation material of resistance to ablation according to claim 4, which is characterized in that described two
Phenolic group propane, 4,4 '-dichloro diphenyl sulfones, Anhydrous potassium carbonate, dimethyl acetamide, toluene, polypropylene glycol, toluene diisocynate
Ester, 2,2- dihydromethyl propionic acid, acetone, dimethyl acetamide, the parts by weight of dibutyl tin dilaurate are 50~60 parts of diphenol
Base propane, 25~30 part 4,4 '-dichloro diphenyl sulfones, 6~8 parts of Anhydrous potassium carbonates, 100~120 parts of dimethyl acetamides, 40~50
Part toluene, 50~60 parts of polypropylene glycols, 25~30 parts of toluene di-isocyanate(TDI)s, 10~12 parts of 2,2- dihydromethyl propionic acids, 100~
120 parts of acetone, 200~240 parts of dimethyl acetamides, 6~8 parts of dibutyl tin dilaurates.
6. a kind of preparation method of composite insulation material of resistance to ablation according to claim 4, which is characterized in that the nitrogen
The rate that is passed through of gas is 30~40mL/min.
7. a kind of preparation method of composite insulation material of resistance to ablation according to claim 1, which is characterized in that step (2)
The specific preparation step of the phenyl siloxane rubber are as follows:
(1) octaphenylcyclotetrasiloxane is added in octamethylcy-clotetrasiloxane, nitrogen protection is passed through, in 80~90 DEG C of water-bath
Under the conditions of with 200~300r/min revolving speed 5~6h of heating stirring, be cooled to 40~60 DEG C and keep the temperature, obtain reaction solution；
(2) potassium hydroxide is added in reaction solution, it is anti-with the stirring of 240~280r/min revolving speed under 90~95 DEG C of water bath condition
3~5h is answered, keeps the temperature, obtains mixed reaction solution；
(3) hexamethyldisiloxane is added in mixed reaction solution, with 300~320r/min under 90~95 DEG C of water bath condition
Revolving speed is stirred to react 30~40min, then heats 10~20min under conditions of being placed in 170~180 DEG C, obtains reaction mechanism liquid；
(4) reaction mechanism liquid is set into vacuum decompression 20~30min of degassing, obtains phenyl siloxane rubber.
8. a kind of preparation method of composite insulation material of resistance to ablation according to claim 7, which is characterized in that the first
Basic ring tetrasiloxane, octaphenylcyclotetrasiloxane, potassium hydroxide, hexamethyldisiloxane parts by weight be 80~100 part of eight first
Basic ring tetrasiloxane, 50~60 parts of octaphenylcyclotetrasiloxanes, 0.5~1.5 part of potassium hydroxide, 1~3 part of two silicon oxygen of hexamethyl
Alkane.
9. a kind of preparation method of composite insulation material of resistance to ablation according to claim 7, which is characterized in that step (1)
The rate that is passed through of the nitrogen is 20~40mL/min.
10. a kind of preparation method of composite insulation material of resistance to ablation according to claim 7, which is characterized in that step (1)
The condition of the decompression degassing is 3~5KPa of pressure.
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