CN109135073B - Ablation-resistant ethylene propylene diene monomer composite material and preparation method thereof - Google Patents
Ablation-resistant ethylene propylene diene monomer composite material and preparation method thereof Download PDFInfo
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- CN109135073B CN109135073B CN201811001907.4A CN201811001907A CN109135073B CN 109135073 B CN109135073 B CN 109135073B CN 201811001907 A CN201811001907 A CN 201811001907A CN 109135073 B CN109135073 B CN 109135073B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/02—Flame or fire retardant/resistant
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- 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
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Abstract
The invention provides an ablation-resistant ethylene propylene diene monomer composite material and a preparation method thereof, belonging to the technical field of modification of high polymer materials. Experimental data of an embodiment show that the ablation-resistant ethylene propylene diene monomer composite material provided by the invention has a linear ablation rate of 0.116mm/s and a carbonization rate of 0.2321 mm/s.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, and particularly relates to an ablation-resistant ethylene propylene diene monomer composite material and a preparation method thereof.
Background
The inner insulating material is an important component of the solid rocket motor and the propellant charge, located between the motor casing and the solid propellant. The inner heat-insulating material has the important function of preventing the shell of the combustion chamber of the engine from reaching the temperature which endangers the structural integrity of the shell under the high-temperature, high-combustion-gas-flow and particulate matter erosion environments in the solid rocket engine without losing strength and burning through, thereby ensuring the normal work of the solid rocket engine. Ethylene-propylene-diene monomer (EPDM) is a terpolymer of ethylene, propylene and a non-conjugated diene, and is a low-unsaturation rubber, saturated in the main chain and unsaturated in the side chains. Its density is the lowest among all rubbers, and the ideal mechanical properties and ablation properties can be achieved by the cooperation of appropriate auxiliaries. Therefore, the heat insulating material of epdm has been greatly developed since the 70 s, and the application range thereof is also becoming wider. Because the rubber matrix material can not meet the environmental requirements of high temperature, high pressure and high speed air flow scouring in the combustion chamber of the solid rocket engine, in the prior art, various fillers such as silicon dioxide, powdery phenolic resin, ammonium polyphosphate and the like are added to improve the scouring resistance and the ablation resistance of the internal heat-insulating material. However, with the development of technology and the research on new propellants, the operating temperature and pressure of the combustion chamber are further increased, and it is imperative to obtain an inner insulating material having superior ablation resistance.
Disclosure of Invention
In view of the above, the present invention aims to provide an ablation-resistant ethylene propylene diene monomer composite material and a preparation method thereof.
The invention provides an ablation-resistant ethylene propylene diene monomer composite material which is prepared from the following raw materials in parts by mass:
the flame retardant comprises trapezoidal polyphenyl vinyl silsesquioxane with a structure shown in a formula I;
in the formula I, the ratio of m to n is 10: 1-100;
the ablation-resistant filler is silicon dioxide and phenolic resin;
the synergistic resin is terpene resin and/or chlorosulfonated polyethylene.
Preferably, the flame retardant further comprises aluminum diethylphosphinate.
Preferably, the number ratio of phenyl to vinyl in the trapezoidal polyphenylvinyl silsesquioxane is 9-1: 1.
preferably, theThe ablation-resistant fiber is aramid pulp, poly-p-phenylene benzobisoxazole fiber or F12-aramid fibres.
Preferably, the activators are zinc oxide and stearic acid.
Preferably, the silane coupling agent is bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide and/or gamma-aminopropyltriethoxysilane.
Preferably, the accelerator is N-cyclohexyl-2 benzothiazole sulfenamide and/or diphenyl guanidine.
Preferably, the vulcanizing agent is sulfur and/or dicumyl peroxide.
The invention also provides a preparation method of the composite material, which comprises the following steps:
plasticating and mixing ethylene propylene diene monomer rubber with a plasticizing auxiliary agent, ablation-resistant fibers, an activating agent, a flame retardant, synergistic resin, a silane coupling agent, ablation-resistant filler, an accelerating agent and a vulcanizing agent in sequence to obtain plasticated rubber;
and sequentially performing blank forming, standing at room temperature and vulcanizing on the plasticated rubber to obtain the ablation-resistant ethylene propylene diene monomer composite material.
