CN116606398B - Fluorine-containing macromolecular bonding agent and preparation method and application thereof - Google Patents
Fluorine-containing macromolecular bonding agent and preparation method and application thereof Download PDFInfo
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- CN116606398B CN116606398B CN202310541727.XA CN202310541727A CN116606398B CN 116606398 B CN116606398 B CN 116606398B CN 202310541727 A CN202310541727 A CN 202310541727A CN 116606398 B CN116606398 B CN 116606398B
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- fluorine
- bonding agent
- containing macromolecular
- macromolecular bonding
- solid propellant
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- 239000007767 bonding agent Substances 0.000 title claims abstract description 91
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 86
- 239000011737 fluorine Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004449 solid propellant Substances 0.000 claims abstract description 63
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- TYCFGHUTYSLISP-UHFFFAOYSA-M 2-fluoroprop-2-enoate Chemical compound [O-]C(=O)C(F)=C TYCFGHUTYSLISP-UHFFFAOYSA-M 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000004014 plasticizer Substances 0.000 claims description 10
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 150000001540 azides Chemical class 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002360 explosive Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 8
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 7
- -1 acrylic ester Chemical class 0.000 description 7
- 239000003380 propellant Substances 0.000 description 7
- 239000013022 formulation composition Substances 0.000 description 5
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 4
- 230000006978 adaptation Effects 0.000 description 4
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 4
- AGCQZYRSTIRJFM-UHFFFAOYSA-N triethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCOCCO[N+]([O-])=O AGCQZYRSTIRJFM-UHFFFAOYSA-N 0.000 description 4
- IPPYBNCEPZCLNI-UHFFFAOYSA-N trimethylolethane trinitrate Chemical compound [O-][N+](=O)OCC(C)(CO[N+]([O-])=O)CO[N+]([O-])=O IPPYBNCEPZCLNI-UHFFFAOYSA-N 0.000 description 4
- RDLIBIDNLZPAQD-UHFFFAOYSA-N 1,2,4-butanetriol trinitrate Chemical compound [O-][N+](=O)OCCC(O[N+]([O-])=O)CO[N+]([O-])=O RDLIBIDNLZPAQD-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- LZLKDWBQTGTOQY-UHFFFAOYSA-N trinitramide Inorganic materials O=N(=O)N(N(=O)=O)N(=O)=O LZLKDWBQTGTOQY-UHFFFAOYSA-N 0.000 description 2
- JAEMWNGTMVISQW-UHFFFAOYSA-N 1,1-dinitroethene Chemical group [O-][N+](=O)C(=C)[N+]([O-])=O JAEMWNGTMVISQW-UHFFFAOYSA-N 0.000 description 1
- IPLRZPREFHIGIB-UHFFFAOYSA-N 2,2-dinitropropan-1-ol Chemical compound OCC(C)([N+]([O-])=O)[N+]([O-])=O IPLRZPREFHIGIB-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 239000000006 Nitroglycerin Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DNBZRBSJOJZJKV-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(=O)C(C)=C.CCCCOC(=O)C=C DNBZRBSJOJZJKV-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FUHQFAMVYDIUKL-UHFFFAOYSA-N fox-7 Chemical compound NC(N)=C([N+]([O-])=O)[N+]([O-])=O FUHQFAMVYDIUKL-UHFFFAOYSA-N 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- GAGSAAHZRBTRGD-UHFFFAOYSA-N oxirane;oxolane Chemical compound C1CO1.C1CCOC1 GAGSAAHZRBTRGD-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/009—Wetting agents, hydrophobing agents, dehydrating agents, antistatic additives, viscosity improvers, antiagglomerating agents, grinding agents and other additives for working up
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/12—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being two or more oxygen-yielding compounds
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Combustion & Propulsion (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a fluorine-containing macromolecular bonding agent, a preparation method and application thereof, wherein the fluorine-containing macromolecular bonding agent has the structural formula:
Description
Technical Field
The invention relates to the technical field of solid propellants, in particular to a fluorine-containing macromolecular bonding agent, a preparation method and application thereof.
