CN117164415A - Boric acid ester type fluorine-containing combustion promoter and preparation method and application thereof - Google Patents
Boric acid ester type fluorine-containing combustion promoter and preparation method and application thereof Download PDFInfo
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- CN117164415A CN117164415A CN202310916784.1A CN202310916784A CN117164415A CN 117164415 A CN117164415 A CN 117164415A CN 202310916784 A CN202310916784 A CN 202310916784A CN 117164415 A CN117164415 A CN 117164415A
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- borate
- fluorine
- combustion promoter
- boric acid
- containing combustion
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 89
- 239000011737 fluorine Substances 0.000 title claims abstract description 89
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 73
- 239000004327 boric acid Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 Boric acid ester Chemical class 0.000 title claims description 22
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003380 propellant Substances 0.000 claims abstract description 48
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000004821 distillation Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 13
- 150000002191 fatty alcohols Chemical class 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-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
- 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 8
- 230000001105 regulatory effect Effects 0.000 description 7
- 239000004449 solid propellant Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 238000004880 explosion Methods 0.000 description 5
- 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 4
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000010702 perfluoropolyether Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OUDRUNXDQLDNNJ-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptane-1,1-diol Chemical compound OC(O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OUDRUNXDQLDNNJ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 2
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 2
- LHJSLDBKUGXPMI-UHFFFAOYSA-N tris(2-methylpropyl) borate Chemical compound CC(C)COB(OCC(C)C)OCC(C)C LHJSLDBKUGXPMI-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- NHEKBXPLFJSSBZ-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluorohexane-1,6-diol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)CO NHEKBXPLFJSSBZ-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GAGSAAHZRBTRGD-UHFFFAOYSA-N oxirane;oxolane Chemical compound C1CO1.C1CCOC1 GAGSAAHZRBTRGD-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of new materials and propellants, and particularly discloses a borate type fluorine-containing combustion promoter, a preparation method and application thereof, wherein the terminal group of the borate type fluorine-containing combustion promoter is a borate group and a hydroxyl group, and a chain segment contains fluorine atoms; the boric acid ester group reacts with a small amount of water in the propellant in the mixing process of the propellant and then is hydrolyzed, and then the boric acid ester group and-OH on the surface of the aluminum powder undergo condensation reaction, so that the boric acid ester group is adsorbed on the surface of the aluminum powder; therefore, the borate type fluorine-containing combustion promoter can realize the in-situ self-assembly of fluorine-containing compounds and aluminum powder in the mixing process of the propellant.
Description
Technical Field
The invention relates to the technical field of new materials and propellants, in particular to a borate type fluorine-containing combustion promoter, a preparation method and application thereof.
Background
Al powder is a common metal fuel in solid propellant, and the specific impact of the propellant is improved by about 1s when 1wt% of aluminum powder is added; however, because the melting point of the Al powder is lower (660 ℃), the Al powder can be melted and coagulated to form larger Al coagulated mass before being ignited, so that the ignition delay time is long, the combustion is insufficient, and the energy cannot be fully exerted; meanwhile, al residues which are insufficiently combusted can be deposited on the surfaces of the engine spray pipe and the throat liner, so that serious negative effects are caused on the engine; therefore, an effective way is needed to improve the combustion efficiency of aluminum powder, and a foundation is laid for fully exerting the energy performance of the solid propellant.
Coating aluminum powder with fluorine-containing polymer is an effective means for reducing agglomeration of aluminum powder, and the reason why the combustion efficiency of aluminum powder can be improved is mainly as follows: (1) the small molecular fluoride generated by decomposing the fluorine-containing polymer can be mixed with Al before aluminum powder is melted 2 O 3 Al reacts to form loose and porous AlF 3 Promoting the rapid ignition of aluminum powder; (2) AlF (AlF) 3 Can sublimate at about 1277 ℃, destroy aluminum agglomerates, reduce aluminum powder condensation and improve aluminum powder combustion efficiency. However, the research shows that the Al/fluoride composite material prepared by coating aluminum powder with fluorine-containing polymer has the following two problems in application: firstly, because the fluorine-containing polymer contains F element with strong electronegativity and C-F bond with high bond energy, the Al/fluoride composite material shows stronger hydrophobicity and oleophobicity, and the technology and mechanical property of the propellant are adversely affected after the fluorine-containing polymer is used; secondly, a large amount of inflammable solvents are needed in the preparation process of the Al/fluoride composite material, so that the difficulty and the risk of the amplified production of the Al/fluoride composite material are high; therefore, al/fluoride composites have not achieved large scale popularization and application in propellants.
