CN116903427B - Nitrate functionalized ionic liquid plasticizer and application thereof - Google Patents
Nitrate functionalized ionic liquid plasticizer and application thereof Download PDFInfo
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- CN116903427B CN116903427B CN202310815247.8A CN202310815247A CN116903427B CN 116903427 B CN116903427 B CN 116903427B CN 202310815247 A CN202310815247 A CN 202310815247A CN 116903427 B CN116903427 B CN 116903427B
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- triazole
- deionized water
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 40
- 239000004014 plasticizer Substances 0.000 title claims abstract description 31
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 27
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 22
- 239000004449 solid propellant Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 150000003852 triazoles Chemical class 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 43
- 229910021641 deionized water Inorganic materials 0.000 claims description 43
- -1 alcohol hydroxyl-substituted triazole bromine salt Chemical class 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 31
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 229920001971 elastomer Polymers 0.000 claims description 16
- 239000000806 elastomer Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- MWZDIEIXRBWPLG-UHFFFAOYSA-N 1-methyl-1,2,4-triazole Chemical compound CN1C=NC=N1 MWZDIEIXRBWPLG-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 5
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 1
- 239000003380 propellant Substances 0.000 abstract description 8
- 239000011230 binding agent Substances 0.000 abstract description 7
- 230000009477 glass transition Effects 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 42
- 239000007787 solid Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 150000007975 iminium salts Chemical class 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 7
- 238000004880 explosion Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- AGCQZYRSTIRJFM-UHFFFAOYSA-N triethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCOCCO[N+]([O-])=O AGCQZYRSTIRJFM-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005474 detonation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GCVXUERSYPSYQA-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl nitrate Chemical compound OCCOCCOCCO[N+]([O-])=O GCVXUERSYPSYQA-UHFFFAOYSA-N 0.000 description 1
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 description 1
- WJVQJXVMLRGNGA-UHFFFAOYSA-N 5-bromopentan-1-ol Chemical compound OCCCCCBr WJVQJXVMLRGNGA-UHFFFAOYSA-N 0.000 description 1
- FCMCSZXRVWDVAW-UHFFFAOYSA-N 6-bromo-1-hexanol Chemical compound OCCCCCCBr FCMCSZXRVWDVAW-UHFFFAOYSA-N 0.000 description 1
- KVMAXYBHCWBBTP-UHFFFAOYSA-N 6-bromodecan-1-ol Chemical compound CCCCC(Br)CCCCCO KVMAXYBHCWBBTP-UHFFFAOYSA-N 0.000 description 1
- MMXRRNUXCHUHOE-UHFFFAOYSA-N 7-bromoheptan-1-ol Chemical compound OCCCCCCCBr MMXRRNUXCHUHOE-UHFFFAOYSA-N 0.000 description 1
- GMXIEASXPUEOTG-UHFFFAOYSA-N 8-bromooctan-1-ol Chemical compound OCCCCCCCCBr GMXIEASXPUEOTG-UHFFFAOYSA-N 0.000 description 1
- USJDOLXCPFASNV-UHFFFAOYSA-N 9-bromononan-1-ol Chemical compound OCCCCCCCCCBr USJDOLXCPFASNV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of functional materials, and particularly relates to an ionic liquid energetic plasticizer for a solid propellant and application thereof. The plasticizer is nitrate functionalized energetic ionic liquid plasticizer, and the energy and the compatibility with a binder system are improved by introducing nitrate functionalized groups on triazole nitrogen-rich cations; the mechanical properties of the propellant are effectively solved by utilizing the low melting point, low viscosity and rich intermolecular force of the ionic liquid. The invention has the beneficial effects that: (1) The nitrate ionic liquid has the characteristics of low melting point and good thermal stability, and is a liquid energetic material with excellent performance; (2) The preparation method of the nitrate ionic liquid has the characteristics of convenient operation and easy purification; (3) After being used as plasticizer for plasticizing HTPB and GAP, the nitrate ionic liquid has the characteristics of low glass transition temperature, good mechanical property and good thermal stability.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to an ionic liquid energetic plasticizer for a solid propellant and application thereof.
