CN114133553A - 3, 3-bis-azidomethyloxetane-ethylene glycol energetic copolyether with alternating multi-block structure and synthesis method thereof - Google Patents
3, 3-bis-azidomethyloxetane-ethylene glycol energetic copolyether with alternating multi-block structure and synthesis method thereof Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- -1 3, 3-bis-azidomethyloxetane-ethylene glycol Chemical compound 0.000 title claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 15
- OSHFQKSCTZKQMP-UHFFFAOYSA-N 3,3-diazido-2-methyloxetane Chemical compound CC1OCC1(N=[N+]=[N-])N=[N+]=[N-] OSHFQKSCTZKQMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004703 alkoxides Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229920001519 homopolymer Polymers 0.000 abstract description 4
- 239000003380 propellant Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 150000001540 azides Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 230000000007 visual effect Effects 0.000 abstract 1
- 229920001400 block copolymer Polymers 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000011345 viscous material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 125000005490 tosylate group Chemical group 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000012656 cationic ring opening polymerization Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
-
- 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
- C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
-
- 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
Abstract
The invention discloses a 3, 3-diaza methyl oxetane-glycol energetic copolyether with an alternate multi-block structure and a synthesis method thereof, wherein the structural formula of an alternate multi-block energetic adhesive is shown as (I):
Description
Technical Field
The invention relates to 3, 3-bis-azidomethyloxetane-ethylene glycol copolyether with an alternate multi-block structure and a synthesis method thereof, and the compound can be used as an energetic adhesive of a solid propellant, belonging to the technical field of high polymer materials.
Background
As an energy-containing adhesive with high nitrogen content, the 3, 3-bis-azidomethyloxetane homopolymer (PBAMO) has the advantages of high energy, good compatibility, low mechanical sensitivity and the like, and can greatly meet the requirement of energy-containing materials on energy. However, the existence of the PBAMO side group hinders the chain rotation of the main chain, and the crystallinity and the glass transition temperature of the adhesive are improved, so that the solid propellant is not resistant to low temperature and has poor toughness in a low-temperature environment.
In order to solve the problem of low-temperature embrittlement of PBAMO, researchers have introduced flexible chains into azide-based energetic binders to lower their glass transition temperatures. Manser et al synthesized a BAMO-THF copolymer by a cationic ring-opening polymerization method, and found that introducing a second monomer THF to copolymerize with BAMO destroys the stereoregularity of PBAMO, eliminates or reduces its crystallinity, and can be used as an adhesive for explosives and powders. (Man ser G E, Fletcher R W, Shaw G C. high olefinic binders, Summary report to office of naval research [ R ]. ONR N-0014-82-C-0800, 1984.) Sreekumar et al have synthesized PBAMO-GAP-PBAMO triblock copolymer using macroinitiator, and GAP is an effective way to improve the mechanical properties of GAP homopolymer by copolymerizing soft segment and BAMO, because the phase separation between soft segment and soft segment can provide excellent mechanical properties for copolymer, and a three-dimensional physical cross-linking network structure can be formed between BAMO molecules. (Sreekumar P, Ang H G. Synthesis and thermal composition of GAP-Poly (BAMO) copolymer [ J ]. Polymer degradation and stabilization, 2007, 92: 1365-. The AMMO impact sensitivity is low, and the thermal stability, the mechanical property and the low-temperature mechanical property are all superior to those of GAP, so that the BAMO-AMMO copolymer obtained by copolymerizing AMMO and BAMO has excellent performance. The use of bamo. ammo copolymers in propellants and propellants has been extensively studied abroad. (Manser G E, Fletcher R W. energy thermal plastic elastomer synthesis, third quality summary of progress on contact [ R ]. ADA196885, 1988.) the main chain of the polyethylene glycol molecule contains a large number of ether bonds, and the flexibility of the molecular chain is good, thus endowing the material with excellent low-temperature characteristics. However, ethylene oxide is difficult to be copolymerized uniformly with a monomer of the oxetane group because of its easy ring-opening property, and thus, studies on the BAMO-EG copolyether have not been conducted.
