CN115849999B - Hydrocarbon fuel-rich propellant and preparation method thereof - Google Patents
Hydrocarbon fuel-rich propellant and preparation method thereof Download PDFInfo
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- CN115849999B CN115849999B CN202211656394.7A CN202211656394A CN115849999B CN 115849999 B CN115849999 B CN 115849999B CN 202211656394 A CN202211656394 A CN 202211656394A CN 115849999 B CN115849999 B CN 115849999B
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- 239000003380 propellant Substances 0.000 title claims abstract description 103
- 239000000446 fuel Substances 0.000 title claims abstract description 91
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 83
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 83
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 238000000859 sublimation Methods 0.000 claims abstract description 11
- 230000008022 sublimation Effects 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 35
- 239000004793 Polystyrene Substances 0.000 claims description 23
- 229920002223 polystyrene Polymers 0.000 claims description 23
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 22
- 238000001179 sorption measurement Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 12
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- -1 glycol monobutyl ether ester Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- AVUYXHYHTTVPRX-UHFFFAOYSA-N Tris(2-methyl-1-aziridinyl)phosphine oxide Chemical compound CC1CN1P(=O)(N1C(C1)C)N1C(C)C1 AVUYXHYHTTVPRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- XYVVCFFJQVMSNN-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) 5-octylcyclopenta-1,3-diene Chemical compound [Fe++].c1cc[cH-]c1.CCCCCCCC[c-]1cccc1 XYVVCFFJQVMSNN-UHFFFAOYSA-N 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- UAGLZAPCOXRKPH-UHFFFAOYSA-N nitric acid;1,2,3-triaminoguanidine Chemical compound O[N+]([O-])=O.NNC(NN)=NN UAGLZAPCOXRKPH-UHFFFAOYSA-N 0.000 claims description 3
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- JETYEYTVNWNEID-UHFFFAOYSA-N 1,6-diisocyanatohexane;5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane Chemical compound O=C=NCCCCCCN=C=O.CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 JETYEYTVNWNEID-UHFFFAOYSA-N 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 19
- 238000002485 combustion reaction Methods 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007847 structural defect Effects 0.000 abstract description 5
- 230000007123 defense Effects 0.000 abstract 1
- 239000013022 formulation composition Substances 0.000 description 13
- 238000009472 formulation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ASVKKRLMJCWVQF-UHFFFAOYSA-N 3-buten-1-amine Chemical compound NCCC=C ASVKKRLMJCWVQF-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- JUTIJVADGQDBGY-UHFFFAOYSA-N anthracene photodimer Chemical compound C12=CC=CC=C2C2C(C3=CC=CC=C33)C4=CC=CC=C4C3C1C1=CC=CC=C12 JUTIJVADGQDBGY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The invention relates to a hydrocarbon fuel-rich propellant formula, which adopts non-sublimated PCU composite fuel as main hydrocarbon fuel, solves the problem that high-energy cage-type hydrocarbon fuel generates structural defects in the propellant storage process due to sublimation, and has the advantages that the interface effect between the hydrocarbon fuel and an adhesive system is stronger due to the application of the non-sublimated PCU composite hydrocarbon fuel, the mechanical property of the propellant is greatly improved, the propellant has better storage stability, and the propellant has higher burning speed and pressure index. The technical requirements of the solid ramjet engine on excellent storage performance, mechanical property and high combustion efficiency of the propellant are met. The method lays a solid foundation for solving the power source requirement problem of the solid ramjet engine of the advanced tactical missile power device and pushing the development process of the advanced tactical missile weapons of the army, and can remarkably improve the fight efficiency of the missile weapons of the army and the national defense strength of China.
Description
Technical Field
The invention belongs to the field of fuel-rich propellants for solid ramjet engines, and relates to a hydrocarbon fuel-rich propellant for a solid ramjet engine and a preparation method thereof.
Background
The solid-ramjet engine organically combines the advantages of a solid rocket engine and an air suction engine. Oxygen in the air is used as an oxidant, so that the energy of the propellant is greatly improved; the internal surface compression air inlet principle is adopted, complex structures such as rotating parts and the like are omitted, and the engine structure is simplified. Therefore, the missile taking the solid impact engine as power has the characteristics of small volume, light weight and long range, can realize the whole-course powered flight, and enhances the burst prevention capability and the final attack capability of the missile.