To solve the above problems, it is considered to add a fluoropolymer as an additive directly to a solid propellant, but it still has the following problems in practical use: firstly, the fluoropolymer is not physically compatible with the adhesive, and the uniformity of the propellant is seriously affected; and the commercial fluorine-containing polymer lacks functional groups, cannot be directionally acted on the surface of the aluminum powder, and cannot fully exert the effect of catalyzing the combustion of the aluminum powder, so that the using effect cannot meet the using requirement of a formula.
Disclosure of Invention
Aiming at the problems, the research of the in-situ self-assembled fluorine-containing combustion promoter which contains functional groups and can directionally act on the surface of the aluminum powder in the mixing process of the propellant is of great significance; a first object of the present invention is to provide a borate type fluorine-containing combustion promoter having a borate group and a hydroxyl group as terminal groups; the boric acid ester group reacts with a small amount of water in the propellant in the mixing process of the propellant and then is hydrolyzed, and then the boric acid ester group and-OH on the surface of the aluminum powder undergo condensation reaction, so that the boric acid ester group is adsorbed on the surface of the aluminum powder; therefore, the borate type fluorine-containing combustion promoter can realize the in-situ self-assembly of fluorine-containing compounds and aluminum powder in the mixing process of the propellant.
The second object of the present invention is to provide a method for producing a borate type fluorine-containing combustion promoter.
The third object of the invention is to provide an application of the borate type fluorine-containing combustion promoter.
The first technical scheme adopted by the invention is as follows: a borate type fluorine-containing combustion promoter comprises borate groups and hydroxyl groups as terminal groups, wherein fluorine atoms are contained in chain segments.
Preferably, the structure of the borate type fluorine-containing combustion promoter is as follows: :
wherein R is 1 ＝C n H 2n-1 (n≤4)，R 2 ＝C a H b F c O d (a、b、c≥4，d≥0)。
The second technical scheme adopted by the invention is as follows: a method for preparing the borate type fluorine-containing combustion promoter according to the first technical scheme, comprising the following steps:
s1: reacting boric acid with low molecular fatty alcohol, and esterifying to generate primary boric acid ester;
s2: and the primary boric acid ester and fluorine-containing dihydric alcohol are subjected to transesterification reaction to generate the boric acid ester type fluorine-containing combustion accelerator.
Preferably, in the step S1, the molar ratio of boric acid to low-molecular fatty alcohol is 1:3-1:6.
Preferably, the low molecular fatty alcohol in the step S1 is one or more of ethanol, n-propanol, isopropanol, n-butanol and isobutanol.
Preferably, the step S1 includes:
mixing boric acid with low-molecular fatty alcohol, heating, stirring, and esterifying to generate primary boric acid ester after reflux reaction; the primary borate is obtained by distillation under reduced pressure.
Preferably, the molar ratio of the primary borate to the fluorine-containing diol in the step S2 is 1:1-1:2.
Preferably, the fluorine-containing diol in the step S2 is 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, 2, 3-tetrafluoro-1, 4-butanediol, 2,3, 4-hexafluoro-1, 5-pentanediol 2,3, 4, 5-octafluoro-1, 6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1, 1-heptanediol one or more of 1H, 8H-dodecafluoro-1, 8-octanediol, 1H, 9H-perfluoro-1, 9-nonanediol, and perfluoropolyether diol.
Preferably, the step S2 includes:
mixing the primary borate with fluorine-containing dihydric alcohol, heating, stirring, and carrying out reflux reaction to obtain a borate type fluorine-containing combustion promoter; the borate type fluorine-containing combustion promoter is obtained by reduced pressure distillation.
The third technical scheme adopted by the invention is as follows: use of a borate type fluorine-containing combustion promoter in the preparation of a propellant.
