CN110760131B - Benzoxazine resin/ethylene propylene diene monomer composite heat insulating layer and preparation method thereof - Google Patents
Benzoxazine resin/ethylene propylene diene monomer composite heat insulating layer and preparation method thereof Download PDFInfo
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- CN110760131B CN110760131B CN201910803547.8A CN201910803547A CN110760131B CN 110760131 B CN110760131 B CN 110760131B CN 201910803547 A CN201910803547 A CN 201910803547A CN 110760131 B CN110760131 B CN 110760131B
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- 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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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Abstract
The invention relates to a benzoxazine resin/ethylene propylene diene monomer rubber composite heat insulation layer and a preparation method thereof, belonging to the technical field of solid rocket motor heat insulation. The composite heat insulation layer comprises the following raw materials in parts by mass: 100 parts of ethylene propylene diene monomer, 30-100 parts of benzoxazine resin, 10-15 parts of ablation-resistant fiber, 3-30 parts of solid filler, 6-12 parts of a flame-retardant system, 2-5 parts of a process additive and 4.5-9 parts of a vulcanization system; the vulcanizing system comprises a vulcanizing agent, a co-vulcanizing catalyst and an accelerator, wherein the vulcanizing agent is at least one of sulfur, dicumyl peroxide and benzoyl peroxide, and the co-vulcanizing catalyst is 2-methylimidazole or 4-methylimidazole. The heat insulating layer has excellent thermal property, mechanical property and process property of the ethylene propylene diene monomer heat insulating layer, has good compatibility with various propellants and shell materials, and also has high carbon formation rate and ablation resistance (the line ablation rate is 0.02 mm/s-0.06 mm/s).
Description
Technical Field
The invention belongs to the technical field of solid rocket engine heat insulation, and relates to a benzoxazine resin/ethylene propylene diene monomer rubber composite heat insulation layer and a preparation method thereof.
Background
The heat insulating layer of the solid rocket engine is a heat insulating layer material which is adhered between the inner surface of the shell and the propellant, and most heat is taken away through continuous decomposition and ablation of the heat insulating material when the engine works so as to relieve the heat transfer of high-temperature gas to the shell and avoid the shell from reaching the temperature which endangers the structural integrity, thereby ensuring the normal work of the engine. With the use of high-energy propellant in modern war and the design of high specific impulse engine, the temperature and pressure endured by the engine combustion chamber during working will be further increased compared with the ordinary engine, which puts more strict requirements on the structure and performance of the heat insulating layer. The material of the heat-insulating layer is required to have good ablation resistance and good body performance (tensile strength, elongation and density) and bonding performance (bonding strength between metals) at the same time.
The Ethylene Propylene Diene Monomer (EPDM) rubber-based heat insulation layer has the advantages of high thermal decomposition temperature, high elongation at break, good thermal-oxidative aging resistance, large filling coefficient and the like, has good compatibility with various propellants and shell materials, and is a heat insulation material which is the most complete type, the most stable performance and the most wide application of the solid rocket engine products at home and abroad at present.
However, since the ethylene propylene diene monomer rubber-based heat insulation layer is widely applied in the 80 th of the 20 th century, the ablation resistance of the ethylene propylene diene monomer rubber-based heat insulation layer cannot be obviously improved by the technical progress of ablation-resistant filler/fiber and flame retardant, and the linear ablation rate is between 0.07mm/s and 0.20 mm/s.
Disclosure of Invention
The technical problem solved by the invention is as follows: the composite heat insulating layer has excellent thermal performance, mechanical performance and technological performance of ethylene propylene diene monomer, good compatibility with various propellants and shell materials, high carbon formation rate and ablation resistance (the line ablation rate is 0.02-0.06 mm/s).