Preferably, the vulcanizing temperature is 160-170 ℃, the vulcanizing time is 30-60 min, and the vulcanizing pressure is 10-15 MPa.
The beneficial technical effects are as follows: the invention provides an ablation-resistant ethylene propylene diene monomer composite material and a preparation method thereof. Experimental data of an embodiment show that the ablation-resistant ethylene propylene diene monomer composite material provided by the invention has a linear ablation rate of 0.116mm/s and a carbonization rate of 0.2321 mm/s.
Detailed Description
The invention provides an ablation-resistant ethylene propylene diene monomer composite material which is prepared from the following raw materials in parts by mass:
the flame retardant comprises trapezoidal polyphenyl vinyl silsesquioxane with a structure shown in a formula I;
in the formula I, the ratio of m to n is 10: 1-100;
the ablation-resistant filler is silicon dioxide and phenolic resin;
the synergistic resin is terpene resin and/or chlorosulfonated polyethylene.
In the present invention, the flame retardant comprises trapezoidal polyphenylvinylsilsesquioxane having the structure shown in formula I.
In the invention, the preparation method of the trapezoidal polyphenyl vinyl silsesquioxane with the structure shown in the formula I comprises the following steps:
mixing phenyl silane, vinyl silane and an organic solvent to obtain a mixed solution;
dropwise adding a catalyst aqueous solution into the mixed solution to perform hydrolysis reaction to obtain a hydrolysate;
heating the hydrolysate to perform a copolycondensation reaction to obtain a copolycondensation product;
and (3) mixing the copolycondensation product with an alcohol solvent to separate out a white solid to obtain the trapezoidal polyphenyl vinyl silsesquioxane with the structure shown in the formula I, wherein the alcohol solvent is absolute ethyl alcohol or absolute methyl alcohol.
According to the invention, phenyl silane, vinyl silane and an organic solvent are mixed to obtain a mixed solution. In the present invention, the molar ratio of the phenylsilane to the vinylsilane is preferably 10:1 to 10: 100.
In the invention, the volume ratio of the total mass of the phenyl silane and the vinyl silane to the organic solvent is preferably 1g: 5-50 mL.
In the present invention, the phenylsilane is preferably phenyltrichlorosilane, phenyltrimethoxysilane or phenyltriethoxysilane.
In the present invention, the vinyl silane is preferably vinyltrichlorosilane, vinyltrimethoxysilane or vinyltriethoxysilane.
In the present invention, the organic solvent is preferably one or more of acetone, petroleum ether, acetonitrile, dichloromethane, chloroform, tetrahydrofuran, pyridine and dioxane.
After the mixed solution is obtained, the catalyst aqueous solution is dripped into the mixed solution to carry out hydrolysis reaction, so that a hydrolysis product is obtained. In the present invention, the catalyst preferably comprises one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, tetramethylammonium hydroxide and tetraethylammonium hydroxide. When the catalyst is preferably a mixture, the mass ratio of the substances in the catalyst is not particularly limited in the present invention, and a mixture of any mass ratio may be used.
In the present invention, the rate of the dropwise addition is preferably dropwise addition.
In the present invention, the mass ratio of the total mass of the phenylsilane and vinylsilane to the catalyst is preferably 1: 0.005-0.1, and the ratio of the mass of the catalyst in the catalyst aqueous solution to the volume of water is preferably 1g: 50-200 mL.
In the present invention, the hydrolysis reaction is preferably performed at normal temperature and pressure without additional heating or cooling. During the hydrolysis, the phenylsilane and vinylsilane form silanol.
After obtaining the hydrolysis product, the invention heats the hydrolysis product to carry out copolycondensation reaction, thus obtaining the copolycondensation product. In the invention, the temperature of the copolycondensation reaction is preferably 40-80 ℃, more preferably 60-70 ℃, and the time of the copolycondensation reaction is preferably 12-72 h, more preferably 24-36 h.