Background
The composite solid propellant generally adopts isocyanate as a curing agent, and the molding principle is that a polyurethane crosslinked network is formed by reacting an adhesive with terminal hydroxyl groups with the isocyanate curing agent. However, the isocyanate curing agent is easy to react with water to generate carbon dioxide gas, so that the propellant generates air holes and affects the process and mechanical properties, and the mechanical properties of the propellant produced under different environmental humidity have large fluctuation and affect the quality stability and reliability of the product.
Bonding agents are functional aids for improving the interfacial properties of a solid propellant binder matrix with energetic filler particles by forming a modulus transition layer on the surface of the filler particles to inhibit "dewetting" of the propellant. The bonding agent is mostly a small molecular polar compound, one end of the bonding agent is connected with an inorganic oxidant, and polymerization reaction is carried out on the surface of the bonding agent to form a high-modulus tearing-resistant layer; the other end is connected with the adhesive matrix into a whole through certain chemical reactions, so that the bonding of the interface layer is enhanced, and the mechanical property of the propellant is improved. In the prior art, most bonding agents are aziridine and derivatives thereof, alkanolamine and derivatives thereof, polyamine and derivatives thereof, organosilane, organic phthalate esters and the like, but macromolecular bonding agents with fluorine-containing structures are not applied to solid propellants.
Disclosure of Invention
The invention provides a fluorine-containing macromolecular bonding agent, a preparation method and application thereof, wherein the fluorine-containing macromolecular bonding agent solid propellant has the characteristics of high mechanical property in a wide temperature range, medium and high strength, high elongation and high modulus, meets the requirements of high filling, high interface reliability, adaptation to complex environments, has stable performance under wide-range change conditions and has long service life.
The specific technical scheme is as follows: a fluorine-containing macromolecular bonding agent has the following structural formula:
wherein x is 0.5-2.0; y is 0.2 to 1.0; z is 0.2 to 1.0; n is 1000-50000.
A method for preparing a fluorine-containing macromolecular bonding agent, comprising:
Adding acrylonitrile, 2-fluoroacrylate, hydroxy acrylate, initiator and polymerization inhibitor into acetone solvent, stirring to react, settling and washing the reaction system after the reaction is completed to obtain the fluorine-containing macromolecular bonding agent.
Preferably, the stirring reaction condition is 60-65 ℃ and the stirring time is 6-7 hours.
Preferably, the molar ratio of the acrylonitrile to the 2-fluoroacrylate to the hydroxy acrylate is 1.0:0.1-0.5:0.1-0.5.
Preferably, the initiator is azobisisobutyronitrile and the polymerization inhibitor is mercaptoethanol.
Preferably, the molar ratio of the acrylonitrile to the 2-fluoroacrylate to the hydroxy acrylate to the azodiisobutyronitrile to the mercaptoethanol is 1.0:0.1-0.5:0.1-0.5:0.01-0.10:0.01-0.10.
Use of a fluorine-containing macromolecular bonding agent in the preparation of a solid propellant comprising a fluorine-containing macromolecular bonding agent and a further component.
Preferably, the mass fraction of the fluorine-containing macromolecular bonding agent in the solid propellant is 0.02-5.0%.
Preferably, the other components include: azide binders, nitrate plasticizers, oxidants, explosives, fuels, curing agents and functional aids.
Preferably, the mass fractions of the other components are respectively: 8-15% of azide adhesive, 8-15% of nitrate plasticizer, 30-50% of oxidant, 5-15% of explosive, 17-20% of fuel, 0.5-1% of curing agent and 1-3% of functional auxiliary agent.