The technical scheme of the invention is as follows:
a benzoxazine resin/ethylene propylene diene monomer rubber composite heat insulation layer comprises the following raw materials in parts by mass:
100 parts of ethylene propylene diene monomer;
30-100 parts of benzoxazine resin;
10-15 parts of ablation-resistant fiber;
3-30 parts of a solid filler;
6-12 parts of a flame-retardant system;
2-5 parts of a process auxiliary agent;
4.5-9 parts of a vulcanization system;
the vulcanizing system comprises a vulcanizing agent, a co-vulcanizing catalyst and an accelerator, wherein the vulcanizing agent is at least one of sulfur, dicumyl peroxide and benzoyl peroxide, and the co-vulcanizing catalyst is 2-methylimidazole or 4-methylimidazole. 2. The benzoxazine resin/ethylene-propylene-diene monomer composite thermal insulation layer according to claim 1, wherein the flame retardant system comprises a flame retardant and a flame retardant aid, the flame retardant is at least one of (2-chloroethyl) phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tolylene-diphenyl phosphate, dibromomethane, dichlorobromomethane, melamine or melamine polyphosphate, and the flame retardant aid is antimony trioxide and/or magnesium hydroxide.
In an optional embodiment, the flame retardant is formed by mixing 1-3 parts by mass of (2-chloroethyl) phosphate and 1-3 parts by mass of melamine polyphosphate, and the flame retardant auxiliary agent is 1-3 parts by mass of antimony trioxide.
In an alternative embodiment, the accelerator is at least one of 2-mercaptobenzothiazole, triallylisocyanurate, trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, tetramethylthiuram disulfide, and dibenzothiazole disulfide.
In an optional embodiment, the vulcanizing agent is composed of 2 to 4 parts by mass of dicumyl peroxide and 1 to 2 parts by mass of sulfur, the mass of the co-vulcanization catalyst is 0.5 to 1% of the mass of the benzoxazine resin, and the accelerator is at least one of 1 to 2 parts by mass of 2-mercaptobenzothiazole, triallyl isocyanurate, trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, tetramethylthiuram disulfide and diphenyldibenzothiazole disulfide.
In an optional embodiment, the ablation-resistant fiber is one or a combination of more than two of carbon fiber, aramid pulp, aluminum borate whisker, silicon carbide whisker and poly-p-phenylene benzobisoxazole fiber.
In an optional embodiment, the solid filler is any one or a combination of two or more of silica, silicon carbide, zirconium boride, titanium boride, silicon hexaboride, zinc oxide, mica powder or aerogel.
In an optional embodiment, the process aid is any one or a combination of more than two of triethanolamine, dibutyl sebacate, dibutyl phthalate, dioctyl phthalate, stearic acid, hydroxyl silicone oil, KH550 or KH 570.
A preparation method of a benzoxazine resin/ethylene propylene diene monomer rubber composite heat insulating layer comprises the following steps:
weighing raw materials according to the raw material proportion of any one of claims 1 to 9;
secondly, plasticating the weighed ethylene propylene diene monomer rubber, and then adding the weighed solid filler for mixing to obtain a mixed material;
step three, adding the weighed benzoxazine resin into the mixture obtained in the step two, and blending at 50-80 ℃;
step four, adding the weighed ablation-resistant fibers, the flame-retardant system and the process auxiliary agent into the blend obtained in the step three for mixing, wherein the mixing temperature is 20-50 ℃, and a raw material for mixing the benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer is obtained;
placing the raw material obtained in the step four at the temperature of 20-30 ℃ for standing for 24-48 h, adding the weighed vulcanization system, open milling at the temperature of 20-50 ℃, and discharging;
and sixthly, after the sheet is produced, vulcanizing to obtain the benzoxazine resin/ethylene propylene diene monomer composite heat insulation layer.
In an optional embodiment, the vulcanizing system in the sixth step includes a vulcanizing agent, a co-vulcanizing catalyst and an accelerator, the vulcanizing agent is composed of 2 to 4 parts by mass of dicumyl peroxide and 1 to 2 parts by mass of sulfur, the mass of the co-vulcanizing catalyst is 0.5 to 1% of the mass of the benzoxazine resin, the accelerator is 1 to 2 parts by mass of at least one of 2-mercaptobenzothiazole, triallylisocyanurate, trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, tetramethylthiuram disulfide and dibenzothiazyl disulfide, the vulcanizing temperature is 150 to 160 ℃, the vulcanizing time is 1 to 2 hours, and the vulcanizing pressure is 10 to 20 MPa.