The solid-ramjet engine uses a fuel-rich propellant as a power source, wherein the fuel content reaches 30-50%, so that the fuel performance is one of key factors for determining whether the potential excellent performance of the solid-ramjet engine can be fully exerted, and the boron-containing fuel-rich propellant has a very high heat value and is the first-choice propellant of the solid-ramjet engine. However, due to certain characteristics of boron itself, its use in certain particular fields is restricted.
In order to make up for the shortages of the boron-containing fuel-rich propellant in certain application fields, the application range of the solid-ramjet engine is expanded, and the solid hydrocarbon fuel-rich propellant with excellent ignition performance, high combustion efficiency, wen Shizhong combustion, high gas yield, less condensed phase, relatively clean gas and less residue is developed in developed western countries.
The hydrocarbon fuel-rich propellant adopts high-density hydrocarbon fuel as main fuel, the performance of the hydrocarbon fuel determines the performance of the propellant, and particularly under the use environment of limited volume such as a solid ramjet engine, the energy generated by the fuel per unit volume is needed to be considered, so the hydrocarbon fuel is required to have the density and the volume heat value as high as possible for improving the energy performance of the propellant, and in an HTPB system, the density and the volume heat value of the hydrocarbon fuel are required to be ensured to be obviously higher than those of a pure HTPB adhesive.
High tension cage-shaped hydrocarbon fuel pentacyclic (5.4.0.0) 2,6 .0 3,10 .0 5,9 ]Undecane (PCU) density of 1.239g/cm 3 The mass heat value is 44.5MJ/Kg, and the volume heat value is 54.5MJ/dm 3 Is a high-energy hydrocarbon fuel, and the research finds that under the same geometric shape and thermodynamic conditions, the ignition speed of the PCU is an order of magnitude higher than that of the HTPB, and the release heat of the PCU in the combustion process is twice that of the HTPB.
The high density cage compound PCU has high energy, high density characteristics, but the hydrocarbon propellant employing PCU as fuel has poor storage properties due to its extreme sublimation. Patent ZL201510940390.5 discloses thermoplastic hydrocarbon propellants using PCU as fuel, achieving a fast response, but a large number of needle-hole structure defects appear in the propellant after half a year of storage of the propellant using PCU.
Patent ZL201910030750.6 uses PCU as hydrocarbon fuel, GAP system as binder system and acrylic acid polyethylene glycol monobutyl ether/acrylonitrile/3-butene-1-amine/butyl acrylate copolymer, the structural stability of the propellant is greatly enhanced, the propellant has no structural defect after half a year of storage, however, the propellant is found to start to have structural defect after one year of storage, and the propellant has lower energy performance due to the adoption of GAP binder system and has low strength due to the characteristic of PCU.
The patent ZL201811598676.X adopts non-sublimated hydrocarbon fuel to prepare the propellant, the propellant has higher energy performance and combustion performance, compared with the prior hydrocarbon propellant formulation, the mechanical performance of the propellant prepared by adopting the non-sublimated hydrocarbon fuel is greatly improved, structural defects are not generated after the propellant is placed for several years, the mechanical performance of the propellant is not changed, the service life of the propellant can reach more than 15 years, and the patent ZL201811598676.X also indicates that only the non-sublimated hydrocarbon can be used as the propellant fuel for the propellant formulation.
Therefore, as long as the problem that the PCU generates structural defects in the storage process due to sublimation is solved, the PCU has extremely wide application prospect in the solid ramjet engine.