Background
The solid propellant is a composite material with various energy-containing components (metal fuel, oxidant, etc.) wrapped by adhesive, and is a power source of missile and space vehicle, and is a main component of solid rocket power device. The energy of the solid propellant is an important index for determining the carrying capacity of equipment, the energy of the propellant is continuously improved on the basis of ensuring the mechanical property and the thermo-mechanical property, and the development of the high-energy insensitive propellant is the development direction of the current solid propellant. In the solid propellant component, the adhesive is a system which reacts with the curing agent under specific temperature conditions to generate an elastomer and plays a role in bonding, and the adhesive accounts for about 10-15 percent, and the performance of the adhesive greatly influences the energy and mechanical properties of the solid propellant. Hydroxyl-terminated polybutadiene (HTPB) is the most commonly used binder system for solid propellants, and when the solids content in the binder system increases, the mechanical properties of the solid propellant decrease, which affects the performance properties of the solid propellant.
The plasticizer is an auxiliary agent material added for improving the plasticity of the composite solid propellant and reducing the glass transition temperature. At present, the plasticizer materials commonly used in solid propellants mainly include dioctyl adipate (DOA), dioctyl sebacate (DOS), dioctyl phthalate (DOP), dibutyl Phthalate (DPB) and the like. The plasticizers have better compatibility with the binder system, so that the process performance and mechanical performance of the propellant can be effectively improved, but the addition of the inert plasticizers can greatly lose the energy of the solid propellant. To address this problem, an increasing number of energetic plasticizers are being used in propellants in place of traditional conventional plasticizers. Common energetic plasticizers mainly comprise azide, nitro, nitrate and ammonium nitrate functionalized energetic plasticizers, but the energetic plasticizers have poor compatibility with binder systems, so that low-temperature performance and mechanical performance are reduced, and development of novel energetic plasticizers for binder systems for solid propellants is urgently needed, so that the sensitivity of the solid propellants is reduced and the energy is kept unchanged.
Disclosure of Invention
In order to solve the technical problems, the invention provides a nitrate functionalized energetic ionic liquid plasticizer. The mechanical properties of the propellant are effectively solved by utilizing the low melting point, low viscosity and rich intermolecular force of the ionic liquid. Meanwhile, the energy and the compatibility with a binder system are improved by introducing nitrate functional groups on triazole nitrogen-rich cations. The specific research scheme is as follows:
an energetic plasticizer for nitrate functionalized ionic liquid, which has the following structural general formula:
wherein n is more than or equal to 3.
The synthetic route of the ionic liquid is as follows:
The method comprises the steps of reacting 1-methyl-1, 2, 4-triazole with bromohydrin to generate alcohol hydroxyl substituted triazole bromate, then carrying out ion exchange on the alcohol hydroxyl substituted triazole bromate and LiNTf 2 to obtain alcohol hydroxyl substituted NTf 2 salt, and finally further nitrifying alcohol hydroxyl to obtain nitric acid functionalized ionic liquid. The preparation process comprises the following steps:
(1) Adding 1-methyl-1, 2, 4-triazole and bromohydrin with different chain lengths into a single-neck flask at the temperature of 70 ℃ according to the ratio of 1:1.2, stirring, reacting for 8-10 hours to obtain white solid, washing with anhydrous diethyl ether, filtering, and drying in vacuum to obtain triazole bromate substituted by alcoholic hydroxyl groups;
(2) Dissolving the alcohol hydroxyl-substituted triazole bromine salt obtained in the step (1) in a proper amount of deionized water, weighing LiNTf 2, dissolving in a proper amount of deionized water, mixing and stirring the solution and the solution, immediately layering, continuously stirring for 12 hours, separating a lower product, and washing with the deionized water to obtain alcohol hydroxyl-substituted triazole NTf 2 salt;
(3) Adding acetic anhydride into a three-mouth bottle provided with a low-temperature reflux cooling device, dropping fuming nitric acid after dropping to-10-0 ℃, stirring until the system temperature is stabilized at-10-0 ℃, and slowly adding the alcohol hydroxyl substituted triazole NTf 2 salt prepared in the step (2); and after the material is added, the temperature is controlled at 0-5 ℃ to continue to react for 3-12 h, after the reaction is finished, the reaction solution is poured into an ice-water mixture, and is kept stand for 1-3 h, and ethyl acetate is used for extraction, washing, drying and rotary evaporation to remove the ethyl acetate, thus obtaining nitrate functionalized triazole NTf 2 salt.
Further:
Repeatedly washing the triazole bromine salt substituted by the alcoholic hydroxyl group obtained in the step (1) by using anhydrous diethyl ether, and drying to obtain a pure product;
the molar ratio of the 1-methyl-1, 2, 4-triazole to the bromohydrin in the step (1) is controlled to be 1-1.5:1;
the purification of the step (2) adopts deionized water for repeated washing, liquid separation and rotary evaporation until no precipitate exists in the product;
The ratio of the anhydride to fuming nitric acid in the step (3) is 1-5:1; the ratio of fuming nitric acid to raw materials is 2-10:1.