Compared with the prior art, the invention has the beneficial effects that:
the tensile strength of the composite heat insulating layer product is 7MPa to 9MPa, the elongation at break is 100 percent to 300 percent, the linear ablation rate is 0.02mm/s to 0.06mm/s, and the density is 1.00g/cm3～1.15g/cm3The hardness is 80-100, the bonding strength between the alloy and metal is 2.5-4.0 MPa, and the alloy can meet the development requirements of next generation weaponry on high speed, high altitude, high thrust, light weight and safety.
Drawings
Fig. 1 is a macroscopic picture before and after an ablation experiment of the benzoxazine resin/ethylene propylene diene monomer composite heat insulating layer provided in example 1 of the present invention, wherein the left side is the picture before ablation;
fig. 2 is SEM pictures before and after the ablation experiment of the benzoxazine resin/epdm rubber composite thermal insulation layer provided in example 1 of the present invention, wherein the picture before ablation is shown on the left side.
Detailed Description
The invention is further illustrated by the following examples.
The embodiment of the invention provides a benzoxazine resin/ethylene propylene diene monomer composite heat insulating layer which comprises the following raw materials in parts by mass:
100 parts of ethylene propylene diene monomer;
30-100 parts of benzoxazine resin;
10-15 parts of ablation-resistant fiber;
3-30 parts of a solid filler;
6-12 parts of a flame-retardant system;
2-5 parts of a process auxiliary agent;
4.5-9 parts of a vulcanization system;
the vulcanizing system comprises a vulcanizing agent, a co-vulcanizing catalyst and an accelerator, wherein the vulcanizing agent is at least one of sulfur, dicumyl peroxide and benzoyl peroxide, and the co-vulcanizing catalyst is 2-methylimidazole or 4-methylimidazole. Specifically, in the embodiment of the invention, the ethylene propylene diene monomer is a terpolymer of ethylene, propylene and non-conjugated diene; the benzoxazine resin is a compound containing N and O hexa-oxazine rings in the structure, and can be any one or the combination of more than two of bisphenol A type benzoxazine, bisphenol F type benzoxazine, DMA type benzoxazine, DCPD type benzoxazine, phenol type benzoxazine or DOPO type benzoxazine; the ablation-resistant fiber can be ablation-resistant fiber for a heat insulating layer of a conventional solid rocket engine, and is preferably one or a combination of more than two of carbon fiber, aramid pulp, aluminum borate whisker, silicon carbide whisker and PBO (poly-p-phenylene benzobisoxazole) fiber; the solid filler can be a solid filler for a heat insulating layer of a conventional solid rocket engine, and preferably is any one or the combination of more than two of silicon dioxide, silicon carbide, zirconium boride, titanium boride, silicon hexaboride, zinc oxide, mica powder or aerogel; the process aid is preferably any one or a combination of more than two of triethanolamine, dibutyl sebacate, dibutyl phthalate, dioctyl phthalate, stearic acid, hydroxyl silicone oil, KH550 or KH 570; the flame-retardant system preferably comprises a flame retardant and a flame-retardant auxiliary agent, the flame retardant is preferably at least one of (2-chloroethyl) phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate, cresyl-diphenyl phosphate, dibromomethane, dichlorobromomethane, melamine or melamine polyphosphate, and the flame-retardant auxiliary agent is preferably antimony trioxide and/or magnesium hydroxide; the accelerator is preferably at least one of 2-mercaptobenzothiazole, triallylisocyanurate, trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, tetramethylthiuram disulfide and dibenzothiazole disulfide. .