Disclosure of Invention
The technical problem solved by the invention is to provide a hydrocarbon fuel-rich propellant, which adopts PCU which is easy to sublimate as a raw material, and the hydrocarbon fuel is obtained by adsorption and other treatments of other components and is not sublimated: the hydrocarbon fuel of the invention takes porous polystyrene with high heat value and low density and porous structure as a matrix, takes polyethylene glycol monobutyl ether acrylate/acrylonitrile/allylamine/propenol/hydroxyethyl acrylate copolymer with polyfunctional groups as an auxiliary matrix, adsorbs PCU with high density and is easy to sublimate, and under the combined action of the porous structure of the porous polystyrene and the polyethylene glycol monobutyl ether acrylate/acrylonitrile/allylamine/propenol/hydroxyethyl acrylate copolymer, the sublimation of the PCU is inhibited, the physical property of the prepared composite hydrocarbon fuel is stable, the sublimation phenomenon can not occur below 90 ℃, the structure defect caused by sublimation in the storage process of the prepared propellant can not occur, and the problem of the structure defect caused by the sublimation in the storage process of the propellant of the high-energy cage-type hydrocarbon fuel is solved.
The technical scheme adopted by the invention is as follows: PCU with high density, high energy performance and sublimation characteristic is adsorbed by adopting porous polystyrene with low density and porous structure, under the combined action of the porous structure of porous polystyrene and the copolymer of polyethylene glycol monobutyl ether acrylate/acrylonitrile/allylamine/allyl alcohol/hydroxyethyl acrylate, the sublimation of PCU is inhibited, the stability is greatly enhanced, and the density of the prepared composite hydrocarbon fuel is 1.20g/cm 3 The mass heat value is 44.8MJ/Kg, and the volume heat value is 53.6MJ/dm 3 。
Compared with the common propellant containing PCU, the propellant adopting the composite hydrocarbon fuel has the advantages that the storage stability and the mechanical property are greatly improved, the combustion performance of the propellant is improved, the energy release efficiency is effectively improved, the generation of condensed phases is reduced, the requirement of the propellant on the storage performance is met, and the requirements of the solid ramjet engine on the performances of the propellant such as energy, technology, combustion and the like are also met.
A hydrocarbon fuel-rich propellant, characterized by: comprises the following components in percentage by mass:
composite hydrocarbon fuel: 27-45%;
oxidizing agent: 28-38%;
auxiliary metal fuel: 8-15%;
an adhesive system: 17-25%;
functional auxiliary agent: 0.5 to 4 percent;
the composite hydrocarbon fuel takes porous polystyrene (HPS) as a matrix, and sublimates easily under the combined action of a composite auxiliary agent of polyethylene glycol monobutyl ether acrylate/acrylonitrile/allylamine/allyl alcohol/hydroxyethyl acrylate copolymer (PANE) to form a high-density cage-type hydrocarbon pentacyclic [5.4.0.0 ] 2,6 .0 3,10 .0 5,9 ]Undecane is compounded with porous polystyrene to prepare stable non-sublimated compound hydrocarbon fuel (HPSPCU), and the particle size of the HPSPCU is 20-50 mu m.
The research shows that the PCU can be adsorbed by the active carbon, the silicon dioxide, the hyperbranched resin and the like with porous structures, and the PCU after adsorption can not sublimate at a lower temperature, so that the storage stability of the PCU can be greatly improved. However, the composite hydrocarbon fuel obtained by adsorbing PCU with activated carbon, silica, or the like has poor combustion performance, and energy performance is difficult to release.
Polystyrene Density 1.04g/cm 3 The mass heat value is 46MJ/Kg, and the volume heat value is 47.8MJ/dm 3 The use of this alone as a propellant fuel reduces the propellant density and hence the volumetric heating value of the propellant due to its lower density. The HPS is matched with the PANE to adsorb the PCU, the HPS has an irregular internal structure and higher binding energy with the PCU, the PCU can be adsorbed in the HPS, the PANE has active functional groups such as amino, hydroxyl and the like, the adsorption between the PCU and the HPS can be further enhanced, and under the action of the PANEThe combination energy of PCU and multi-HPS is stronger, and the PCU and multi-HPS can not sublimate below 90 ℃, so that the requirement of propellant storage stability can be met. The density of the prepared composite hydrocarbon fuel is 1.20g/cm 3 The mass heat value is 44.8MJ/Kg, and the volume heat value is 53.6MJ/dm 3 Can meet the requirements of high density and high heat value of the propellant.