The beneficial effects of the invention are as follows:
The fluorine-containing macromolecular bonding agent provided by the invention is used for preparing the solid propellant, so that the fluorine-containing macromolecular bonding agent solid propellant has the characteristics of high mechanical property in a wide temperature range, medium and high strength, high elongation and high modulus, meets the requirements of high filling, high interface reliability, adaptation to complex environments, has stable performance under wide-range change conditions and has long service life. The fluorine-containing macromolecule bonding agent can be obtained by introducing fluorine-containing groups into acrylic ester, and because of high fluorine electronegativity, C-F bonds are quite stable, fluorine-containing side chains are oriented outwards, shielding protection can be formed for main chains and internal molecules, the original characteristics of acrylic ester are maintained by the modified acrylic ester, the surface tension of the bonding agent is effectively reduced, the surface wettability of the bonding agent to ammonium perchlorate and nitramine explosive is further improved, the bonding effect is enhanced, and the mechanical property of the propellant is improved. The fluorine-containing macromolecular bonding agent is used in the polyether propellant containing nitrate, and has the characteristics of low dosage and excellent mechanical property. The plasticizing ratio of the propellant adopting nitrate plasticizer, poly azide glycidyl ether (GAP), cyclotrimethylene trinitro amine (RDX) and cyclotetramethylene tetranitro amine (HMX) is between 0.8 and 1.8. Nitrate plasticizers such as N-butyl nitrooxyethyl nitrate (BuNENA) and 1,2, 4-butanetriol trinitrate (BTTN), triethylene glycol dinitrate (TEGDN), trimethylolethane trinitrate (TMETN) are used. N-butyl nitrooxyethyl nitramine (BuNENA) plasticizer is one of nitrooxyethyl nitramine energetic plasticizers, and has long N-butyl chain in a molecular structure to provide good molecular flexibility and low freezing point, and has energy groups such as nitramine (-N-NO 2) and nitrate (-O-NO 2) and the like to endow the energy groups with proper energetic characteristics.
Detailed Description
The following detailed description of embodiments of the application provides further details of the embodiments described, and it should be apparent that the embodiments described are merely some, rather than all, examples of the application. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
The terms first, second, and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments described herein may be implemented in other sequences than those described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements that are expressly listed or inherent to such process, method, article, or apparatus.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
Examples
The invention provides a fluorine-containing macromolecular bonding agent, a preparation method and application thereof, wherein the fluorine-containing macromolecular bonding agent is used for a solid propellant, and the fluorine-containing macromolecular bonding agent has the characteristics of high mechanical property in a wide temperature range, medium and high strength, high elongation and high modulus, meets the requirements of high filling, high interface reliability, adaptation to complex environments, has stable performance under wide-range change conditions and long service life.
The chemical modification mechanism of fluorine-containing monomer to acrylic ester is utilized to synthesize the emulsion of the dodecafluoroheptyl methacrylate-butyl acrylate-methyl methacrylate ternary polymerization system, the influence of different polymerization processes on the performance of the copolymerization emulsion is proved to have better performance than that of a pure acrylic ester polymer through the tests of mechanical property, surface property and the like. The fluorine-containing organic polymer material has higher thermal stability and mechanical strength compared with a polymer material without fluorine.
The raw materials and equipment used in the present invention are commercially available. The raw materials comprise: acrylonitrile, 2-fluoroacrylate, hydroxy acrylate, azobisisobutyronitrile (AIBN), mercaptoethanol, acetone and methanol.
The fluorine-containing macromolecular bonding agent provided by the invention has the structural formula:
wherein x is 0.5-2.0; y is 0.2 to 1.0; z is 0.2 to 1.0; n is 1000-50000.
The preparation method of the fluorine-containing macromolecular bonding agent comprises the following steps:
Adding acrylonitrile, 2-fluoroacrylate, hydroxy acrylate, mercaptoethanol and azodiisobutyronitrile with the molar ratio of 1.0:0.1-0.5:0.1-0.5:0.01-0.10:0.01-0.10 into an acetone solvent, stirring for reaction at 60-65 ℃ for 6-7 hours, pouring all components into methanol after the reaction, and sequentially settling and washing to obtain the fluorine-containing macromolecular bonding agent.
Wherein, acrylonitrile, 2-fluoroacrylate and hydroxy acrylate are used as monomers, azo-bis-isobutyronitrile (AIBN) is used as an initiator, mercaptoethanol is used as a polymerization inhibitor, and acetone is used as a solvent.