The benzoxazine resin/ethylene propylene diene monomer composite heat insulating layer provided by the embodiment of the invention takes an ethylene propylene diene monomer and benzoxazine resin co-cured substance as a substrate, and the benzoxazine resin and the ethylene propylene diene monomer are subjected to a co-vulcanization crosslinking reaction process under a certain condition under the action of a co-vulcanization catalytic system to form a benzoxazine resin/ethylene propylene diene monomer double-crosslinking structure, so that the composite heat insulating layer system has excellent thermal property, mechanical property and process property of the ethylene propylene diene monomer heat insulating layer, has good compatibility with various propellants and shell materials, and has high carbon formation rate and ablation resistance (the linear ablation rate is 0.02 mm/s-0.06 mm/s). The benzoxazine resin is subjected to self ring-opening polymerization in the vulcanization process and the polymerization process, no micromolecule is released, and the benzoxazine resin can be cured by self heating without adding a curing agent, so that the processing and forming process of the benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer is simple and easy to implement. But the benzoxazine resin has high requirements on the self-polymerization temperature (not less than 200 ℃), and has the problem of unmatched vulcanization conditions (temperature and time) with an ethylene propylene diene thermal insulation layer (vulcanization temperature is 150 ℃ -160 ℃), so that the benzoxazine resin and the ethylene propylene diene thermal insulation layer have poor compatibility, and the excellent performance of the material is difficult to exert. Therefore, the benzoxazine resin can only be added as a heat-insulating layer filler, but compared with an ethylene propylene diene monomer rubber material, the benzoxazine resin has brittleness and higher density, so that when used as the filler, the benzoxazine resin can obviously reduce the elongation of the ethylene propylene diene monomer heat-insulating layer and simultaneously improve the material density. Therefore, the benzoxazine resin material cannot be used as a heat insulating layer and a filler thereof in conventional cognition, the embodiment of the invention overcomes the technical prejudice, overcomes the coexistence problem between the benzoxazine resin material and the ethylene propylene diene monomer material by adopting a co-vulcanization catalytic system, realizes the preparation of the p-benzoxazine resin/ethylene propylene diene monomer co-vulcanization double-cross-linked system composite heat insulating layer, and finally determines the formula of the filler system, a fiber system, a flame retardant system and a process auxiliary agent through a great amount of experimental research throughout the year, so that the material system is fully compatible and further exerts the optimal performance. Ablation resistance is obtainedThe composite heat insulating layer product with excellent scour resistance has the tensile strength of 7-9 MPa, the elongation at break of 100-300 percent, the linear ablation rate of 0.02-0.06 mm/s and the density of 1.00g/cm3～1.15g/cm3The hardness is 80-100, the bonding strength between the alloy and metal is 2.5-4.0 MPa, and the alloy can meet the development requirements of next generation weaponry on high speed, high altitude, high thrust, light weight and safety.
In an optional embodiment, the flame retardant system consists of a flame retardant and a flame retardant aid, the flame retardant is formed by mixing 1-3 parts by mass of phosphoric acid (2-chloroethyl) ester and 1-3 parts by mass of melamine polyphosphate, and the flame retardant aid is 1-3 parts by mass of antimony trioxide. The benzoxazine resin material to which the present invention relates is a good flame retardant by itself (flame retardant rating: V0). On the basis, a small amount of MPP (melamine polyphosphate), TCEP (tris (2-chloroethyl) phosphate) and Sb are selected2O3The flame-retardant system is formed by combining (flame-retardant auxiliary agents). The flame-retardant system improves the flame-retardant performance of the material, reduces the proportion of MPP and TCEP of the flame retardant, further optimizes the technological performance of the heat-insulating layer, reduces the density of the heat-insulating material and improves the overall performance of the heat-insulating material.
In an optional embodiment, the vulcanizing agent is composed of 4 parts by mass of dicumyl peroxide and 2 parts by mass of sulfur, the mass of the co-vulcanization catalyst 2-methylimidazole is 0.5-1% of the mass of the benzoxazine resin, and the accelerator is at least one of 1-2 parts by mass of 2-mercaptobenzothiazole, triallyl isocyanurate, trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, tetramethylthiuram disulfide and dibenzothiazyl disulfide.
The benzoxazine resin and ethylene propylene diene monomer co-vulcanization catalytic system realizes the synergistic vulcanization co-crosslinking reaction of two material systems in the same temperature and time interval, obviously improves the compatibility between the materials, further optimizes the technological property of the heat insulation layer and fully exerts the excellent properties of the materials.