The invention also provides an application method of the ionic liquid plasticizer, which is specifically applied to the HTPB and GAP solid propellant formulas, and the preparation process is consistent with that of the conventional propellant.
The ionic liquid can also be directly applied to the preparation of adhesive elastomers for propellants, and the adhesive elastomers are specifically as follows:
The preparation method of the HTPB elastomer comprises the steps of weighing and uniformly mixing ionic liquid plasticizer and HTPB prepolymer in a formula amount, removing bubbles in vacuum at 40 ℃, then adding TDI curing agent, uniformly stirring and removing bubbles in vacuum, then transferring the mixture into a preheated polytetrafluoroethylene mold, pumping bubbles at 45 ℃ until no bubbles are ejected, adjusting the temperature to 60 ℃, curing for 5-15 days, and demolding to obtain the HTPB elastomer.
Further, the process for preparing the HTPB elastomer is equally applicable to GAP-based elastomers.
The invention has the beneficial effects that: (1) The nitrate ionic liquid has the characteristics of low melting point and good thermal stability, and is a liquid energetic material with excellent performance; (2) The preparation method of the nitrate ionic liquid has the characteristics of convenient operation and easy purification; (3) The nitrate ionic liquid is used as a plasticizer for plasticizing HTPB, the glass transition temperature is at least-62.95 ℃, the thermal decomposition temperature is 466 ℃, the elongation at break is 623%, compared with a polyurethane material plasticized by DOA, the mechanical property and the thermal stability are greatly improved, and the energy of the nitrate functionalized ionic liquid is far greater than that of DOA.
Detailed Description
The invention will now be described with reference to specific examples, which are intended to be illustrative of the invention and are not intended to limit the scope of the invention.
The embodiment provides 8 nitrate functionalized ionic liquids, and the specific structure and the synthetic route are as follows:
Example 1
This example provides the synthesis of 1- (N-nitrooxypropyl) -3-methyl-1, 2, 4-triazolbis (trifluoromethylsulfonyl) iminium salt (3 a):
(1) 1-methyl-1, 2, 4-triazole (2.47 g,0.03 mol) and 3-bromo-1-propanol (3.45 g,0.025 mol) were reacted at 70 ℃. After 8h, the mixture is sticky and is white solid after 10h, absolute ethyl ether is added to wash the white solid, the product is obtained by filtering, and the product 1-methyl-4-n-propanol-1, 2, 4-triazole bromine salt (1 a) is obtained by vacuum drying for 2-3 h at 40 DEG C
(2) 1-Methyl-4-n-propanolato-1, 2, 4-triazole bromide (5.10 g,0.023 mol) was dissolved in 10mL of deionized water, NTf 2 Li (8.27 g,0.029 mol) was weighed into 10mL of deionized water, and the two solutions were mixed and stirred for 12h. After the reaction, the reaction mixture was washed with deionized water to remove water, thereby obtaining 1-methyl-4-n-propanolato-1, 2, 4-triazole bromide bis (trifluoromethylsulfonyl) imide salt (2 a).
(3) Acetic anhydride (38.60 g,0.33 mol) is added into a three-neck flask, fuming nitric acid (7.48 g,0.12 mol) is slowly added dropwise at the temperature of 0-5 ℃, the temperature is reduced to-10 ℃ after the dropwise addition, and prepared 2a (9.69 g,0.023 mol) is slowly added; after the dripping is finished, controlling the temperature to be 0-5 ℃ for reaction for 12 hours, and then reacting for 2-3 hours at room temperature; after the reaction is finished, pouring the mixed solution into an ice-water mixture, standing for 1h, extracting for 2-3 times by using ethyl acetate, repeatedly washing for 1-2 times by using deionized water, saturated sodium carbonate solution and deionized water in sequence, drying, and removing the ethyl acetate by rotary evaporation to obtain 8.42g of yellow liquid with the yield of 78.5%.
The nuclear magnetic data of the obtained product are as follows:
1H NMR(600MHz,DMSO)δ＝10.09(s,1H),9.20(s,1H),4.60(t,2H),4.37(t,2H),4.11-4.01(m,3H),2.34-2.26ppm(m,2H).13C NMR(151MHz,DMSO)δ＝145.0,143.5,123.1,121.0,118.8,116.7,70.75,44.8,38.9,26.8ppm.