The specific preparation method of the fluorine-containing macromolecular bonding agent used in the following examples 1 to 6 comprises the following steps:
Adding acrylonitrile, 2-fluoroacrylate, hydroxy acrylate, mercaptoethanol and azodiisobutyronitrile with the molar ratio of 1:0.5:0.5:0.05:0.05 into 200ml of acetone solvent, stirring for reaction, wherein the stirring reaction condition is 60-65 ℃, the stirring time is 6-7 hours, after the reaction is finished, pouring all components into methanol, and sequentially settling and washing to obtain the fluorine-containing macromolecular bonding agent.
The invention provides an application of a fluorine-containing macromolecular bonding agent in a solid propellant, which comprises the following components in percentage by mass:
8% -15% of azide adhesive, preferably, the azide adhesive is poly-azide glycidyl ether (GAP) with the number average molecular weight of 2000-10000; 8% -15% of nitrate plasticizer, preferably, the nitrate plasticizer is one or more of N-butyl nitroxylethyl nitrate (BuNENA) and 1,2, 4-butanetriol trinitrate (BTTN), triethylene glycol dinitrate (TEGDN) and trimethylolethane trinitrate (TMETN); 30% -50% of oxidant, preferably Ammonium Perchlorate (AP) with the granularity between 3 mu and 360 mu; 5% -15% of explosive, preferably, the explosive is cyclotrimethylene trinitro amine (RDX), cyclotetramethylene tetranitro amine (HMX), 1-diamino 2, 2-dinitroethylene (FOX-7) and the like; 17% -20% of fuel, preferably aluminum powder (AL) with granularity of 1 mu-100 mu; 0.5 to 1 percent of curing agent, preferably, the curing agent is one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI) and modified hexamethylene polyisocyanate (N-100); 1 to 3 percent of functional auxiliary agent, preferably comprising a curing catalyst, a stabilizer, a combustion performance regulator and the like, and 0.02 to 5 percent of fluorine-containing macromolecular bonding agent.
For convenience of description, the substances and abbreviations are GAP: a polyglycidyl ether of a azide; PTPET: alkynyl-terminated ethylene oxide-tetrahydrofuran copolyethers; NG: nitroglycerin; BTTN:1,2, 4-butanetriol trinitrate; PTPEG: alkynyl polyethylene glycol; a3: a mixture of 2, 2-dinitropropanol formal and 2, 2-dinitropropanol acetal; HMX: cyclic tetramethylene tetranitramine; AP: ammonium perchlorate; AL: aluminum powder; BAG-F: the fluorine-containing macromolecular bonding agent solid propellant component and the performance are as follows.
Example 1
Table 1 shows the components of the first solid propellant in the prior art, and the fluorine-containing macromolecular bonding agent solid propellant provided by the invention is obtained by adding the fluorine-containing macromolecular bonding agent (BAG-F) provided by the invention into the solid propellant in the prior art, wherein the fluorine-containing macromolecular bonding agent accounts for 0.03% of the total mass of the solid propellant in the prior art.
TABLE 1
| Formulation composition | Content (% wt) |
| GAP+PTPET+NG+BTTN | 24 |
| HMX | 36 |
| AP | 18 |
| AL | 18 |
| Functional auxiliary agent | 4 |
Table 2 shows the mechanical properties of the fluorine-containing macromolecular bonding agent solid propellant billets, blank group one was the prior art solid propellant one, experimental group one was the fluorine-containing macromolecular bonding agent solid propellant one (experimental group one was blank group one with BAG-F added at 0.03% of the total mass).
TABLE 2
Example 2
Table 3 shows the components of a second solid propellant in the prior art, and the fluorine-containing macromolecular bonding agent solid propellant provided by the invention is obtained by adding the fluorine-containing macromolecular bonding agent (BAG-F) provided by the invention into the solid propellant in the prior art, wherein the fluorine-containing macromolecular bonding agent accounts for 0.03% of the total mass of the solid propellant in the prior art.