The embodiment of the invention also provides a preparation method of the benzoxazine resin/ethylene propylene diene monomer composite heat insulating layer, which comprises the following steps:
firstly, weighing raw materials according to the raw material proportion of the benzoxazine resin/ethylene propylene diene monomer rubber composite heat-insulating layer provided by the embodiment;
specifically, for detailed description and effects of the raw material ratios, reference is made to the above raw material ratio examples, which are not described herein again;
secondly, plasticating the weighed ethylene propylene diene monomer rubber, and then adding the weighed solid filler for mixing to obtain a mixed material;
specifically, in the second step of the present invention, plasticating and mixing may be performed on an internal mixer, a two-roll mill or a three-roll mill, and the like, but the present invention is not limited thereto, wherein plasticating is preferably performed at 40 ℃ to 60 ℃, and mixing is preferably performed at 50 ℃ to 70 ℃;
step three, adding the weighed benzoxazine resin into the mixture obtained in the step two, and blending at 50-80 ℃;
specifically, the number of thin passes in the blending of the step three in the embodiment of the invention is preferably 25-35, so that the resin is fully dispersed in the ethylene propylene diene monomer, and the two are uniformly mixed.
Step four, adding the weighed ablation-resistant fibers, the flame-retardant system and the process auxiliary agent into the blend obtained in the step three for mixing, wherein the mixing temperature is 20-50 ℃, and a raw material for mixing the benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer is obtained;
specifically, the number of passes during mixing in this step is preferably 25 to 35, so as to ensure uniform mixing. .
Placing the raw material obtained in the step four at the temperature of 20-30 ℃ for standing for 24-48 h, adding the weighed vulcanization system, open milling at the temperature of 20-50 ℃, and discharging;
specifically, in the step, the thin passing is preferably carried out for at least 20 times, and then the sheet is taken out;
and sixthly, after the sheet is produced, vulcanizing to obtain the benzoxazine resin/ethylene propylene diene monomer composite heat insulation layer.
The benzoxazine resin prepared by the preparation method provided by the embodiment of the inventionThe ethylene propylene diene monomer composite heat insulating layer has excellent ablation resistance and scouring resistance, the tensile strength of the composite heat insulating layer product is 7MPa to 9MPa, the elongation at break is 100 to 300 percent, the linear ablation rate is 0.02mm/s to 0.06mm/s, and the density is 1.00g/cm3～1.15g/cm3The hardness is 80-100, the bonding strength between the alloy and metal is 2.5-4.0 MPa, and the alloy can meet the development requirements of next generation weaponry on high speed, high altitude, high thrust, light weight and safety.
In an optional embodiment, the vulcanizing system in the sixth step includes a vulcanizing agent, a co-vulcanizing catalyst and an accelerator, the vulcanizing agent is composed of 2 to 4 parts by mass of dicumyl peroxide and 1 to 2 parts by mass of sulfur, the mass of the co-vulcanizing catalyst is 0.5 to 1% of the mass of the benzoxazine resin, the accelerator is 1 to 2 parts by mass of at least one of 2-mercaptobenzothiazole, triallylisocyanurate, trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, tetramethylthiuram disulfide and dibenzothiazyl disulfide, the vulcanizing temperature is 150 to 160 ℃, the vulcanizing time is 1 to 2 hours, and the vulcanizing pressure is 10 to 20 MPa.
The following are some specific examples of the present invention, and the raw materials used in each example are commercially available. Among them, the benzoxazine resin was CB7150 benzoxazine resin purchased from the university of sichuan.
Example 1
The benzoxazine resin/ethylene propylene diene monomer composite heat insulation layer provided by the embodiment comprises the following raw material components, by mass, 100 parts of ethylene propylene diene monomer, 60 parts of benzoxazine resin, 10 parts of aramid fiber, 10 parts of silicon dioxide, 2 parts of silicon carbide, 3 parts of phosphoric acid (2-chloroethyl) ester, 2 parts of melamine polyphosphate, 3 parts of dibutyl sebacate, 2 parts of KH 5502, 1 part of sulfur, 0.6 part of 2-methylimidazole, 3 parts of dicumyl peroxide and 3 parts of antimony trioxide, wherein the composite heat insulation layer has the tensile strength of 7-9 MPa, the elongation at break of 150%, the linear ablation rate of 0.03mm/s and the density of 1.08g/cm3The hardness was 88, and the adhesion strength with metal was 3.2 MPa. Macroscopic pictures before and after ablation experiment are shown in figure 1The SEM picture is shown in figure 2, and as can be seen from figures 1 and 2, the benzoxazine resin/ethylene propylene diene monomer rubber composite heat-insulating layer has good compatibility and carbon bonding property, and a carbon layer formed after ablation is compact, so that the ablation resistance and the scouring resistance of the heat-insulating layer can be effectively improved.