The temperature rise rate of the temperature rise is not particularly limited in the present invention, and a temperature rise rate known to those skilled in the art may be used.
After the copolycondensation product is obtained, the copolycondensation product is mixed with an alcohol solvent to precipitate a white solid, and the trapezoidal polyphenylvinyl silsesquioxane with the structure shown in the formula I is obtained, wherein the alcohol solvent is absolute ethyl alcohol or absolute methyl alcohol.
In the invention, the volume ratio of the copolycondensation product to the alcohol solvent is preferably 1: 5-50.
After white solid is separated out, the ladder-shaped polyphenyl vinyl silsesquioxane with the structure shown in the formula I is obtained by preferably sequentially carrying out suction filtration, distilled water washing, ethanol washing and drying. The present invention does not specifically limit the specific modes of the suction filtration, the distilled water washing and the ethanol washing, and can adopt the modes known by those skilled in the art.
In the invention, the drying temperature is preferably 60-120 ℃, more preferably 80 ℃, and the drying time is preferably 8-12 h, more preferably 10 h.
In the invention, the number ratio of phenyl groups to vinyl groups in the trapezoidal polyphenylvinyl silsesquioxane with the structure shown in formula I is preferably 9-1: 1, more preferably 7 to 3: 1, most preferably 5: 1.
in the present invention, the flame retardant further comprises diethyl aluminum hypophosphite and/or zinc borate. When the flame retardant is diethyl aluminum hypophosphite and trapezoidal polyphenyl vinyl silsesquioxane with a structure shown in a formula I, the mass ratio of the diethyl aluminum hypophosphite to the trapezoidal polyphenyl vinyl silsesquioxane with the structure shown in the formula I is preferably 10-1: 1, more preferably 6 to 3: 1; when the flame retardant is zinc borate and trapezoidal polyphenylvinyl silsesquioxane with a structure shown in formula I, the mass ratio of the zinc borate to the trapezoidal polyphenylvinyl silsesquioxane with a structure shown in formula I is preferably 1: 15-2: 1, and more preferably 4: 15-4: 5; when the flame retardant is diethyl aluminum hypophosphite, zinc borate and trapezoidal polyphenylvinyl silsesquioxane with a structure shown in a formula I, the mass ratio of the diethyl aluminum hypophosphite to the zinc borate to the trapezoidal polyphenylvinyl silsesquioxane with the structure shown in the formula I is preferably 12-1: 1, more preferably 7-2: 1.
in the present invention, the mass part of the flame retardant is preferably 30 to 60 parts, and more preferably 45 parts.
In the present invention, the ablation-resistant filler is silica and phenolic resin.
In the invention, the mass ratio of the silicon dioxide to the phenolic resin is preferably 2-0.5: 1, more preferably 1: 1.
in the present invention, the ablation-resistant filler is preferably 40 to 55 parts by mass, and more preferably 40 to 50 parts by mass.
In the present invention, the synergistic resin is a terpene resin and/or chlorosulfonated polyethylene.
In the invention, when the synergistic resin is terpene resin and chlorosulfonated polyethylene, the mass ratio of the terpene resin to the chlorosulfonated polyethylene is preferably 2-0.5: 1, more preferably 1: 1.
in the invention, the mass part of the synergistic resin is preferably 10-15 parts.
In the present invention, the ablation-resistant fiber is preferably aramid pulp, poly-p-phenylene benzobisoxazole fiber or F12-aramid fibres.
In the invention, the ablation-resistant fiber is preferably 6-8 parts by mass.
In the present invention, the plasticizing aid is preferably paraffin oil.
In the present invention, the activating agents are preferably zinc oxide and stearic acid.
In the invention, the mass part of the activating agent is preferably 6-8 parts.
In the present invention, the silane coupling agent is preferably bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide and/or gamma-aminopropyltriethoxysilane or a mixture thereof.