Disclosure of Invention
The invention aims to provide 3, 3-diazacyclomethyloxetane-glycol copolyether with an alternating multi-block structure and a synthesis method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
polyethylene glycol (PEG) and 3, 3-bis-azidomethyloxetane homopolymer (PBAMO) are used as raw materials, KOH is used as a catalyst, and nucleophilic substitution reaction is carried out to obtain the alternating segmented azide type energetic adhesive. The synthesis method is simple, the obtained alternating multi-block BAMO-EG energetic copolyether can endow the propellant with better mechanical property, and the structural formula is as follows:
the BAMO-EG energetic copolyether with an alternating multi-block structure comprises the following specific steps:
step 1, adding a 3, 3-bis-azidomethyloxetane oligomer with small molecular weight, tetrahydrofuran and excessive potassium hydroxide into a three-neck flask provided with a magnetic stirring device, a thermometer and a reflux device, and carrying out reflux stirring reaction to obtain a potassium/sodium terminal alkoxide 3, 3-bis-azidomethyloxetane oligomer;
step 2, dropwise adding a tetrahydrofuran solution of polyethylene glycol esterified with end-toluene sulfonic acid into the potassium/sodium end-alkoxide 3, 3-bis-azidomethyloxetane oligomer, carrying out reflux stirring reaction, and filtering to obtain yellow liquid after the reaction is finished;
step 3, removing the tetrahydrofuran solvent in the yellow liquid by rotary evaporation, dissolving the tetrahydrofuran solvent in dichloromethane, adjusting the pH value to be neutral by using a hydrochloric acid aqueous solution and a sodium chloride saturated aqueous solution, drying the anhydrous sodium sulfate, and then, drying by rotary evaporation; then petroleum ether and methanol are used for extraction to remove cyclic ether and low molecular oligomer, and the BAMO-EG energetic copolyether with an alternating multi-block structure is obtained.
Preferably, in step 1, the molecular weight of the 3, 3-bis-azidomethyloxetane oligomer is Mn 186-930.
Preferably, in the step 1, the volume ratio of the 3, 3-bis-azidomethyloxetane oligomer to the tetrahydrofuran is 1: 1-3.
Preferably, in step 1, the catalyst may be potassium hydroxide, sodium hydride, sodium methoxide, etc.
Preferably, in the step 2, the molar ratio of the sodium/potassium terminal alkoxide 3, 3-diazacyclomethyloxetane to the polyethylene glycol p-toluenesulfonate is 1-2: 1.
Preferably, in the step 2, the volume ratio of the polyethylene glycol p-toluenesulfonate to the tetrahydrofuran is 1: 1-3.
Preferably, in the step 2, the reflux reaction time is 12-48 h.
Preferably, in the step 3, the concentration of the hydrochloric acid aqueous solution is not higher than 2 mol/L.
Compared with the prior art, the invention has the following advantages:
the invention gets rid of the common cationic polymerization copolymerization method in the prior art, realizes the polycondensation among oligomers by a Wilson ether synthesis method, and successfully obtains the BAMO-EG energetic copolyether with an alternate multi-block structure.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
1.05g of PBAMO (Mn 301, 3.5mmol) was dissolved in 10mL of THF, 2.24g of KOH (40mmol) was added, and the system was transferred to a constant temperature oil bath at 65 ℃. A THF solution of 1.12g of a terminal tosylate polyethylene glycol (Mn 510, 2.2mmol) was slowly dropped into the above reaction system, and after the dropping was completed, the reaction system was allowed to continue at 65 ℃ for 24 hours. The crude product was then filtered and rotary evaporated, dissolved in dichloromethane and washed to neutrality with distilled water. Drying with anhydrous magnesium sulfate, vacuum filtering, rotary steaming, sequentially adding petroleum ether with boiling point of 60-90 deg.C and methanol, washing, and rotary steaming to obtain yellow viscous substance (0.78g)
And (3) structural identification:
FT-IR Infrared: PEG-OTS passing through p-toluenesulfonylAfter acylation to obtain tosylate polyethylene glycol, infrared hydroxyl 3000-3500cm-1Disappearance proves that the end group of the polyethylene glycol is completely modified. The hydroxyl peak of PBMO-EG prepared by PBMO and PEG-OTS is obviously reduced compared with PBMO, and the p-toluenesulfonyl chloride is 1000-1500 cm--1The characteristic peak of (2) disappears.