TABLE 3 Table 3
| Formulation composition | Content (% wt) |
| GAP+PTPEG+A3 | 24.5 |
| HMX | 27 |
| AP | 27 |
| AL | 18 |
| Functional auxiliary agent | 3.5 |
Table 4 shows the mechanical properties of the fluorine-containing macromolecular bonding agent solid propellant billets, blank group two was the prior art solid propellant, test group two was the fluorine-containing macromolecular bonding agent solid propellant (test group two was blank group two with BAG-F added at 0.03% of the total mass).
TABLE 4 Table 4
Example 3
Table 5 shows the components of the solid propellant three in the prior art, and the fluorine-containing macromolecular bonding agent solid propellant provided by the invention is obtained by adding the fluorine-containing macromolecular bonding agent (BAG-F) provided by the invention into the solid propellant in the prior art, wherein the fluorine-containing macromolecular bonding agent accounts for 0.03% of the total mass of the solid propellant in the prior art.
TABLE 5
Table 6 shows the mechanical properties of the fluorine-containing macromolecular bonding agent solid propellant billets, blank group three was the prior art solid propellant three, experimental group three was the fluorine-containing macromolecular bonding agent solid propellant three (experimental group three was blank group three plus BAG-F at 0.03% of the total mass).
TABLE 6
Example 4
Table 7 shows the components of a solid propellant in the prior art, and the fluorine-containing macromolecular bonding agent solid propellant provided by the invention is obtained by adding the fluorine-containing macromolecular bonding agent (BAG-F) provided by the invention into the solid propellant in the prior art, wherein the fluorine-containing macromolecular bonding agent accounts for 0.04% of the total mass of the solid propellant in the prior art.
TABLE 7
| Formulation composition | Content (% wt) |
| GAP+PTPET+NG+BTTN | 24 |
| RDX | 18 |
| AP | 36 |
| AL | 18 |
| Functional auxiliary agent | 4 |
Table 8 shows the mechanical properties of the fluorine-containing macromolecular bonding agent solid propellant billets, blank group four was the prior art solid propellant four, test group four was the fluorine-containing macromolecular bonding agent solid propellant four (test group four was blank group four with BAG-F added at 0.04% of the total mass).
TABLE 8
Example 5
Table 9 shows the components of the solid propellant five in the prior art, and the fluorine-containing macromolecular bonding agent solid propellant provided by the invention is obtained by adding the fluorine-containing macromolecular bonding agent (BAG-F) provided by the invention into the solid propellant in the prior art, wherein the fluorine-containing macromolecular bonding agent accounts for 0.05% of the total mass of the solid propellant in the prior art.
TABLE 9
| Formulation composition | Content (% wt) |
| GAP+PTPET+NG+BTTN | 22 |
| HMX | 20 |
| AP | 36 |
| AL | 18 |
| Functional auxiliary agent | 4 |
Table 10 shows the mechanical properties of the fluorine-containing macromolecular bonding agent solid propellant billets, blank group five was the prior art solid propellant five, experimental group five was the fluorine-containing macromolecular bonding agent solid propellant five (experimental group five was the blank group five with BAG-F added at 0.05% of the total mass).
Table 10
Example 6
Table 11 shows the composition of the solid propellant six in the prior art, and the fluorine-containing macromolecular bonding agent solid propellant provided by the invention is obtained by adding the fluorine-containing macromolecular bonding agent (BAG-F) provided by the invention into the solid propellant in the prior art, wherein the fluorine-containing macromolecular bonding agent accounts for 0.04% of the total mass of the solid propellant in the prior art.
TABLE 11
| Formulation composition | Content (% wt) |
| GAP+PTPET+NG+BTTN | 25 |
| HMX | 17 |
| AP | 34 |
| AL | 20 |
| Functional auxiliary agent | 4 |
Table 12 shows the mechanical properties of the fluorine-containing macromolecular bonding agent solid propellant billets, blank six as the prior art solid propellant six, test six as the fluorine-containing macromolecular bonding agent solid propellant six (test six as blank six plus BAG-F accounting for 0.04% of the total mass).