Example 2
This example provides the synthesis of 1- (N-nitroxypentyl) -3-methyl-1, 2, 4-triazolbis (trifluoromethylsulfonyl) iminium salt (3 c):
(1) 1-methyl-1, 2, 4-triazole (9.97 g,0.12 mol) and 5-bromo-1-pentanol (16.70 g,0.10 mol) were reacted at 70 ℃. After 8h, the mixture is sticky and is white solid after 10h, absolute ethyl ether is added to wash the white solid, the product is obtained by filtering, and the product is obtained by vacuum drying for 2-3 h at 40 ℃ to obtain the product 1-methyl-4-n-amyl alcohol-1, 2, 4-triazole bromine salt (1 c)
(2) 1-Methyl-4-n-pentanoyl-1, 2, 4-triazole bromide (20.62 g,0.080 mol) was dissolved in 10mL of deionized water, NTf 2 Li (28.40 g,0.098 mol) was weighed into 10mL of deionized water, and mixed and stirred for 12h. After the reaction, the reaction mixture was washed with deionized water to remove water, thereby obtaining 1-methyl-4-n-pentanoyl-1, 2, 4-triazole bromide bis (trifluoromethylsulfonyl) imide salt (2 c).
(3) Acetic anhydride (36.44 g,0.33 mol) is added into a three-neck flask, fuming nitric acid (7.02 g,0.12 mol) is slowly added dropwise at the temperature of 0-5 ℃, the temperature is reduced to-10 ℃ after the dropwise addition, and prepared 2c (9.88 g,0.022 mol) is slowly added; after the dripping is finished, controlling the temperature to be 0-5 ℃ for reaction for 12 hours, and then reacting for 2-3 hours at room temperature; after the reaction is finished, pouring the mixed solution into an ice-water mixture, standing for 1h, extracting for 2-3 times by using ethyl acetate, repeatedly washing for 1-2 times by using deionized water, saturated sodium carbonate solution and deionized water in sequence, drying, and removing the ethyl acetate by rotary evaporation to obtain 8.26g of yellow liquid with the yield of 75%.
The nuclear magnetic data of the obtained product are as follows:
1H NMR(600MHz,DMSO)δ＝10.07(s,1H),9.17(d,1H),4.52(t,2H),4.28-4.25(m,2H),4.07(d,3H),1.88(dd,2H),1.79-1.64(m,2H),1.46-1.33ppm(m,2H).13C NMR(151MHz,DMSO)δ＝144.8,143.2,123.1,121.0,118.8,116.7,73.7,47.5,39.0,28.7,25.7,22.4,22.0ppm.
Example 3
This example provides the synthesis of 1- (N-nitrooxyhexyl) -3-methyl-1, 2, 4-triazolbis (trifluoromethylsulfonyl) iminium salt (3 d):
(1) 1-methyl-1, 2, 4-triazole (7.48 g,0.090 mol) and 6-bromo-1-hexanol (13.58 g,0.075 mol) were reacted at 70 ℃. After 8h, the mixture is sticky and is white solid after 10h, absolute ethyl ether is added to wash the white solid, the product is obtained by filtering, and the product 1-methyl-4-n-hexanol-1, 2, 4-triazole bromine salt (1 d) is obtained by vacuum drying for 2-3 h at 40 DEG C
(2) 1-Methyl-4-n-hexanol-1, 2, 4-triazole bromide (20.78 g,0.078 mol) was dissolved in 10mL of deionized water, NTf 2 Li (24.84 g,0.086 mol) was weighed into 10mL of deionized water, and the two solutions were mixed and stirred for 12h. After the reaction, the reaction mixture was washed with deionized water to remove water, thereby obtaining 1-methyl-4-n-hexanol-1, 2, 4-triazole bromide bis (trifluoromethylsulfonyl) imide salt (2 d).
(3) Acetic anhydride (30.6 g,0.30 mol) is added into a three-neck flask, fuming nitric acid (6.3 g,0.10 mol) is slowly added dropwise at the temperature of 0-5 ℃, the temperature is reduced to-10 ℃ after the dropwise addition, and the prepared 2d (4.63 g, 0.010mol) is slowly added; after the dripping is finished, controlling the temperature to be 0-5 ℃ for reaction for 12 hours, and then reacting for 2-3 hours at room temperature; after the reaction is finished, pouring the mixed solution into an ice-water mixture, standing for 1h, extracting for 2-3 times by using ethyl acetate, repeatedly washing for 1-2 times by using deionized water, saturated sodium carbonate solution and deionized water in sequence, drying, and removing the ethyl acetate by rotary evaporation to obtain 3.83g of yellow liquid with the yield of 75%.