In the present invention, the accelerator is preferably N-cyclohexyl-2-benzothiazolesulfenamide and/or diphenylguanidine. When the accelerator is N-cyclohexyl-2-benzothiazole sulfonamide and diphenyl guanidine, the mass ratio of the N-cyclohexyl-2-benzothiazole sulfonamide to the diphenyl guanidine is not particularly limited, and the accelerators can be mixed in any proportion.
In the present invention, the mass part of the accelerator is preferably 1.5 to 4 parts, and more preferably 2.5 parts.
In the present invention, the vulcanizing agent is preferably sulfur and/or dicumyl peroxide. When the vulcanizing agents are sulfur and dicumyl peroxide, the mass ratio of the sulfur to the dicumyl peroxide is not particularly limited, and the sulfur and the dicumyl peroxide can be mixed in any proportion.
The invention also provides a preparation method of the composite material, which comprises the following steps:
plasticating and mixing ethylene propylene diene monomer rubber with a plasticizing auxiliary agent, ablation-resistant fibers, an activating agent, a flame retardant, synergistic resin, a silane coupling agent, ablation-resistant filler, an accelerating agent and a vulcanizing agent in sequence to obtain plasticated rubber;
and sequentially performing blank forming, standing at room temperature and vulcanizing on the plasticated rubber to obtain the ablation-resistant ethylene propylene diene monomer composite material.
The ethylene propylene diene monomer rubber is plasticated and mixed with a plasticizing auxiliary agent, ablation-resistant fibers, an activating agent, a flame retardant, synergistic resin, a silane coupling agent, ablation-resistant filler, an accelerator and a vulcanizing agent in sequence to obtain plasticated rubber.
In the invention, after each raw material is added, the mixture is plasticated and mixed uniformly, and then the next raw material is added. For example, after the ethylene propylene diene monomer and the plasticizing auxiliary agent are plasticated and mixed uniformly, the flame retardant is added for plasticating and mixing uniformly, and the like.
In the invention, the plasticizing auxiliary agent is beneficial to wrapping the roller by the ethylene propylene diene monomer rubber, so the plasticizing auxiliary agent is added firstly; the ablation resistant fibers are added earlier to increase dispersion time; the ablation-resistant filler is added after the silane coupling agent, so that the silane coupling agent is favorably dispersed, the rubber strength is improved, and the vulcanizing agent is finally added to prevent the matrix from being crosslinked and cured in the mixing process.
After the plasticated rubber is obtained, the plasticated rubber is sequentially subjected to blank forming, room-temperature standing and vulcanization to obtain the ablation-resistant ethylene propylene diene monomer composite material.
The method of forming the preform in the present invention is not particularly limited, and a method of forming a preform known to those skilled in the art may be selected.
In the invention, the standing time at room temperature is preferably 16-24 h, more preferably 18-20 h, the loose rubber macromolecules accumulate structural fatigue due to the action of external mechanical force in the rubber mixing process, and time is provided for further uniform dispersion of various additives in the plasticated rubber, so that the dispersion process which is not completed in time in the plastication is completed.
In the invention, the vulcanization temperature is preferably 160-170 ℃, and more preferably 160-165 ℃; the vulcanizing time is preferably 30-60 min, more preferably 40-55 min, most preferably 45-50 min, and the vulcanizing pressure is preferably 10-15 MPa, more preferably 15 MPa.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Preparation of trapezoidal polyphenylvinyl silsesquioxane with structure shown as formula I
1) Adding 17.33g of phenyltrimethoxysilane and 2.38g of vinyltriethoxysilane (the molar ratio of the two is 7:1) into a 500mL three-neck flask with a reflux condenser tube, a constant-pressure dropping funnel, a temperature control device and magnetic stirring, adding 200mL of acetone, stirring, dissolving 0.1g of KOH in 10mL of distilled water, slowly dropwise adding the aqueous solution of KOH into the three-neck flask for about 30min, heating to 60 ℃ after dropwise adding, and reacting for 12h to obtain a light yellow reaction solution.
