CN115353631A - 3, 3-bis-azidomethyloxetane-3-methyltetrahydrofuran energetic copolyether and synthesis method thereof - Google Patents
3, 3-bis-azidomethyloxetane-3-methyltetrahydrofuran energetic copolyether and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses a 3, 3-bis-azidomethyloxetane-3-methyltetrahydrofuran energetic copolyether and a synthesis method thereof, wherein the energetic adhesive has a structural formula shown as (I):
Description
Technical Field
The invention relates to a 3, 3-diazacyclomethyloxetane-3-methyltetrahydrofuran copolymer and a synthesis method thereof, and belongs to the technical field of high polymer materials, wherein the compound can be used as an energetic adhesive of a solid propellant.
Background
Each monomer unit of the poly 3, 3-bis-azidomethyloxetane (PBAMO) contains two azidomethyl groups, the high nitrogen content ensures that the PBAMO has very high heat of formation, can improve the energy level of the propellant, and the PBAMO has good compatibility with a nitrate plasticizer and low mechanical sensitivity, thereby meeting the requirements of high energy, insensitive feeling and low vulnerability of the solid propellant. However, due to the existence of side chain azide groups, the flexibility of PBAMO molecular chains is poor, and the PBAMO adhesive has high crystallinity due to a highly symmetrical molecular chain structure, so that the PBAMO adhesive has the problems of high glass transition temperature, high crystallinity and poor mechanical property, and the application of the PBAMO adhesive in solid propellants is limited.
At present, copolymerization modification is a main technical means for improving the comprehensive performance of the adhesive, and flexible chains such as polytetrahydrofuran, polyethylene glycol and the like are introduced into PBAMO molecular chains, so that the regularity of molecular chain structures can be effectively broken, the crystallinity is reduced, the flexibility of the molecular chains is improved, and the mechanical property and the processing property of the adhesive are improved. Sa Heng et al, in "New energy-containing Binder BAMO", summarize the physico-chemical properties of BAMO-THF copolymers, and the glass transition temperature of the BAMO-THF copolymer is-61 ℃ at a molar ratio of 60/40, which is greatly reduced compared to the BAMO polymer. Droxixiang et al, in 3,3-Synthesis of bis (azidomethyl) oxetane/tetrahydrofuran copolyether, synthesized the BAMO-THF copolyether by bulk polymerization, and by controlling the amount of initiator and monomer, the polymer molecular weight can be controlled. Azide glycidyl ether-1, 2-Epoxyhexane linear Copolymers were synthesized by Hafner et al in polymers based on GAP and 1,2-Epoxyhexane as a formulating prepolymer for energy Binder Systems by cationic ring-opening polymerization. The introduction of the n-butyl side chain can play a role of an internal plasticizer, and the intermolecular force and the intramolecular force between polymer main chains are reduced, so that the adhesive has lower viscosity and glass transition temperature, and tests show that the lowest glass transition temperature of the copolymer can reach-60 ℃.
Disclosure of Invention
The invention aims to provide a 3, 3-diazacyclomethyloxetane-3-methyltetrahydrofuran copolymer and a synthesis method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
the alternating segmented azide energetic binder is obtained by taking poly-3-methyltetrahydrofuran (P3-MeTHF) and a bis-azidomethyloxetane homopolymer (PBAMO) as raw materials and KOH as a reducing agent through nucleophilic substitution reaction. The synthesis method is simple, the sequence structure of the obtained BAMO-3-MeTHF energy-containing copolyether is adjustable, the performance of an adhesive can be adjusted, and the solid propellant has better mechanical properties, and the structural formula is as follows:
the BAMO-3-MeTHF energy-containing copolyether comprises the following specific steps:
step 2, dropwise adding a tetrahydrofuran solution containing P-toluenesulfonylated poly-3-methyltetrahydrofuran (P3-MeTHF-OTS) into the potassium terminal alkoxide 3, 3-bis-azidomethyloxetane oligomer or the sodium terminal alkoxide 3, 3-bis-azidomethyloxetane oligomer, refluxing, stirring and reacting, and filtering to obtain a white liquid after the reaction is finished;
and 3, removing the tetrahydrofuran solvent in the white liquid by rotary evaporation, dissolving in dichloromethane, adjusting the pH value to be neutral by using alkene hydrochloric acid and a saturated aqueous solution of sodium chloride, separating an organic phase, drying by using anhydrous sodium sulfate, filtering, carrying out rotary evaporation, extracting by using methanol and a mixed solution of petroleum ether and dichloromethane to remove a cyclic ether compound and a low molecular oligomer, and drying to obtain the BAMO-3-MeTHF energy-containing copolyether with an alternating multi-block structure.