The preparation method of the composite hydrocarbon fuel comprises the following steps: high density caged hydrocarbon pentacyclic [5.4.0.0 ] in dry environment at a mass ratio of 4.6:1 2,6 .0 3,10 .0 5,9 ]Adding undecane and porous polystyrene into a dry three-dimensional mixer, vacuumizing at normal temperature to remove air therein, sealing the container when the system pressure is less than 0.1atm, mixing at normal temperature for 1 hr, then raising the temperature to 60 deg.C, mixing at 60 deg.C for 2 hr, cooling to normal temperature in the mixed state, continuing mixing for 1 hr, repeating heating, mixing, cooling and mixing for 4 times to obtain pentacyclic [5.4.0.0 ] 2,6 .0 3,10 .0 5,9 ]Fully sublimating undecane and forming adsorption with porous polystyrene, naturally cooling to room temperature, adding a composite additive with the mass fraction of 2% of that of the porous polystyrene, heating to 60 ℃ under the condition of 0.1atm, mixing for 5 hours, cooling to room temperature, discharging, sublimating at 30 ℃ for 24 hours, and recovering free pentacyclic [5.4.0.0 ] 2,6 .0 3,10 .0 5,9 ]Undecane, to give pentacyclic [5.4.0.0 ] 2,6 .0 3,10 .0 5,9 ]And the mass ratio of undecane to porous polystyrene is 4:1.
Because PCU is very easy to sublimate, the system is required to be quickly vacuumized to 0.1atm at normal temperature, in order to improve the sublimation adsorption efficiency, the system is heated, the glass transition temperature of polystyrene is 80 ℃, the mixing temperature is required to be below 80 ℃, the mixing adsorption efficiency is highest at about 60 ℃ through test verification, and in order to ensure the adsorption efficiency of HPS on PCU, the mixed adsorption of heating and cooling for many times is adopted. The PANE as a compounding auxiliary agent is added after the PANE is needed, and if the PANE is added simultaneously with the PCU and the HPS, the PANE can be attached to the surface of the HPS to block pores, so that the adsorption is affected.
The porous polystyrene has a porosity of 80% and a particle size of 20-40 μm.
HPS with the porosity of 80% has the optimal adsorption effect, HPS with smaller particle size must be selected for preventing HPS from being broken due to mechanical vibration in the mixing process due to high porosity, HPS with the particle size of 20-40 mu m is not too fine for guaranteeing the adsorption effect, HPS can be prevented from being broken in the mixing process, good adsorption effect is achieved, and the particle size of the prepared composite hydrocarbon fuel is not changed greatly.
The oxidant is one or the combination of Ammonium Perchlorate (AP), potassium perchlorate (KP) and triaminoguanidine nitrate (TAGN), and the particle size of the oxidant is 0.5-400 mu m.
The auxiliary metal fuel is one or a combination of aluminum (Al), magnesium (Mg) and boron (B), and the grain diameter is 1-10 mu m.
The adhesive system comprises an adhesive, a curing agent, and a plasticizer; wherein the binder is hydroxyl-terminated polybutadiene (HTPB); the curing agent is one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and 4,4' -dicyclohexylmethane diisocyanate (HMDI); the plasticizer is carborane methyl caproate (HCME) or carborane methyl Butyrate (BCME).
The functional auxiliary agent is tris [1- (2-methyl) aziridinyl]Phosphine Oxide (MAPO), triphenylbismuth (TPB), ferric acetylacetonate (FeAA), ferric oxide (Fe) 2 O 3 ) A combination of one or more of Octyl Ferrocene (OFC), iron Polyacrylate (PAAF), copper 3-amino-1, 2, 4-triazole perchlorate (ACP), N-diphenyl-p-phenylenediamine (DPPD), N-phenyl-2-naphthylamine (anti-aging agent D), N-phenyl-N-cyclohexane-based p-phenylenediamine (anti-aging agent 4010).
The invention also provides a preparation method of the hydrocarbon fuel-rich propellant, which comprises the following steps:
step one, weighing and mixing propellant: weighing the components in proportion in a dry environment, adding functional additives into an adhesive, uniformly mixing to obtain premixed slurry, sequentially adding the composite hydrocarbon fuel, the auxiliary metal fuel and the oxidant into a vertical mixer, uniformly mixing, adding a curing agent, continuously mixing, controlling the mixing temperature to be 30-50 ℃ and the mixing time to be 70-110 min, and discharging until the system is completely and uniformly mixed to obtain slurry;
pouring and solidifying the propellant: and (3) carrying out vacuum casting on the slurry, and solidifying for 5-8 days in a drying environment at 50-70 ℃ to prepare the hydrocarbon-rich fuel propellant.