The beneficial effects of the technical scheme are that:
(1) The terminal group of the borate type fluorine-containing combustion promoter provided by the invention is a borate group and a hydroxyl group; the boric acid ester group reacts with a small amount of water in the propellant in the mixing process of the propellant and then is hydrolyzed, and then the boric acid ester group and-OH on the surface of the aluminum powder undergo condensation reaction, so that the boric acid ester group is adsorbed on the surface of the aluminum powder; therefore, the borate type fluorine-containing combustion promoter can realize the in-situ self-assembly of fluorine-containing compounds and aluminum powder in the mixing process of the propellant; the hydroxyl groups in the terminal groups of the borate type fluorine-containing combustion promoter can react with the curing agent and enter the adhesive matrix network.
(2) The borate type fluorine-containing combustion promoter provided by the invention has the advantages of simple preparation method, readily available raw materials, low risk, easily controlled process conditions and product quality, and good compatibility with propellants.
(3) The borate type fluorine-containing combustion promoter disclosed by the invention is added into the propellant, and can fully exert the combustion-supporting effect of fluorine-containing compounds on aluminum powder after directionally acting on the surface of the aluminum powder in the mixing process of the propellant, so that the combustion efficiency of the aluminum powder is improved, the heat of explosion of the propellant is improved by more than 5%, and the energy performance of the propellant is effectively improved.
(4) The borate type fluorine-containing combustion promoter provided by the invention can be used as an additive to improve the energy performance of the propellant, has wide application prospect in polyether type solid propellants such as HTPE, PET, GAP, and has no negative influence on the mechanical property, safety property and the like of the composite solid propellant.
Drawings
FIG. 1 is an infrared spectrum of a borate type fluorine-containing combustion promoter according to an embodiment of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples, which should be understood to those skilled in the art that variations and modifications can be made without departing from the principles of the invention, and these should also be considered to be within the scope of the invention.
What is not described in detail in the present specification belongs to the known technology of those skilled in the art.
The invention discloses a borate type fluorine-containing combustion promoter, wherein the terminal group of the borate type fluorine-containing combustion promoter is a borate group and a hydroxyl group, and a chain segment contains fluorine atoms, and the structure of the borate type fluorine-containing combustion promoter is as follows:
wherein R is 1 ＝C n H 2n-1 (n≤4)，R 2 ＝C a H b F c O d (a、b、c≥4，d≥0)；
The infrared spectrum of the borate type fluorine-containing combustion promoter is shown in figure 1.
The invention also discloses a preparation method of the borate type fluorine-containing combustion promoter, which comprises the following steps:
s1: boric acid reacts with low molecular fatty alcohol, and primary boric acid ester is generated through esterification: mixing boric acid with low-molecular fatty alcohol, heating, stirring, and esterifying to generate primary boric acid ester after reflux reaction; obtaining a primary borate by distillation under reduced pressure; the method specifically comprises the following substeps:
s1-1: adding boric acid and low molecular fatty alcohol into a reaction device (such as a flask), wherein the molar ratio of the boric acid to the low molecular fatty alcohol is 1:3-1:6; the low molecular fatty alcohol is one or more of ethanol, n-propanol, isopropanol, n-butanol and isobutanol;
s1-2: heating the reaction device in an oil bath, installing a condensing pipe, a water separator, starting a stirring device to stir, and adjusting the reaction temperature to 70-130 ℃; reflux reaction is carried out to generate primary boric acid ester; when the water yield of the water separator is more than or equal to the calculated water yield value (the molar ratio of the calculated water yield value to the boric acid input in the step S1-1 is 3:1), the whole reflux reaction device is replaced by a reduced pressure distillation device;
s1-3: performing reduced pressure distillation to obtain primary boric acid ester;
the reaction temperature is kept between 70 and 130 ℃, a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa) is started after normal pressure distillation is carried out until no distillate exists, and vacuum distillation is carried out until no distillate exists; the reaction temperature is adjusted to 100-180 ℃, a receiving bottle is replaced, a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa) is started, and the primary boric acid ester is obtained through distillation.