Nuclear magnetism: 1H-NMR (CDCl)3500 MHz): delta 3.5-3.6 (CH in PEG)2-O), delta 3.3-3.4 (CH in BDO)2-O)，δ3.23-3.28(CH2-N3) 3.18-3.23 (CH in BAMO)2-O), 1.44-1.64 (C-CH in THF)2-C)。
The data above show that the synthesized compound is a BAMO-EG energetic copolyether with an alternating multiblock structure.
Example 2
0.93g of pbamoo (Mn 301, 3.1mmol) was dissolved in 20mL of THF, 2.32g of KOH (41mmol) was added, and the system was transferred to a constant temperature oil bath at 65 ℃. A THF solution of 1..01g of terminal tosylate glycol (Mn ═ 460, 2.2mmol) was slowly added dropwise to the above reaction system, and after completion of the addition, the reaction system was allowed to continue at 65 ℃ for 24 hours. The crude product was then filtered and rotary evaporated, dissolved in dichloromethane and washed to neutrality with distilled water. Drying with anhydrous magnesium sulfate, vacuum filtering, rotary steaming, sequentially adding petroleum ether with boiling point of 60-90 deg.C and methanol, washing, and rotary steaming to obtain yellow viscous substance (0.65 g).
Example 3
0.95g of PBAMO (Mn 367, 2.6mmol) was dissolved in 20mL of THF, 2.01g of KOH (36mmol) was added, and the system was transferred to a constant temperature oil bath at 65 ℃. A THF solution of 0.83g of terminal tosyl glycol (Mn 460, 1.8mmol) was slowly added dropwise to the above reaction system, and after completion of the addition, the reaction system was allowed to continue at 65 ℃ for 24 hours. The crude product was then filtered and rotary evaporated, dissolved in dichloromethane and washed to neutrality with distilled water. Drying with anhydrous magnesium sulfate, vacuum filtering, rotary steaming, sequentially adding petroleum ether with boiling point of 60-90 deg.C and methanol, washing, and rotary steaming to obtain yellow viscous substance (0.52 g).
FIG. 1 is a schematic representation of a BAMO-EG alternating multi-block copolymer prepared in example 1;
FIG. 2 is a Fourier infrared signature spectrum of the BAMO-EG alternating multi-block copolymer prepared in example 1;
FIG. 3 is the NMR spectrum of the BAMO-EG alternating multi-block copolymer of example 1;
FIG. 4 is a schematic representation of a BAMO-EG alternating multi-block copolymer prepared in example 2;
FIG. 5 is the NMR spectrum of the BAMO-EG alternating multi-block copolymer of example 2;
FIG. 6 is a schematic representation of a BAMO-EG alternating multi-block copolymer prepared in example 3; (ii) a
FIG. 7 shows the NMR spectrum of the BAMO-EG alternating copolymer of example 3.
Claims (10)
1. A3, 3-bis-azidomethyloxetane-glycol energetic copolyether with an alternate multi-block structure and a synthesis method thereof, wherein the structural formula of the alternate multi-block energetic adhesive is shown as (I)
Wherein m is 1 to 4, n is 1 to 4, l is 1 to 4, and k is 1 to 10 and is an integer.