2) Pouring the reaction liquid obtained in the step 1) into 3L of absolute ethyl alcohol under the stirring condition, stirring for 30min, standing for about 1h to obtain a solution with a colorless and transparent upper layer and a white precipitate lower layer, carrying out suction filtration on the solution, repeatedly washing the solution with distilled water and absolute ethyl alcohol for three times, and drying the filter cake in a vacuum oven at 60 ℃ for 10 hours to finally obtain the trapezoidal polyphenylvinylsilsesquioxane with the structure shown in the formula I.
The ablation-resistant ethylene propylene diene monomer composite material comprises the following raw materials in parts by mass:
ethylene propylene diene monomer 100 parts
Paraffin oil 5 parts
Aramid fiber pulp 7 parts
5 portions of zinc oxide
Stearic acid 1 part
4 portions of zinc borate
30 parts of diethyl aluminum hypophosphite
5 parts of ladder-shaped polyphenyl vinyl silsesquioxane with a structure shown as formula I prepared in the above manner
Terpene resin 5 parts
Chlorosulfonated polyethylene 5 parts
5 parts of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide
Silicon dioxide 20 parts
20 parts of boron phenolic resin
2 portions of N-cyclohexyl-2 benzothiazole sulfonamide
0.5 part of diphenyl guanidine
Dicumyl peroxide 4 parts
0.8 portion of sulfur
The preparation method of the ablation-resistant ethylene propylene diene monomer composite material comprises the following steps:
1) plasticating and uniformly mixing ethylene propylene diene monomer and paraffin oil on a double-roller open mill to obtain a mixture I; adding aramid pulp into the mixture I, and then plasticating and uniformly mixing to obtain a mixture II; sequentially adding zinc oxide and stearic acid into the mixture II, and plasticating and uniformly mixing to obtain a mixture III; sequentially adding zinc borate, diethyl aluminum hypophosphite (ADP) and trapezoidal polyphenyl vinyl silsesquioxane into the mixture III, and plasticating and uniformly mixing to obtain a mixture IV; sequentially adding terpene resin and chlorosulfonated polyethylene into the mixed material IV, and plasticating and uniformly mixing to obtain a mixed material V; adding bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide into the mixture V, plasticating and uniformly mixing to obtain a mixture VI; adding silicon dioxide and boron phenolic resin into the mixture VI, and plasticating and uniformly mixing to obtain a mixture VII; sequentially adding N-cyclohexyl-2-benzothiazole sulfenamide (CZ) and diphenyl guanidine (D) into the mixture VII, and then plasticating and uniformly mixing to obtain a mixture VIII; and (3) sequentially adding dicumyl peroxide and sulfur into the mixture VIII, and then plasticating and uniformly mixing to obtain plasticated rubber.
2) Prefabricating the plasticated rubber obtained in the step 1) into a blank according to the shape of a mould, standing at room temperature for 16 hours, and vulcanizing to obtain an ablation-resistant ethylene propylene diene monomer composite material containing trapezoidal polystyrene-based silsesquioxane; the vulcanization temperature is 160 ℃, the time is 45 minutes, and the pressure is 15 MPa.
Example 2
The trapezoidal polyphenylvinylsilsesquioxane having the structure represented by formula I prepared in example 1 was 10 parts by mass, and the kinds, the amounts and the preparation methods of other raw materials were completely the same as those of example 1. And obtaining the ablation-resistant ethylene propylene diene monomer composite material.
Example 3
The trapezoidal polyphenylvinylsilsesquioxane having the structure represented by formula I prepared in example 1 was 15 parts by mass, and the kinds, the amounts and the preparation methods of other raw materials were completely the same as those of example 1. And obtaining the ablation-resistant ethylene propylene diene monomer composite material.
Example 4
The trapezoidal polyphenylvinylsilsesquioxane having the structure represented by formula I prepared in example 1 was 15 parts by mass, the aluminum diethylphosphinate was 40 parts by mass, and the kinds, the amounts and the preparation methods of other raw materials were exactly the same as those of example 1. And obtaining the ablation-resistant ethylene propylene diene monomer composite material.