Preferably, in step 1, the molecular weight of the PBAMO oligomer is Mn = 186-930.
Preferably, in step 1, the volume ratio of the PBAMO oligomer to the tetrahydrofuran is 1: 1-4.
Preferably, in step 1, the catalyst may be potassium hydroxide, sodium hydride, sodium methoxide, or sodium hydroxide.
Preferably, in the step 2, the molar ratio of the potassium/sodium end alkoxide PBAMO to the P3-MeTHF-OTS subjected to end-to-toluene sulfonylation is 1-3: 1.
Preferably, in the step 2, the volume ratio of the p-toluenesulfonylated poly-3-methyltetrahydrofuran to tetrahydrofuran is 1: 1-4.
Preferably, in the step 2, the reflux reaction time is 12 to 72 hours.
Preferably, in the step 3, the concentration of the hydrochloric acid aqueous solution is not higher than 2 mol.L -1 。
Compared with the prior art, the invention has the following advantages:
the invention gets rid of the commonly used cation ring-opening copolymerization method at present, and realizes the condensation polymerization between the oligomers through the nucleophilic substitution reaction of the Williamson ether synthesis method. The molecular chain sequence structure of the BAMO-3-MeTHF copolymer can be changed by adjusting the molecular weight and the reaction time of the oligomer, the mechanical property of the BAMO-based energetic copolyether can be effectively adjusted, and the BAMO-3-MeTHF energetic copolyether with different block unit numbers is finally obtained.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
1.73g of PBAMO (Mn =354, 4.89mmol) was dissolved in 5.5mL THF, 2.0g KOH (35.64 mmol) was added, and the system was moved into a constant temperature oil bath at 65 ℃. A mixed solution of 0.8g (1.93 mmol) of poly-3-methyltetrahydrofuran p-toluenesulfonylated and 3mL of THF was slowly dropped into the above reaction system, and the reaction system was allowed to continue at 65 ℃ for 25 hours after the dropping. After the reaction is finished, white liquid is filtered out, tetrahydrofuran solvent in the white liquid is evaporated in a rotary mode, the crude product is dissolved in dichloromethane, and 1 mol.L of the dichloromethane is used successively -1 The diluted hydrochloric acid and saturated brine are washed to be neutral. The organic phase was separated, dried over anhydrous magnesium sulfate, filtered and rotary evaporated in sequence to give a yellow viscous liquid. Extracting the liquid with methanol, extracting with mixed solution of petroleum ether and dichloromethane, and decanting the upper layerThe organic phase and the remaining phase were dried to give a clear yellow viscous liquid, i.e., BAMO-3-MeTHF energy-containing copolyether (1.02 g). Gel permeation chromatography tests the molecular weight of the sample to obtain: number average molecular weight Mn =2270, polydispersity PDI =1.28.
And (3) structure identification:
FT-IR Infrared: after the 3-MeTHF is subjected to p-toluenesulfonylation to obtain 3-MeTHF-OTS, the infrared hydroxyl group is 3000-3500cm -1 Disappearance, which proves that the end group of P3-MeTHF has been completely modified. The hydroxyl peak of BAMO-3-MeTHF copolyether prepared by PBAMO and P3-MeTHF-OTS is obviously reduced compared with PBAMO, and the characteristic peak of P-toluenesulfonyl chloride 1000-1500 disappears.
Nuclear magnetism: 1 H-NMR(500MHz，CDCl 3 )：3.35-3.60ppm(2H，O-CH 2 -C in 3-MeTHF)，3.26ppm (4H，O-CH 2 -N 3 )，3.20-3.23ppm(4H，O-CH 2 -C in PBAMO)，1.70-1.80ppm(1H，-CH-CH 3 in 3-MeTHF)，1.55ppm(2H，C-CH 2 -C in 3-MeTHF)，0.85ppm(3H，-CH 3 in 3-MeTHF).
the data above show that the synthesized compound is a BAMO-3-MeTHF energy-containing copolyether binder with an alternating multiblock structure.