Compared with the prior art, the invention has the advantages that:
1. HPS is matched with PANE to adsorb PCU, the HPS has an irregular porous structure, PCU can be effectively adsorbed, the PANE has an active functional group to strengthen the adsorption between the PCU and the HPS, the combination of the PCU and the HPS is tighter under the combined action of the PCU and the HPS, the PCU and the HPS cannot sublimate below 90 ℃, and the requirement of propellant storage stability can be met.
2. HPS with a porous structure is used as a matrix, and PANE with an active functional group is used as an auxiliary base material, so that the interface effect between a hydrocarbon fuel system and an adhesive system is stronger, and the mechanical property of the propellant is greatly improved.
3. By adopting an adsorption type hydrocarbon fuel system, small-molecule PCU compounds with excellent combustion performance are adsorbed by a porous structure hydrocarbon matrix, PCU cannot escape at a lower temperature, and PCU rapidly escapes and burns at a higher temperature in the propellant combustion process, so that the heat loss caused by hydrocarbon fuel pyrolysis is reduced, and the combustion performance of the propellant is greatly improved.
Detailed Description
The following is a detailed description of specific embodiments.
Example 1
Preparation of HPSPCU
Weighing 46kg of PCU and 10kg of HPS with the porosity of 80% and the particle size of 20 mu m in a dry environment, adding into a dry three-dimensional mixer, vacuumizing at normal temperature to remove air therein, sealing a container when the system pressure is less than 0.1atm, mixing at normal temperature for 1 hour, then raising the temperature to 60 ℃, mixing at 60 ℃ for 2 hours, naturally cooling to normal temperature in a mixed state, continuing mixing for 1 hour, repeatedly raising the temperature, mixing and cooling for 4 times, fully sublimating PCU and forming adsorption with porous polystyrene, naturally cooling to the room temperature, adding 200g of PANE, vacuumizing to 0.1atm, raising the temperature to 60 ℃ under the condition of 0.1atm, mixing for 5 hours, lowering the temperature to the room temperature, discharging, sublimating at 30 ℃ for 24 hours, recovering PCU5.8kg, and obtaining 49.8kg of composite hydrocarbon fuel, wherein the mass ratio of PCU to HPS in the composite hydrocarbon fuel is 4:1, and the particle size of the composite hydrocarbon fuel is 21 mu m.
Example 2
Preparation of HPSPCU
Weighing 92kg of PCU and 20kg of HPS with the porosity of 80% and the particle size of 30 mu m in a dry environment, adding into a dry three-dimensional mixer, vacuumizing at normal temperature to remove air therein, sealing a container when the system pressure is less than 0.1atm, mixing at normal temperature for 1 hour, then raising the temperature to 60 ℃, mixing at 60 ℃ for 2 hours, naturally cooling to normal temperature in a mixed state, continuing mixing for 1 hour, repeatedly raising the temperature, mixing and cooling for 4 times, fully sublimating PCU and forming adsorption with porous polystyrene, naturally cooling to the room temperature, adding 400g of PANE, vacuumizing to 0.1atm, raising the temperature to 60 ℃ under the condition of 0.1atm, mixing for 5 hours, lowering the temperature to the room temperature, discharging, sublimating at 30 ℃ for 24 hours, recovering PCU11.8kg, and obtaining 100.2kg of composite hydrocarbon fuel, wherein the mass ratio of PCU to HPS in the composite hydrocarbon fuel is 4:1, and the particle size of the composite hydrocarbon fuel is 32 mu m.