Table 12
According to the mechanical properties of the solid propellant billets of the fluorine-containing macromolecular bonding agents in the embodiments 1 to 6, the dosage of the fluorine-containing macromolecular bonding agent in the solid propellant is known, and the fluorine-containing macromolecular bonding agent provided by the invention has the characteristics of low dosage and excellent mechanical properties. After the fluorine-containing macromolecular bonding agent is added, the surface wettability of the bonding agent to ammonium perchlorate and nitrate explosive is improved, the bonding effect is enhanced, and the data show that the fluorine-containing macromolecular bonding agent solid propellant has excellent high-low temperature mechanical property and normal temperature mechanical property, and the tensile strength and the elongation are obviously improved.
The fluorine-containing macromolecular bonding agent maintains the original characteristics of the bonding agent, effectively reduces the surface tension of the bonding agent and improves the heat resistance of the bonding agent.
The fluorine-containing macromolecular bonding agent, the preparation method and the application thereof provided by the invention have the characteristics of high mechanical property in a wide temperature range, medium and high strength, high elongation and high modulus, meet the requirements of high filling, high interface reliability, adaptation to complex environments, stable performance under wide-range change conditions and long service life.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (10)
1. A fluorine-containing macromolecular bonding agent, which is characterized by having the following structural formula:
；
Wherein x is 0.5-2.0; y is 0.2-1.0; z is 0.2 to 1.0; n is 1000 to 50000.
2. A method of preparing the fluorine-containing macromolecular bonding agent according to claim 1, comprising:
Adding acrylonitrile, 2-fluoroacrylate, hydroxy acrylate, initiator and polymerization inhibitor into acetone solvent, stirring to react, settling and washing the reaction system after the reaction is completed to obtain the fluorine-containing macromolecular bonding agent.
3. The method for preparing a fluorine-containing macromolecular bonding agent according to claim 2, wherein the stirring reaction condition is 60-65 ℃ and the stirring time is 6-7 hours.
4. The method for preparing a fluorine-containing macromolecular bonding agent according to claim 2, wherein the molar ratio of acrylonitrile, 2-fluoroacrylate and hydroxy acrylate is 1.0:0.1-0.5:0.1-0.5.
5. The method for producing a fluorine-containing macromolecular bonding agent according to claim 2, wherein the initiator is azobisisobutyronitrile and the polymerization inhibitor is mercaptoethanol.
6. The method for preparing a fluorine-containing macromolecular bonding agent according to claim 5, wherein the molar ratio of acrylonitrile, 2-fluoroacrylate, hydroxy acrylate, azobisisobutyronitrile and mercaptoethanol is 1.0:0.1-0.5:0.1-0.5:0.01-0.10:0.01-0.10.
7. Use of a fluorine-containing macromolecular bonding agent according to claim 1 for the preparation of a solid propellant comprising a fluorine-containing macromolecular bonding agent and other components.
8. The use of the fluorine-containing macromolecular bonding agent according to claim 7 in the preparation of a solid propellant, wherein the mass fraction of the fluorine-containing macromolecular bonding agent in the solid propellant is 0.02-5.0%.
9. Use of a fluorine-containing macromolecular bonding agent according to claim 7 in the preparation of a solid propellant, wherein the further components comprise: an azide adhesive, a nitrate plasticizer, an oxidant, an explosive, a fuel, a curing agent and a functional auxiliary agent;
the functional auxiliary agent comprises: one or more of curing catalyst, stabilizer and combustion performance regulator.
10. Use of a fluorine-containing macromolecular bonding agent according to claim 9 for the preparation of a solid propellant, wherein the other components are in mass fractions of: 8-15% of an azide adhesive, 8-15% of a nitrate plasticizer, 30-50% of an oxidant, 5-15% of an explosive, 17-20% of a fuel, 0.5-1% of a curing agent and 1-3% of a functional auxiliary agent.
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