S2: the primary boric acid ester and fluorine-containing dihydric alcohol are subjected to transesterification reaction to generate boric acid ester type fluorine-containing combustion promoter: mixing the primary borate with fluorine-containing dihydric alcohol, heating, stirring, and carrying out reflux reaction to obtain a borate type fluorine-containing combustion promoter; obtaining a borate type fluorine-containing combustion promoter through reduced pressure distillation; the method specifically comprises the following substeps:
s2-1: adding primary boric acid ester and fluorine-containing dihydric alcohol in a molar ratio of 1:1-1:2 into a reaction device (such as a flask);
s2-2: heating the reaction device in an oil bath, installing a condensing tube, starting a stirring device for stirring, and adjusting the reaction temperature to 95-120 ℃;
s2-3: the reaction temperature is kept between 95 and 120 ℃, after the reflux reaction is carried out for 1 to 4 hours, a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa) is started, the distillation time is more than 3 hours, the distillation is reduced to no distillate, and the temperature is naturally reduced to the room temperature, thus obtaining the borate type fluorine-containing combustion promoter.
Wherein, the fluorine-containing dihydric alcohol is 4, 4-trifluoro-3- (trifluoromethyl) -1,3 butanediol, 2, 3-tetrafluoro-1, 4-butanediol, 2,3, 4-hexafluoro-1, 5-pentanediol 2,3, 4, 5-octafluoro-1, 6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoro-1, 1-heptanediol, 1H, 8H-dodecafluoro-1, 8-octanediol, 1H, 9H-perfluoro-1, 9-nonanediol, perfluoropolyether diol, or a combination thereof.
The borate type fluorine-containing combustion promoter provided by the invention is used as a functional additive of the propellant, and accounts for 0.5% -5% of the total mass of the propellant; the borate type fluorine-containing combustion promoter has wide application prospect in polyether type solid propellants such as HTPE, PET, GAP, and the energy performance of the propellant is improved by more than 5% compared with the energy performance of the propellant without the fluorine-containing combustion promoter.
Example 1
24.73g boric acid and 103.76g n-butanol are placed in a 250mL three-neck flask, a stirring paddle, a stirring motor, a condenser pipe and a water separator are arranged, the reaction temperature is regulated to 120 ℃, and after the water yield of the water separator is more than 21.60mL, the whole reflux reaction device is converted into a reduced pressure distillation device; keeping the reaction temperature at 120 ℃, distilling at normal pressure until no distillate exists, starting a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa), decompressing and distilling out excessive n-butyl alcohol, replacing a receiving bottle, adjusting the reaction temperature to 170 ℃, starting the vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa), distilling to obtain tri-n-butyl borate, and preserving in a dark place.
23.00g of tri-n-butyl borate and 120.00g of perfluoropolyether glycol (molecular weight 1200) were placed in a 250mL three-necked flask, and a reduced pressure distillation apparatus was mounted; the reaction temperature is regulated to 115 ℃ for 3 hours, a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa) is started, reduced pressure distillation is carried out for 4 hours, and the temperature is reduced to room temperature, thus obtaining the borate type fluorine-containing combustion accelerator A.
Example 2
24.73g boric acid and 120.20g ethanol are placed in a 250mL three-neck flask, a stirring paddle, a stirring motor, a condensing tube and a water separator are arranged, the reaction temperature is adjusted to be 85 ℃, and after the water yield of the water separator is more than 21.60mL, the whole reflux reaction device is converted into a reduced pressure distillation device; keeping the reaction temperature at 85 ℃, distilling at normal pressure until no distillate exists, starting a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa), decompressing and distilling out excessive ethanol, replacing a receiving bottle, adjusting the reaction temperature to 110 ℃, starting the vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa), distilling to obtain triethyl borate, and preserving in a dark place.
29.20g of triethylborate and 42.42g of 2,3, 4-hexafluoro-1, 5-pentanediol were placed in a 250mL three-necked flask, and a reduced pressure distillation apparatus was mounted; the reaction temperature is regulated to 105 ℃, the reaction is carried out for 2 hours, a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa) is started, the vacuum distillation is carried out for 3 hours, and the temperature is reduced to the room temperature, thus obtaining the borate type fluorine-containing combustion accelerator B.