Example 3
Preparation of HPSPCU
Weighing 115kg of PCU and 25kg of HPS with the porosity of 80% and the particle size of 40 mu m in a dry environment, adding into a dry three-dimensional mixer, vacuumizing at normal temperature to remove air therein, sealing a container when the system pressure is less than 0.1atm, mixing at normal temperature for 1 hour, then raising the temperature to 60 ℃, mixing at 60 ℃ for 2 hours, naturally cooling to normal temperature in a mixed state, continuing mixing for 1 hour, repeatedly raising the temperature, mixing and cooling for 4 times, fully sublimating PCU and forming adsorption with porous polystyrene, naturally cooling to the room temperature, adding 500g of PANE, vacuumizing to 0.1atm, raising the temperature to 60 ℃ under the condition of 0.1atm, mixing for 5 hours, lowering the temperature to the room temperature, discharging, sublimating at 30 ℃ for 24 hours, recovering PCU14.7kg, and obtaining 124.8kg of composite hydrocarbon fuel, wherein the mass ratio of PCU to HPS in the composite hydrocarbon fuel is 4:1, and the particle size of the composite hydrocarbon fuel is 43 mu m.
Example 4
A hydrocarbon fuel-rich propellant has a formulation shown in Table 1 and the resulting propellant properties shown in Table 2.
TABLE 1 propellant formulation composition
Table 2 Properties of the propellants obtained from the formulations shown in Table 1
Example 5
A hydrocarbon fuel-rich propellant has a formulation shown in Table 3 and the resulting propellant properties shown in Table 4.
TABLE 3 propellant formulation composition
Table 4 Properties of the propellant obtained from the formulations shown in Table 3
Example 6
A hydrocarbon fuel-rich propellant has a formulation shown in Table 5 and the resulting propellant properties shown in Table 6.
TABLE 5 propellant formulation composition
Table 6 Properties of the propellant obtained from the formulations shown in Table 5
Example 7
A hydrocarbon fuel-rich propellant having a formulation composition as shown in Table 7 and resulting propellant properties as shown in Table 8.
TABLE 7 propellant formulation composition
Table 8 Properties of the propellant obtained from the formulations shown in Table 7
Example 8
A hydrocarbon fuel-rich propellant having a formulation composition as shown in Table 9 and resulting propellant properties as shown in Table 10.
TABLE 9 propellant formulation composition
Table 10 Properties of the propellant obtained from the formulations shown in Table 9
Example 9
A hydrocarbon fuel-rich propellant having a formulation composition as shown in Table 11 and resulting propellant properties as shown in Table 12.
TABLE 11 propellant formulation composition
Table 12 Properties of the propellant obtained from the formulations shown in Table 11
To verify the practical effect produced by the present invention, comparative examples are used for further illustration.
Comparative example 1
In this example, PCU, HPS and PANE are used for direct charging, the proportion is completely consistent with the proportion of the compound hydrocarbon fuel in the invention, and the propellant formula is the same as in example 6. Tables 13 and 14 below list formulation composition and properties, respectively, for comparison.
TABLE 13 propellant formulation composition
TABLE 14 Property of propellant
It can be seen from example 6 and comparative example 1 that the present invention uses PCU, HPS and PANE to directly replace the composite hydrocarbon fuel, the propellant with the same pressure point has higher burning rate and higher pressure index, but the mechanical property of the propellant is greatly reduced, the storage performance is greatly reduced, and the air holes appear in the propellant after half a year of storage, so that the structural integrity is difficult to maintain.
Comparative example 2
To further demonstrate the beneficial effects of the present invention, the present example uses a hydrocarbon propellant formulation closest to that of example 7, the following table 15 shows the formulation composition of a hydrocarbon-rich fuel propellant closest to that of example 7, the main difference from example 7 being that the hydrocarbon fuel used in patent zl201811598676.X, the hydrocarbon fuel type used in example 1, is dianthracene, and table 16 shows the properties of the corresponding resulting propellant.