The preparation method of the benzoxazine resin/ethylene propylene diene monomer composite heat insulation layer material comprises the following steps:
step one, mixing materials according to raw material components of the composite heat insulating layer material;
plasticating ethylene propylene diene monomer rubber on a double-roller open mill to form a uniform roll, uniformly mixing the roll with a solid filler to obtain a mixed material, and blending the mixed material with benzoxazine resin by adopting an equal viscosity processing method, wherein the mixing temperature is 60 ℃, and the thin passing is carried out for 30 times; finally, uniformly mixing the ablation-resistant fiber, the flame retardant, the process aid and the mixture on a double-roll open mill at the mixing temperature of 30 ℃ for 25 times to obtain a raw material for mixing the benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer;
step three, placing the mixed heat insulation layer raw material in a temperature environment of 25 ℃ for standing for 24 hours, then carrying out open milling on an open mill, adding a vulcanization system, carrying out 30 ℃ temperature, uniformly mixing the vulcanization system and the mixed heat insulation layer raw material, carrying out thin passing for 20 times to obtain a uniform state, and then carrying out sheet production;
after the sheet is taken out, putting the material in a mould, and vulcanizing by using a flat vulcanizing machine; the curing temperature is 155 ℃, the time is 1h, and the pressure is 10MPa, so that the benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer is obtained.
Example 2
The benzoxazine resin/ethylene propylene diene monomer composite heat insulation layer provided by the embodiment comprises the following raw material components of 100 parts by mass of ethylene propylene diene monomer, 40 parts by mass of benzoxazine resin, 10 parts by mass of aramid pulp, 15 parts by mass of silicon dioxide, 5 parts by mass of zirconium boride, 5 parts by mass of (2-chloroethyl) phosphate, 5 parts by mass of dichlorobromomethane, 3 parts by mass of dibutyl sebacate, 2 parts by mass of KH 5502, 2 parts by mass of sulfur, 0.2 part by mass of 2-methylimidazole, 1.5 parts by mass of dicumyl peroxide, and antimony trioxide2 parts by mass, the tensile strength of the composite heat insulating layer is 7 MPa-9 MPa, the elongation at break is 232 percent, the thread ablation rate is 0.04mm/s, and the density is 1.08g/cm3The hardness was 90, and the adhesion strength to metal was 3.6 MPa.
The preparation method of the benzoxazine resin/ethylene propylene diene monomer composite heat insulation layer material comprises the following steps:
step one, batching according to the material components of the composite heat insulation layer;
plasticating ethylene propylene diene monomer rubber on a double-roller open mill to form a uniform roll, uniformly mixing the roll with a solid filler to obtain a mixed material, and blending the mixed material with benzoxazine resin by adopting an equal viscosity processing method, wherein the mixing temperature is 80 ℃, and the thin passing is carried out for 30 times; finally, uniformly mixing the ablation-resistant fiber, the flame retardant, the process aid and the mixture on a double-roll open mill at the mixing temperature of 40 ℃ to obtain a raw material for mixing the benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer;
step three, placing the mixed heat insulation layer raw material in a temperature environment of 20 ℃ for standing for 48h, then carrying out open milling on an open mill, adding a vulcanization system, carrying out temperature of 40 ℃, uniformly mixing the vulcanization system and the mixed heat insulation layer raw material, carrying out thin passing for 20 times to obtain a uniform state, and then carrying out sheet production;
after the sheet is taken out, putting the material in a mould, and vulcanizing by using a flat vulcanizing machine; the curing temperature is 150 ℃, the time is 2 hours, and the pressure is 20MPa, so that the benzoxazine resin/ethylene propylene diene monomer composite heat insulating layer is obtained.