Example 3
24.73g boric acid and 96.16g normal propyl alcohol are placed in a 250mL three-neck flask, a stirring paddle, a stirring motor, a condenser pipe and a water separator are arranged, the reaction temperature is regulated to be 100 ℃, and after the water yield of the water separator is more than 21.60mL, the whole reflux reaction device is converted into a reduced pressure distillation device; keeping the reaction temperature at 100 ℃, distilling at normal pressure until no distillate exists, starting a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa), decompressing and distilling out excessive n-propanol, replacing a receiving bottle, adjusting the reaction temperature to 150 ℃, starting the vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa), distilling to obtain tri-n-propyl borate, and preserving in a dark place.
37.61g of tri-n-propyl borate and 52.42g 2,2,3,3,4,4,5,5-octafluoro-1, 6-hexanediol are placed in a 250mL three-neck flask, and a reduced pressure distillation device is installed; the reaction temperature is regulated to 110 ℃, the reaction is carried out for 3 hours, a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa) is started, the reduced pressure distillation is carried out for 4 hours, and the temperature is reduced to the room temperature, thus obtaining the borate type fluorine-containing combustion promoter C.
Example 4
24.73g boric acid and 103.76g isobutanol are placed in a 250mL three-neck flask, a stirring paddle, a stirring motor, a condenser pipe and a water separator are arranged, the reaction temperature is regulated to be 110 ℃, and after the water yield of the water separator is more than 21.60mL, the whole reflux reaction device is converted into a reduced pressure distillation device; keeping the reaction temperature at 110 ℃, distilling at normal pressure until no distillate exists, starting a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa), decompressing and distilling out excessive n-butanol, replacing a receiving bottle, adjusting the reaction temperature to 160 ℃, starting the vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa), distilling to obtain triisobutyl borate, and storing in a dark place.
46.00g of triisobutyl borate and 72.4g of 1H, 8H-dodecafluoro-1, 8-octanediol were placed in a 250mL three-necked flask, and a reduced pressure distillation apparatus was mounted; the reaction temperature is regulated to 115 ℃ for 2 hours, a vacuum pump (the vacuum degree is less than or equal to 0.0075 MPa) is started, reduced pressure distillation is carried out for 5 hours, and the temperature is reduced to room temperature, thus obtaining the borate type fluorine-containing combustion accelerator D.
Example 5
The borate type fluorine-containing combustion promoter A prepared in the above example 1 is used for preparing PET propellant, the borate type fluorine-containing combustion promoter A accounts for 1% of the propellant, the propellant comprises hydroxyl-terminated ethylene oxide-tetrahydrofuran copolyether (PET), toluene Diisocyanate (TDI), nitroglycerin (NG), 1,2, 4-butanetriol trinitrate (BTTN), ammonium Perchlorate (AP), cyclotetramethylene tetranitramine (HMX), aluminum (Al), borate type fluorine-containing combustion promoter A and functional components, the content of the specific components is shown in Table 1, the usability is shown in Table 2, and the explosion heat test method in the invention refers to QJ1359-1988 constant temperature method of the explosion heat test method of composite solid propellant.
TABLE 1PET propellant composition
TABLE 2 use Properties of borate type fluorine-containing Combustion promoter A in PET propellant
Example 6
The borate type fluorine-containing combustion promoter B prepared in the above example 2 is used for preparing a PEG propellant, the borate type fluorine-containing combustion promoter B accounts for 2% of the propellant, the propellant comprises polyethylene glycol (PEG), toluene Diisocyanate (TDI), nitroglycerin (NG), 1,2, 4-butanetriol trinitrate (BTTN), ammonium Perchlorate (AP), cyclotetramethylene tetranitramine (HMX), aluminum (Al), the borate type fluorine-containing combustion promoter B and functional components, the specific component content is shown in Table 3, and the service performance is shown in Table 4.
TABLE 3PEG propellant composition
TABLE 4 use Properties of borate type fluorine-containing Combustion promoter B in PEG propellant
| Name of the name | Heat of explosion, J/g | Residue aliveAluminum, wt% |
| KB-3 | 6314.7 | 1.05 |
| KB-4 | 6870.9 | 0.12 |
Example 7
The borate type fluorine-containing combustion promoter C prepared in the above example 3 was used for the preparation of GAP propellant, the borate type fluorine-containing combustion promoter C accounts for 1.5% of the propellant, the propellant composition comprises poly azide glycidyl ether (GAP), toluene Diisocyanate (TDI), nitroglycerin (NG), 1,2, 4-butanetriol trinitrate (BTTN), ammonium Perchlorate (AP), cyclo-tetramethylene tetranitramine (HMX), (Al), borate type fluorine-containing combustion promoter C and functional components, the specific component content is shown in Table 5, and the service performance is shown in Table 6.