Example 5
Except for trapezoidal polyphenylvinylsilsesquioxane having the structure shown in formula I and chlorosulfonated polyethylene prepared in example 1, the kinds, the amounts and the preparation methods of other raw materials were exactly the same as those of example 1. And obtaining the ablation-resistant ethylene propylene diene monomer composite material.
Comparative example 1
Except for trapezoidal polyphenylvinylsilsesquioxane having the structure shown in formula I prepared in example 1, the kinds, the amounts and the preparation methods of other raw materials were exactly the same as those of example 1. And obtaining the ethylene propylene diene monomer composite material.
And (3) testing the mechanical property and ablation experiment of the ablation-resistant ethylene propylene diene monomer composite material obtained in the embodiment 1-4.
The mechanical property test condition is that a Shanghai Dejie DXLL-5000 type electronic tensile testing machine is adopted for testing. The tensile rate of the dumbbell specimen is 200mm/min and the temperature is room temperature according to GB/T528-2009 measurement.
The test conditions of the ablation experiment are as follows: the method adopts an oxygen-acetylene ablation test device, and is carried out according to GJB323A-96, the ablation distance is 10mm, the ablation time is 20s, the nozzle diameter is 2mm, and the oxygen flow is 0.42m3S, acetylene flow 0.31m3The wire ablation rate can be expressed as: line ablation rate (original thickness-residual thickness of carbon-containing layer)/ablation time
The test results are: in the embodiment 1, the ablation-resistant ethylene propylene diene monomer rubber composite material has the tensile strength of 9.5MPa, the elongation at break of 71 percent, the linear ablation rate of 0.119mm/s and the carbonization rate of 0.2321 mm/s; in the embodiment 2, the tensile strength of the ablation-resistant ethylene propylene diene monomer rubber composite material is 9.3MPa, the elongation at break is 74%, the linear ablation rate is 0.131mm/s, and the carbonization rate is 0.2334 mm/s; the tensile strength of the ablation-resistant EPDM composite material in example 3 was 4.1MPa, the elongation at break was 287%, the linear ablation rate was 0.116mm/s, and the carbonization rate was 0.2327 mm/s. In example 4, the ablation-resistant ethylene propylene diene monomer rubber composite material has a tensile strength of 3.8MPa, an elongation at break of 265%, a thread ablation rate of 0.109mm/s and a carbonization rate of 0.2289 mm/s; in example 5, the ablation-resistant EPDM composite material has a tensile strength of 4MPa, an elongation at break of 211%, a linear ablation rate of 0.138mm/s, and a carbonization rate of 0.2458 mm/s; the EPDM obtained in comparative example 1 has a tensile strength of 4.1MPa, an elongation at break of 358%, a thread ablation rate of 0.134mm/s, and a carbonization rate of 0.2335 mm/s.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An ablation-resistant ethylene propylene diene monomer composite material is prepared from the following raw materials in parts by mass:
the flame retardant comprises trapezoidal polyphenyl vinyl silsesquioxane with a structure shown in a formula I;
in the formula I, the ratio of m to n is 10: 1-100;
the ablation-resistant filler is silicon dioxide and phenolic resin;
the synergistic resin is terpene resin and/or chlorosulfonated polyethylene.
2. The composite material of claim 1, wherein the flame retardant further comprises diethyl aluminum hypophosphite and/or zinc borate.
3. The composite material according to claim 1 or 2, wherein the ladder-shaped polyphenylvinylsilsesquioxane has a number ratio of phenyl groups to vinyl groups of 9 to 1: 1.
4. the composite material of claim 1, wherein the ablation-resistant fiber is aramid pulp, poly-p-phenylene benzobisoxazole fiber, or F12-aramid fibres.