The nuclear magnetic data of the obtained product are as follows:
1H NMR(600MHz,DMSO)δ＝10.06(s,1H),9.19(s,1H),4.52(t,2H),4.24(t,2H),4.06(s,3H),1.88-1.80(m,2H),1.72-1.63(m,2H),1.42-1.30ppm(m,4H).13C NMR(151MHz,DMSO)δ＝144.9,143.2,123.1,121.0,118.8,116.7,74.1,47.7,39.0,29.1,26.2,25.3,24.8ppm.
Example 4
This example provides the synthesis of 1- (N-nitroxoheptyl) -3-methyl-1, 2, 4-triazolbis (trifluoromethylsulfonyl) iminium salt (3 e):
(1) 1-methyl-1, 2, 4-triazole (7.47 g,0.090 mol) and 7-bromo-1-heptanol (14.78 g,0.075 mol) were reacted at 70 ℃. After 8h, the mixture is sticky and is white solid after 10h, absolute ethyl ether is added to wash the white solid, the product is obtained by filtering, and the product is obtained by vacuum drying for 2-3 h at 40 ℃ to obtain the product 1-methyl-4-n-heptanol-1, 2, 4-triazole bromine salt (1 e)
(2) 1-Methyl-4-n-heptanol-1, 2, 4-triazole bromine salt (10.01 g,0.036 mol) was dissolved in 10mL of deionized water, li NTf 2 (12.39 g,0.043 mol) was weighed and dissolved in 10mL of deionized water, and the mixture was stirred for 12 hours to effect a sufficient reaction. After the reaction, the reaction mixture was washed with deionized water to remove water, thereby obtaining 1-methyl-4-n-heptanol-1, 2, 4-triazole bromide bis (trifluoromethylsulfonyl) imide salt (2 e).
(3) Acetic anhydride (50.40 g,0.42 mol) is added into a three-neck flask, fuming nitric acid (8.96 g,0.77 mol) is slowly added dropwise at the temperature of 0-5 ℃, the temperature is reduced to-10 ℃ after the dropwise addition, and prepared 2e (10.50 g,0.22 mol) is slowly added; after the dripping is finished, controlling the temperature to be 0-5 ℃ for reaction for 12 hours, and then reacting for 2-3 hours at room temperature; after the reaction is finished, pouring the mixed solution into an ice-water mixture, standing for 1h, extracting for 2-3 times by using ethyl acetate, repeatedly washing for 1-2 times by using deionized water, saturated sodium carbonate solution and deionized water in sequence, drying, and removing the ethyl acetate by rotary evaporation to obtain 9.22g of yellow liquid with the yield of 80%.
The nuclear magnetic data of the obtained product are as follows:
1H NMR(600MHz,DMSO)δ＝10.06(s,1H),9.19(s,1H),4.51(t,2H),4.28-4.18(m,2H),4.06(s,3H),1.88-1.78(m,2H),1.71-1.62(m,2H),1.39-1.28ppm(m,6H).13C NMR(151MHz,DMSO)δ＝144.9,143.2,123.5,121.0,118.8,116.7,74.2,47.8,39.1,29.2,28.2,26.5,25.2ppm.
Example 5
This example provides the synthesis of 1- (N-nitroxyl) -3-methyl-1, 2, 4-triazolbis (trifluoromethylsulfonyl) iminium salt (3 f):
(1) 1-methyl-1, 2, 4-triazole (8.68 g,0.10 mol) and 8-bromo-1-octanol (18.00 g,0.086 mol) were reacted at 70 ℃. After 8h, the mixture is sticky and is white solid after 10h, absolute ethyl ether is added to wash the white solid, the product is obtained by filtering, and the product 1-methyl-4-n-octanol-1, 2, 4-triazole bromine salt (1 f) is obtained by vacuum drying for 2-3 h at 40 DEG C
(2) 1-Methyl-4-n-octanol-1, 2, 4-triazole bromide (17.59 g,0.060 mol) was dissolved in 10mL of deionized water, li NTf 2 (20.67 g,0.072 mol) was weighed and dissolved in 10mL of deionized water, and the mixture was stirred for 12 hours to effect a sufficient reaction. After the reaction, the reaction mixture was washed with deionized water to remove water, thereby obtaining 1-methyl-4-n-octanol-1, 2, 4-triazole bromide bis (trifluoromethylsulfonyl) imide salt (2 f).