2. A3, 3-bis-azidomethyloxetane-glycol energetic copolyether with an alternate multi-block structure and a synthesis method thereof are characterized by comprising the following steps:
step 1, adding a 3, 3-bis-azidomethyloxetane oligomer with small molecular weight, tetrahydrofuran and a catalyst into a three-neck flask provided with a magnetic stirring device, a thermometer and a reflux device, and carrying out reflux stirring reaction to obtain a potassium/sodium terminal alkoxide 3, 3-bis-azidomethyloxetane oligomer;
step 2, dropwise adding a tetrahydrofuran solution containing polyethylene glycol (PEG-OTS) p-toluenesulfonate into the potassium/sodium terminal alkoxide 3, 3-bis-azidomethyloxetane oligomer, carrying out reflux stirring reaction, and filtering to obtain a dark yellow liquid after the reaction is finished;
and 3, removing the tetrahydrofuran solvent in the yellow liquid by rotary evaporation, dissolving in dichloromethane, adjusting the pH value to be neutral by using a hydrochloric acid aqueous solution and a sodium chloride saturated aqueous solution, drying by using anhydrous sodium sulfate, filtering, and drying by rotary evaporation. Then petroleum ether and methanol are adopted for extraction to remove cyclic ether compounds and low molecular oligomers, and the BAMO-EG energetic copolyether with an alternating multi-block structure is obtained.
3. The method of claim 2, wherein in step 1, the molecular weight of the 3, 3-bis-azidomethyloxetane oligomer is Mn 186-930.
4. The method according to claim 2, wherein in step 1, the volume ratio of the 3, 3-bis-azidomethyloxetane oligomer to the PEG-OTS is 1: 1-3.
5. The method according to claim 2, wherein in step 1, the catalyst is potassium hydroxide, sodium hydride, sodium methoxide, or the like.
6. The method according to claim 2, wherein in step 2, the molecular weight of the polyethylene glycol p-toluenesulfonate (PEG-OTS) is 39 g-550.
7. The preparation method of claim 2, wherein in the step 2, the molar ratio of the sodium/potassium 3, 3-diazacyclomethyloxetane terminated oligomer to the polyethylene glycol p-toluenesulfonate is 1-2: 1.
8. The preparation method according to claim 2, wherein in the step 2, the volume ratio of the polyethylene glycol p-toluenesulfonate to the tetrahydrofuran is 1: 1-3.
9. The preparation method according to claim 2, wherein in the step 2, the reflux reaction time is 12-72 hours.
10. The method according to claim 2, wherein in step 3, the concentration of the aqueous hydrochloric acid solution is not higher than 2 mol/L.
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| CN115368554A (en) * | 2022-08-02 | 2022-11-22 | 南京理工大学 | 3-azidomethyl-3-methyl oxetane-3-methyltetrahydrofuran energetic copolyether and synthesis method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010047072A1 (en) * | 2000-05-02 | 2001-11-29 | Sanderson Andrew J. | Chain-extended poly(bis-azidomethyloxetane), and combustible cartridge cases and ammunition comprising the same |
| CN111440307A (en) * | 2020-04-09 | 2020-07-24 | 苏州大学 | High-functionality azide glue and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010047072A1 (en) * | 2000-05-02 | 2001-11-29 | Sanderson Andrew J. | Chain-extended poly(bis-azidomethyloxetane), and combustible cartridge cases and ammunition comprising the same |
| CN111440307A (en) * | 2020-04-09 | 2020-07-24 | 苏州大学 | High-functionality azide glue and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| GING-HO HSIUE ET AL.: ""Triblock Copolymers Based on Cyclic Ethers: Preparation and Properties of Tetrahydrofuran and 3, 3-Bis ( azidomethyl ) Oxetane Triblock Copolymers"", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY 》, vol. 32, no. 11, 31 December 1994 (1994-12-31), pages 2155 - 2159 * |
| UGO BARBIERI ET AL.: ""Synthesis of Energetic Polyethers from Halogenated Precursors"", 《MACROMOL. SYMP.》, no. 234, 31 December 2006 (2006-12-31), pages 51 - 58 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368554A (en) * | 2022-08-02 | 2022-11-22 | 南京理工大学 | 3-azidomethyl-3-methyl oxetane-3-methyltetrahydrofuran energetic copolyether and synthesis method thereof |
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