5. The composite material according to claim 1, characterized in that the activators are zinc oxide and stearic acid.
6. Composite according to claim 1, characterized in that the silane coupling agent is bis- [ γ - (triethoxysilyl) propyl ] tetrasulfide and/or γ -aminopropyltriethoxysilane or a mixture thereof.
7. Composite material according to claim 1, characterized in that the accelerator is N-cyclohexyl-2-benzothiazolesulfenamide and/or diphenylguanidine.
8. Composite according to claim 1, characterized in that the vulcanizing agent is sulphur and/or dicumyl peroxide.
9. A method of preparing a composite material as claimed in any one of claims 1 to 8, comprising the steps of:
plasticating and mixing ethylene propylene diene monomer rubber with a plasticizing auxiliary agent, ablation-resistant fibers, an activating agent, a flame retardant, synergistic resin, a silane coupling agent, ablation-resistant filler, an accelerating agent and a vulcanizing agent in sequence to obtain plasticated rubber;
and sequentially performing blank forming, standing at room temperature and vulcanizing on the plasticated rubber to obtain the ablation-resistant ethylene propylene diene monomer composite material.
10. The preparation method of claim 9, wherein the vulcanization temperature is 160-170 ℃, the vulcanization time is 30-60 min, and the vulcanization pressure is 10-15 MPa.
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| US6518357B1 (en) * | 2000-10-04 | 2003-02-11 | General Electric Company | Flame retardant polycarbonate-silsesquioxane compositions, method for making and articles made thereby |
| SG102047A1 (en) * | 2002-05-02 | 2004-02-27 | Dso Nat Lab | Ladder-like silicone polymers |
| JP2005239886A (en) * | 2004-02-26 | 2005-09-08 | Mitsubishi Electric Corp | Manufacturing method of silicone ladder polymer |
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| CN101838394B (en) * | 2010-06-03 | 2011-11-09 | 北京理工大学 | Method for preparing highly-ordered ladder-like poly-phenyl silsesquioxane |
| CN101891944B (en) * | 2010-07-30 | 2012-05-09 | 北京理工大学 | Application of high-tacticity trapezoidal polyphenyl silsesquioxane in flame retardant polycarbonate |
| CN101942187B (en) * | 2010-09-14 | 2012-01-25 | 北京理工大学 | Application of atactic poly-phenyl silsesquioxane in flame retardant polycarbonate |
| CN102120849B (en) * | 2010-12-15 | 2012-10-24 | 北京理工大学 | Ethylene-propylene-diene monomer (EPDM) ablation-resistant composition containing high-regularity trapezoid polyphenyl silsesquioxane and preparation method thereof |
| RU2464286C1 (en) * | 2011-03-09 | 2012-10-20 | Федеральное государственное унитарное предприятие "Государственный ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП ГНИИХТЭОС) | Method of producing heat-resistant oligoorganosiloxane resins |
| CN102532505B (en) * | 2012-01-09 | 2013-06-12 | 北京理工大学 | Preparation method for polycarbonate-polydimethylsiloxane nano composite and use thereof in flame-retarding polycarbonate |
| CN107400239B (en) * | 2016-05-19 | 2019-07-16 | 中国科学院化学研究所 | A kind of trapezoidal/cage type polysiloxanes and its preparation method and application from sealing end |
| CN107474484A (en) * | 2017-08-22 | 2017-12-15 | 江西省科学院应用化学研究所 | A kind of preparation method of thermostable heat-conductive anti-flaming nano composite material |
| CN107892777A (en) * | 2017-08-25 | 2018-04-10 | 湖北航天化学技术研究所 | Polyhedral oligomeric silsesquioxane modified epdm rubber and preparation method thereof |
| CN107880267B (en) * | 2017-11-17 | 2021-02-05 | 长兴（中国）投资有限公司 | Siloxane-bridged-group trapezoidal polysiloxane blocked by siloxane-bridged silane and preparation method thereof |
| CN108384129A (en) * | 2018-04-10 | 2018-08-10 | 湖北航天化学技术研究所 | A kind of resistance to ablation EPDM rubber insulation of polyhedral oligomeric silsesquioxane filling |
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