(3) Acetic anhydride (32.07 g,0.30 mol) was added to the three-necked flask, fuming nitric acid (6.17 g,0.098 mol) was slowly added dropwise at 0-5 ℃, the temperature was lowered to-10 ℃ after the addition was completed, and prepared 2f (7.00 g,0.014 mol) was slowly added; after the dripping is finished, controlling the temperature to be 0-5 ℃ for reaction for 12 hours, and then reacting for 2-3 hours at room temperature; after the reaction is finished, pouring the mixed solution into an ice-water mixture, standing for 1h, extracting for 2-3 times by using ethyl acetate, repeatedly washing for 1-2 times by using deionized water, saturated sodium carbonate solution and deionized water, drying, and removing the ethyl acetate by rotary evaporation to obtain yellow liquid of 5.83g with the yield of 77%.
The nuclear magnetic data of the obtained product are as follows:
1H NMR(600MHz,DMSO)δ＝10.07(s,1H),9.19(s,1H),4.51(t,2H),4.24(t,2H),4.08(d,3H),1.84(dd,2H),1.70-1.62(m,2H),1.37-1.27ppm(m,8H).13CNMR(151MHz,DMSO)δ＝144.9,143.2,123.1,121.0,118.8,116.7,74.2,47.8,39.0,29.3,28.6,26.4,25.7,25.4ppm.
Example 6
This example provides the synthesis of 1- (N-nitrooxynonyl) -3-methyl-1, 2, 4-triazolbis (trifluoromethylsulfonyl) iminium salt (3 g):
(1) 1-methyl-1, 2, 4-triazole (8.92 g,0.11 mol) and 9-bromo-1-nonanol (20.00 g,0.089 mol) were reacted at 70 ℃. After 8h, the mixture is sticky and is white solid after 10h, absolute ethyl ether is added to wash the white solid, the product is obtained by filtering, and the product 1-methyl-4-n-nonanol-1, 2, 4-triazole bromine salt (1 g) is obtained by vacuum drying for 2-3 h at 40 DEG C
(2) 1-Methyl-4-n-nonanol-1, 2, 4-triazole bromide (23.28 g,0.076 mol) was dissolved in 10mL of deionized water, NTf 2 Li (26.18 g,0.091 mol) was weighed and dissolved in 10mL of deionized water, and the mixture was stirred for 12 hours to effect a sufficient reaction. After the completion of the reaction, the reaction mixture was washed with deionized water to remove water, whereby 1-methyl-4-n-nonanol-1, 2, 4-triazole bromide bis (trifluoromethylsulfonyl) imide salt (2 g) was obtained.
(3) Acetic anhydride (15.31 g,0.15 mol) is added into a three-neck flask, fuming nitric acid (3.15 g,0.050 mol) is slowly added dropwise at the temperature of 0-5 ℃, the temperature is reduced to-10 ℃ after the dropwise addition, and 2g (5.64 g,0.01 mol) of prepared solution is slowly added; after the dripping is finished, controlling the temperature to be 0-5 ℃ for reaction for 12 hours, and then reacting for 2-3 hours at room temperature; after the reaction is finished, pouring the mixed solution into an ice-water mixture, standing for 1h, extracting for 2-3 times by using ethyl acetate, repeatedly washing for 1-2 times by using deionized water, saturated sodium carbonate solution and deionized water, drying, and removing the ethyl acetate by rotary evaporation to obtain yellow liquid 5.08g with the yield of 83%.
The nuclear magnetic data of the obtained product are as follows:
1H NMR(600MHz,DMSO)δ＝10.06(s,1H),9.19(s,1H),4.51(t,2H),4.24(t,2H),4.06(s,3H),1.83(dd,2H),1.69-1.59(m,2H),1.35-1.24ppm(m,10H).13CNMR(151MHz,DMSO)δ＝144.9,143.2,143.2,123.1,121.0,118.8,116.7,74.2,47.8,39.0,29.3,28.9,28.7,26.4,25.8,25.4ppm.
Example 7
This example provides the synthesis of 1- (N-nitrooxydecyl) -3-methyl-1, 2, 4-triazolbis (trifluoromethylsulfonyl) iminium salt (3 h):
(1) 1-methyl-1, 2, 4-triazole (19.13 g,0.076 mol) and 6-bromo-1-decanol (15.00 g,0.062 mol) were reacted at 70 ℃. After 8h, the mixture is sticky and is white solid after 10h, absolute ethyl ether is added to wash the white solid, the product is obtained by filtering, and the product 1-methyl-4-n-decyl alcohol-1, 2, 4-triazole bromine salt (1 h) is obtained by vacuum drying for 2-3 h at 40 DEG C
(2) 1-Methyl-4-n-decyl-1, 2, 4-triazole bromide (17.03 g,0.053 mol) was dissolved in 10mL of deionized water, NTf 2 Li (4.92 g,0.058 mol) was weighed and dissolved in 10mL of deionized water, and the mixture was stirred for 12 hours to effect a sufficient reaction. After the reaction was completed, the reaction mixture was washed with deionized water and water was removed to give 1-methyl-4-n-decanol-1, 2, 4-triazole bromide bis (trifluoromethylsulfonyl) imide salt (2 h).