TABLE 15 propellant formulation composition
TABLE 16 Property of propellant
It can be seen from example 7 and comparative example 2 that example 7 replaced the bianthracene hydrocarbon fuel with the PCU adsorbed composite hydrocarbon fuel and replaced DOS with HCME, with other components and compositions being identical. The strength of the propellant was comparable and the strength did not change after 3 years of storage. The combustion speed and the pressure index of the invention are higher than those of comparative example 2, because adsorbed small molecule PCU escapes from the porous structure in the combustion process, and combustion is easier, the injection efficiency and the combustion efficiency of the invention are better than those of comparative example 2, and therefore, the technical scheme of the invention can improve the storage stability of the propellant, improve the mechanical property of the propellant, and the propellant has higher combustion speed and pressure index.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (6)
1. A hydrocarbon fuel-rich propellant, characterized by: comprises the following components in percentage by mass:
composite hydrocarbon fuel: 27-45%;
oxidizing agent: 28-38%;
auxiliary metal fuel: 8-15%;
an adhesive system: 17-25%;
functional auxiliary agent: 0.5 to 4 percent;
the composite hydrocarbon fuel takes porous polystyrene as a matrix, and cage-type hydrocarbon pentacyclic [5.4.0.0 ] is prepared under the action of a composite additive polyethylene glycol monobutyl ether acrylate/acrylonitrile/allylamine/allyl alcohol/hydroxyethyl acrylate copolymer 2 ,6 .0 3,10 .0 5,9 ]Undecane and the porous polystyrene matrix are compounded to prepare the composite hydrocarbon fuel, and the particle size of the composite hydrocarbon fuel is 20-50 mu m;
the preparation method of the composite hydrocarbon fuel comprises the following steps:
s1, weighing high-density cage-type hydrocarbon pentacyclic [5.4.0.0 ] in a dry environment according to a mass ratio of 4.6:1 2,6 .0 3, 10 .0 5,9 ]Undecane and porous polystyrene are added into a dry three-dimensional mixer, air in the mixer is removed by normal temperature vacuum pumping, the container is closed when the system pressure is less than 0.1atm, and the mixture is mixed for 1 hour at normal temperature;
s2, raising the temperature to 60 ℃, mixing for 2 hours at 60 ℃, then cooling to room temperature in a mixed state, and continuing mixing for 1 hour;
s3, repeating the heating-mixing-cooling-mixing process in the step S2 for 4 times to enable the pentacyclic [5.4.0.0 ] 2,6 .0 3,10 .0 5,9 ]Undecane sublimates and forms adsorption with porous polystyrene;
s4, adding an acrylic acid polyethylene glycol monobutyl ether ester/acrylonitrile/allylamine/allyl alcohol/hydroxyethyl acrylate copolymer composite additive accounting for 2% of the mass of the porous polystyrene at room temperature, heating to 60 ℃ under the condition of 0.1atm, mixing for 5 hours, cooling to room temperature, and discharging;
s5, recovering free pentacyclic [5.4.0.0 ] by sublimation at 30 ℃ for 24 hours 2,6 .0 3,10 .0 5,9 ]Undecane, to give pentacyclic [5.4.0.0 ] 2,6 .0 3,10 .0 5,9 ]The mass ratio of undecane to porous polystyrene is 4:1.
2. The hydrocarbon-rich fuel propellant of claim 1, wherein: the porous polystyrene has a porosity of 80% and a particle size of 20-40 μm.
3. The hydrocarbon-rich fuel propellant of claim 1, wherein: the oxidant is one or a combination of ammonium perchlorate, potassium perchlorate and triaminoguanidine nitrate, and the particle size of the oxidant is 0.5-400 mu m.
4. The hydrocarbon-rich fuel propellant of claim 1, wherein: the auxiliary metal fuel is one or the combination of aluminum, magnesium and boron, and the grain diameter is 1-10 mu m.
5. The hydrocarbon-rich fuel propellant of claim 1, wherein: the adhesive system comprises an adhesive, a curing agent, and a plasticizer; wherein the binder is hydroxyl-terminated polybutadiene; the curing agent is one or more of hexamethylene diisocyanate isophorone diisocyanate and 4,4' -dicyclohexylmethane diisocyanate; the plasticizer is carborane methyl caproate and/or carborane methyl butyrate.
6. The hydrocarbon-rich fuel propellant of claim 1, wherein: the functional auxiliary agent is one or a combination of more of tris [1- (2-methyl) aziridinyl ] phosphine oxide, triphenylbismuth, ferric acetylacetonate, ferric oxide, octyl ferrocene, ferric polyacrylate, 3-amino-1, 2, 4-triazole copper perchlorate, N-diphenyl-p-phenylenediamine, N-phenyl-2-naphthylamine and N-phenyl-N-cyclohexane-p-phenylenediamine.
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