Embodiment 3
The benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer provided by the embodiment comprises the following raw material components of 100 parts by mass of ethylene propylene diene monomer, 30 parts by mass of benzoxazine resin, 15 parts by mass of aramid fiber, 15 parts by mass of silicon dioxide, 5 parts by mass of silicon carbide, 5 parts by mass of phosphoric acid (2-chloroethyl) ester, 1 part by mass of stearic acid, 1 part by mass of triethanolamine, 2 parts by mass of KH 5502, 2 parts by mass of sulfur, 1 part by mass of 2-methylimidazole, 1 parts by mass of accelerator M and 2 parts by mass of TMTD, and has the tensile strength of 9MPa, the elongation at break of 286 percent and the linear ablation rate of 0 percent06mm/s, density 1.06g/cm3The hardness was 88, and the adhesion strength to metal was 3.5 MPa.
The preparation method of the benzoxazine resin/ethylene propylene diene monomer composite heat insulation layer material comprises the following steps:
step one, mixing materials according to raw material components of the composite heat insulating layer material;
plasticating ethylene propylene diene monomer rubber on a double-roller open mill to form a uniform roll, uniformly mixing the roll with a solid filler to obtain a mixed material, and blending the mixed material with benzoxazine resin by adopting an equal viscosity processing method, wherein the mixing temperature is 80 ℃, and the thin passing is carried out for 30 times; finally, uniformly mixing the ablation-resistant fiber, the flame retardant, the process aid and the mixture on a double-roll open mill at the mixing temperature of 20 ℃ for 30 times to obtain a raw material for mixing the benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer;
step three, placing the mixed heat insulation layer raw material in a temperature environment of 20 ℃ for standing for 24 hours, then carrying out open milling on an open mill, adding a vulcanization system, carrying out 50 ℃ temperature, uniformly mixing the vulcanization system and the mixed heat insulation layer raw material, carrying out thin passing for 20 times to obtain a uniform state, and then carrying out sheet production;
after the sheet is taken out, putting the material in a mould, and vulcanizing by using a flat vulcanizing machine; the curing temperature is 155 ℃, the time is 1h, and the pressure is 10MPa, so that the benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer is obtained.
Tensile tests on the composite thermal insulation layer in the embodiments of the invention were performed according to the GJB770B-2005 standard. Cutting the heat insulating layer film into dumbbell-shaped test pieces by using a cutter, placing the test pieces for 1h at the temperature of 20 +/-2 ℃, testing on a WDW-5J type electronic universal testing machine, and performing unidirectional stretching at the no-load speed of 100 +/-10 mm/min until the test pieces are broken. The ablation experiment is carried out according to the GJB323A-1996 standard, a sample is 10mm in thickness and a small cylinder with the diameter of 30mm, oxyacetylene is vertically flushed and burnt onto the sample during the test, the diameter of a nozzle is 2mm, the oxygen flow rate is 1512L/h, the acetylene flow rate is 1116L/h, the ablation time is 20s, and the ablation distance is 10 mm.
The implementation case results show that the invention obviously improves the ablation resistance and the anti-scouring capability of the ethylene propylene diene monomer rubber heat insulating layer, has excellent process performance and compatibility, and can meet the development requirements of high speed, high altitude, high thrust, light weight and safety of the next generation of aerospace weaponry.
In other embodiments of the present invention, the components may be selected from other materials listed herein.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to limit the present invention, and those skilled in the art can make variations and modifications of the present invention without departing from the spirit and scope of the present invention by using the methods and technical contents disclosed above.
Claims (10)
1. The benzoxazine resin/ethylene propylene diene monomer rubber composite heat insulation layer is characterized by comprising the following raw materials in parts by mass:
100 parts of ethylene propylene diene monomer;
30-100 parts of benzoxazine resin;
10-15 parts of ablation-resistant fiber;
3-30 parts of a solid filler;
6-12 parts of a flame-retardant system;
2-5 parts of a process auxiliary agent;
4.5-9 parts of a vulcanization system;
the vulcanizing system comprises a vulcanizing agent, a co-vulcanizing catalyst and an accelerator, wherein the vulcanizing agent is at least one of sulfur, dicumyl peroxide and benzoyl peroxide, and the co-vulcanizing catalyst is 2-methylimidazole or 4-methylimidazole.