TABLE 5GAP propellant composition
TABLE 6 use Properties of borate type fluorine-containing Combustion promoter C in GAP propellants
Example 8
The borate type fluorine-containing combustion promoter D prepared in the above example 4 was used for the preparation of GAP propellants, the borate type fluorine-containing combustion promoter D was 0.5% of the propellants, the propellant composition including polyazide glycidyl ether (GAP), toluene Diisocyanate (TDI), nitroglycerin (NG), 1,2, 4-butanetriol trinitrate (BTTN), ammonium Perchlorate (AP), cyclotetramethylene tetranitramine (HMX), aluminum (Al), borate type fluorine-containing combustion promoter D and functional components, the specific component contents are shown in Table 7, and the service performance is shown in Table 8.
TABLE 7GAP propellant composition
Table 8 performance of borate-type fluorine-containing combustion promoter D in GAP propellants
| Name of the name | Heat of explosion, J/g | Residue activated aluminum, wt% |
| KB-5 | 6524.9 | 1.23 |
| KB-7 | 6872.6 | 0.46 |
The invention has been described in detail in connection with the detailed description and the exemplary embodiments, which are exemplary, not exhaustive, and are not limited to the disclosed embodiments; the above description should not be taken as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these all fall within the scope of the present invention; the scope of the invention is defined by the appended claims.
Claims (10)
1. A borate type fluorine-containing combustion promoter is characterized in that the terminal group of the borate type fluorine-containing combustion promoter is a borate group and a hydroxyl group, and a chain segment contains fluorine atoms.
2. The borate type fluorine-containing combustion promoter according to claim 1, wherein the borate type fluorine-containing combustion promoter has the structure as follows:
wherein R is 1 ＝C n H 2n-1 (n≤4)，R 2 ＝C a H b F c O d (a、b、c≥4，d≥0)。
3. A process for the preparation of the borate ester type fluorine-containing combustion promoter according to any one of claims 1 to 2, comprising the steps of:
s1: reacting boric acid with low molecular fatty alcohol, and esterifying to generate primary boric acid ester;
s2: and the primary boric acid ester and fluorine-containing dihydric alcohol are subjected to transesterification reaction to generate the boric acid ester type fluorine-containing combustion accelerator.
4. The method according to claim 3, wherein the molar ratio of boric acid to low-molecular fatty alcohol in step S1 is 1:3 to 1:6.
5. The method according to claim 3, wherein the low molecular weight fatty alcohol in the step S1 is one or more of ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.
6. A method according to claim 3, wherein step S1 comprises:
mixing boric acid with low-molecular fatty alcohol, heating, stirring, and esterifying to generate primary boric acid ester after reflux reaction; the primary borate is obtained by distillation under reduced pressure.
7. The method according to claim 3, wherein the molar ratio of the primary borate to the fluorine-containing diol in the step S2 is 1:1 to 1:2.
8. A process according to claim 3, wherein, the fluorine-containing dihydric alcohol in the step S2 is 4, 4-trifluoro-3- (trifluoromethyl) -1,3 butanediol 2, 3-tetrafluoro-1, 4-butanediol, 2,3, 4-hexafluoro-1, 5-pentanediol 2, 3-tetrafluoro-1, 4-butanediol 2,3, 4-hexafluoro-1, 5-pentanediol.
9. A method according to claim 3, wherein step S2 comprises:
mixing the primary borate with fluorine-containing dihydric alcohol, heating, stirring, and carrying out reflux reaction to obtain a borate type fluorine-containing combustion promoter; the borate type fluorine-containing combustion promoter is obtained by reduced pressure distillation.
10. Use of a borate-type fluorine-containing combustion promoter according to any one of claims 1 to 2 or a borate-type fluorine-containing combustion promoter produced according to the production method of any one of claims 3 to 9 in the production of a propellant.
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