(3) Acetic anhydride (29.78 g,0.27 mol) was added to the three-necked flask, fuming nitric acid (5.73 g,0.091 mol) was slowly added dropwise at 0-5 ℃, the temperature was lowered to-10 ℃ after the dropwise addition, and the prepared 2h (7.00 g,0.013 mol) was slowly added; after the dripping is finished, controlling the temperature to be 0-5 ℃ for reaction for 12 hours, and then reacting for 2-3 hours at room temperature; after the reaction is finished, pouring the mixed solution into an ice-water mixture, standing for 1h, extracting for 2-3 times by using ethyl acetate, repeatedly washing for 1-2 times by using deionized water, saturated sodium carbonate solution and deionized water, drying, and removing the ethyl acetate by rotary evaporation to obtain 6.57g of yellow liquid with the yield of 89%.
The nuclear magnetic data of the obtained product are as follows:
1H NMR(600MHz,DMSO)δ＝10.06(s,1H),9.19(s,1H),4.50(t,2H),4.24(t,2H),4.07(d,3H),1.83(dd,2H),1.69-1.61(m,2H),1.34-1.23ppm(m,12H).13CNMR(151MHz,DMSO)δ＝144.9,143.2,123.1,121.0,118.8,116.7,74.28,61.1,47.8,39.0,29.3,29.1,28.9,28.7,26.4,25.8,25.5ppm.
Example 8
This example provides an HTPB elastomer.
The preparation method comprises the steps of weighing ionic liquid plasticizer (1.15 g) and HTPB prepolymer (10 g) according to the formula amount, uniformly mixing, removing bubbles in vacuum at 40 ℃, adding TDI curing agent (0.804 g), uniformly stirring, removing bubbles in vacuum, transferring the mixture into a preheated polytetrafluoroethylene mold, vacuumizing at 45 ℃ to remove bubbles until no bubbles are ejected, adjusting the temperature to 60 ℃, curing for 5-15 days, and demolding to obtain the HTPB elastomer.
Comparative example 1;
TABLE 1 thermo-mechanical Properties of HTPB elastomer
Note that: [a] A loss factor; [b] Glass transition temperature; [c] Storage modulus; [d] Crosslink density; [e] Decomposition temperature; [f] Tensile strength; [g] Elongation at break
And weighing and uniformly mixing DOA plasticizer and HTPB prepolymer in a formula amount, removing bubbles in vacuum at 40 ℃, adding TDI curing agent, stirring uniformly, removing bubbles in vacuum, transferring the mixture to a preheated polytetrafluoroethylene mold, vacuumizing at 45 ℃ to remove bubbles until no bubbles are ejected, adjusting the temperature to 60 ℃, curing for 5-15 days, and demolding to obtain the HTPB elastomer.
The elastomeric materials were subjected to performance testing and the results are shown in table 1, where the glass transition temperature of the ionic liquid plasticized material was comparable to the glass transition temperature of the DOA plasticized material, but the ionic liquid plasticized HTPB elastomer had a greater elongation at break than the DOA plasticized HTPB elastomer, and also had a higher thermal stability than the DOA plasticized HTPB elastomer.
Comparative example 2:
TABLE 2 physicochemical Properties of nitrate functionalized ionic liquids
Note that: [a] melting point; [b] A onset decomposition temperature; [c] peak temperature; [d] density; [e] Viscosity of the product
As shown in Table 2, the physicochemical properties of the ionic liquid and the dicarboxylic triethylene glycol nitrate TEGDN were measured, and the result shows that the melting point of the ionic liquid is far less than TEGDN, the thermal decomposition temperature at the highest decomposition rate is about 100 ℃ higher than TEGDN, and the density is also more than TEGDN (1.34 g.cm 3, 25 ℃). The energy calculation results are shown in Table 3, and the detonation velocity and detonation pressure are slightly greater than TEGDN. The calculation method used in table 3 is as follows:
according to the density functional theory, the B3LYP/def-TZVP method is combined with the atomic structure configuration of Gaussian09 software, and the ORCA software is used for calculating single-point energy, wherein the calculation method is PWPB/def 2-QZVPP. Correction was performed by DFT-D3, enthalpy was calculated by Multiwfn software, and enthalpy of formation was calculated by the Bern-Haber energy cycle method. The anion/cation of the ionic liquid is respectively disassembled into a small molecular structure through an isobond reaction, then the formation enthalpy of the small molecules is calculated through an atomization energy method, and the energy of a single gas phase atom is calculated through a G4MP2 method and Gaussian09 software. And calculating the explosion temperature, explosion pressure and explosion speed by utilizing Explo software. The calculation process requires knowledge of the enthalpy of formation of the substance and the density of the substance, the molecular formula of the substance, and the molecular weight.