2. The benzoxazine resin/ethylene-propylene-diene monomer composite thermal insulation layer according to claim 1, wherein the flame retardant system comprises a flame retardant and a flame retardant aid, the flame retardant is at least one of (2-chloroethyl) phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tolylene-diphenyl phosphate, dibromomethane, dichlorobromomethane, melamine or melamine polyphosphate, and the flame retardant aid is antimony trioxide and/or magnesium hydroxide.
3. The benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer according to claim 2, wherein the flame retardant is formed by mixing 1-3 parts by mass of (2-chloroethyl) phosphate and 1-3 parts by mass of melamine polyphosphate, and the flame retardant auxiliary agent is 1-3 parts by mass of antimony trioxide.
4. The benzoxazine resin/ethylene-propylene-diene monomer composite thermal insulation layer of claim 1, wherein the accelerator is at least one of 2-mercaptobenzothiazole, triallyl isocyanurate, trimethylolpropane trimethacrylate, N' -m-phenylene bismaleimide, tetramethylthiuram disulfide, and dibenzothiazyl disulfide.
5. The benzoxazine resin/ethylene propylene diene monomer composite heat insulation layer according to claim 4, wherein the vulcanizing agent is formed by combining 2-4 parts by mass of dicumyl peroxide and 1-2 parts by mass of sulfur, the mass of the co-vulcanization catalyst is 0.5-1% of the mass of the benzoxazine resin, and the mass of the accelerator is 1-2 parts by mass.
6. The benzoxazine resin/ethylene propylene diene monomer composite thermal insulation layer according to claim 1, wherein the ablation resistant fiber is one or a combination of more than two of carbon fiber, aramid pulp, aluminum borate whisker, silicon carbide whisker and poly-p-phenylene benzobisoxazole fiber.
7. The benzoxazine resin/ethylene propylene diene monomer composite thermal insulation layer according to claim 1, wherein the solid filler is any one or a combination of more than two of silica, silicon carbide, zirconium boride, titanium boride, silicon hexaboride, zinc oxide, mica powder or aerogel.
8. The benzoxazine resin/ethylene propylene diene monomer composite thermal insulation layer according to claim 1, wherein the process aid is any one or a combination of more than two of triethanolamine, dibutyl sebacate, dibutyl phthalate, dioctyl phthalate, stearic acid, hydroxyl silicone oil, KH550 or KH 570.
9. The preparation method of the benzoxazine resin/ethylene propylene diene monomer rubber composite heat insulating layer is characterized by comprising the following steps:
weighing raw materials according to the raw material proportion of any one of claims 1 to 8;
secondly, plasticating the weighed ethylene propylene diene monomer rubber, and then adding the weighed solid filler for mixing to obtain a mixed material;
step three, adding the weighed benzoxazine resin into the mixture obtained in the step two, and blending at 50-80 ℃;
step four, adding the weighed ablation-resistant fibers, the flame-retardant system and the process auxiliary agent into the blend obtained in the step three for mixing, wherein the mixing temperature is 20-50 ℃, and a raw material for mixing the benzoxazine resin/ethylene propylene diene monomer composite heat-insulating layer is obtained;
placing the raw material obtained in the step four at the temperature of 20-30 ℃ for standing for 24-48 h, adding the weighed vulcanization system, open milling at the temperature of 20-50 ℃, and discharging;
and sixthly, after the sheet is produced, vulcanizing to obtain the benzoxazine resin/ethylene propylene diene monomer composite heat insulation layer.
10. The preparation method of the benzoxazine resin/ethylene propylene diene monomer composite heat insulating layer according to claim 9, wherein the curing system in the sixth step comprises a curing agent, a co-curing catalyst and an accelerator, wherein the curing agent is formed by combining 2-4 parts by mass of dicumyl peroxide and 1-2 parts by mass of sulfur, the mass of the co-curing catalyst is 0.5-1% of the mass of the benzoxazine resin, the mass of the accelerator is 1-2 parts by mass, the curing temperature is 150-160 ℃, the curing time is 1-2 h, and the curing pressure is 10-20 MPa.
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