TABLE 3 enthalpy of formation and explosion parameters for nitrate ionic liquids
Note that: [a] enthalpy of cation formation; [b] enthalpy of anion formation; [c] enthalpy of ionic liquid formation; [d] lattice energy; [e] explosion heat; [f] explosion temperature; [g] detonation pressure; [h] explosion velocity; [i] oxygen balance
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The nitrate functionalized ionic liquid plasticizer is characterized by having the following structural general formula:
Wherein n is more than or equal to 3;
the synthetic route of the ionic liquid is as follows:
The preparation process comprises the following steps:
(1) Adding 1-methyl-1, 2, 4-triazole and bromohydrin with different chain lengths into a single-neck flask at the temperature of 70 ℃ according to the ratio of 1:1.2, stirring, reacting for 8-10h, washing with anhydrous diethyl ether, filtering, and vacuum drying to obtain triazole bromate substituted by alcoholic hydroxyl;
(2) Dissolving the alcohol hydroxyl-substituted triazole bromine salt obtained in the step (1) in a proper amount of deionized water, weighing LiNTf 2, dissolving in a proper amount of deionized water, mixing the two, stirring and reacting for 12 hours, separating a lower product, and washing with the deionized water to obtain the alcohol hydroxyl-substituted triazole NTf 2 salt;
(3) Adding acetic anhydride into a three-mouth bottle provided with a low-temperature reflux cooling device, dropping fuming nitric acid after dropping to-10-0 ℃, stirring until the system temperature is stabilized at-10-0 ℃, and slowly adding the alcohol hydroxyl substituted triazole NTf 2 salt prepared in the step (2); and after the material is added, the temperature is controlled at 0-5 ℃ to continue to react for 3-12 h, after the reaction is finished, the reaction solution is poured into an ice-water mixture, and is kept stand for 1-3 h, and ethyl acetate is used for extraction, washing, drying and rotary evaporation to remove the ethyl acetate, thus obtaining nitrate functionalized triazole NTf 2 salt.
2. The nitrate functionalized ionic liquid plasticizer according to claim 1, wherein the alcohol hydroxyl substituted triazole bromine salt obtained in the step (1) is repeatedly washed by anhydrous diethyl ether, and dried to obtain a pure product.
3. The nitrate functionalized ionic liquid plasticizer according to claim 1, wherein the molar ratio of 1-methyl-1, 2, 4-triazole to bromohydrin in step (1) is controlled between 1:1 and 1.5.
4. The nitrate functionalized ionic liquid plasticizer according to claim 1, wherein the lower product of step (2) is repeatedly washed with deionized water, separated into liquid, and spin-steamed until there is no precipitate in the product.
5. The nitrate functionalized ionic liquid plasticizer according to claim 1, wherein the mass ratio of acetic anhydride to fuming nitric acid in the step (3) is 1-5:1; the mass ratio of fuming nitric acid to the alcohol hydroxyl substituted triazole NTf 2 salt is 2-10:1.
6. The method of using a nitrate functionalized ionic liquid plasticizer according to any of claims 1 to 5, wherein the nitrate functionalized ionic liquid plasticizer is applied to HTPB, GAP type solid propellant formulations.
7. A preparation method of an HTPB elastomer, which comprises the steps of weighing and uniformly mixing a nitrate functionalized ionic liquid plasticizer and an HTPB prepolymer in a formula amount according to any one of claims 1-5, removing bubbles in vacuum at 40 ℃, then adding a TDI curing agent, uniformly stirring and removing bubbles in vacuum, transferring the mixture into a preheated polytetrafluoroethylene mold, removing bubbles in vacuum, adjusting the temperature to 60 ℃, curing for 5-15 days, and demolding to obtain the HTPB elastomer.
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