Example 2
1.73g of PBAMO (Mn =354, 4.89mmol) was dissolved in 5.5mL of THF, 2.0g of KOH (35.64 mmol) was added, and the system was transferred into a constant temperature oil bath at 65 ℃. A mixed solution of 0.8g (1.93 mmol) of poly-3-methyltetrahydrofuran p-toluenesulfonylated and 3mL of THF was slowly dropped into the above reaction system, and the reaction system was allowed to continue at 65 ℃ for 24 hours after the dropping. After the reaction is finished, white liquid is filtered out, tetrahydrofuran solvent in the white liquid is evaporated in a rotary mode, the crude product is dissolved in dichloromethane, and 1 mol.L of the dichloromethane is used successively -1 The diluted hydrochloric acid and saturated brine are washed to be neutral. The organic phase was separated, dried over anhydrous magnesium sulfate, filtered and rotary evaporated in sequence to give a yellow viscous liquid. The liquid is extracted by methanol, and then extracted by a mixed solution of petroleum ether and dichloromethane again, an upper organic phase is poured out, and the residual phase is dried to finally obtain a clear yellow viscous liquid, namely the BAMO-3-MeTHF energy-containing copolyether (1.13 g). Gel permeation chromatography test theMolecular weight of the sample was obtained: number average molecular weight Mn =2660, polydispersity PDI =1.42.
Example 3
1.60g of PBAMO (Mn =426,3.75mmol) was dissolved in 5mL of THF, 2.0g of KOH (35.64 mmol) was added, and the system was transferred into a constant temperature oil bath at 65 ℃. A mixed solution containing 0.86g (2.08 mmol) of terminal tosylated poly-3-methyltetrahydrofuran and 2.6mL of THF was slowly dropped into the above reaction system, and the reaction system was allowed to continue at 65 ℃ for 24 hours after the dropping. After the reaction is finished, white liquid is filtered out, tetrahydrofuran solvent in the white liquid is evaporated in a rotary mode, the crude product is dissolved in dichloromethane, and 1 mol.L of the dichloromethane is used successively -1 The diluted hydrochloric acid and saturated brine are washed to be neutral. The organic phase was separated, dried over anhydrous magnesium sulfate, filtered and rotary evaporated in sequence to give a yellow viscous liquid. The liquid is extracted by methanol, and then extracted by a mixed solution of petroleum ether and dichloromethane again, an upper organic phase is poured out, and the residual phase is dried to finally obtain a transparent yellow viscous liquid, namely the BAMO-3-MeTHF energy-containing copolyether (0.98 g). Gel permeation chromatography tests the molecular weight of the sample to obtain: number average molecular weight Mn =1775, polydispersity PDI =1.47.
Drawings
FIG. 1 is a Fourier infrared signature spectrum of the BAMO-3-MeTHF copolymer prepared in example 1;
FIG. 2 is a NMR spectrum of the BAMO-3-MeTHF copolymer prepared in example 1;
FIG. 3 is a gel permeation chromatogram of the BAMO-3-MeTHF copolymers prepared in example 1 and example 2;
FIG. 4 is a Fourier-IR signature spectrum of the BAMO-3-MeTHF copolymer prepared in example 3;
FIG. 5 is a NMR spectrum of the BAMO-3-MeTHF copolymer prepared in example 3;
FIG. 6 is a gel permeation chromatogram of the BAMO-3-MeTHF copolymer prepared in example 3.
Claims (9)
1. A3, 3-bis-azidomethyloxetane-3-methyltetrahydrofuran energetic copolyether, energetic adhesive structural formula is shown as (I)
Wherein m =1 to 5, n =1 to 4, k =1 to 10, and is an integer.
2. A method for synthesizing 3, 3-diazacyclomethyloxetane-3-methyltetrahydrofuran energetic copolyether is characterized by comprising the following specific steps:
step 1, adding 3, 3-bis-azidomethyloxetane oligomer, 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 end alkoxide 3, 3-bis-azidomethyloxetane oligomer or a sodium end alkoxide 3, 3-bis-azidomethyloxetane oligomer;
step 2, dropwise adding a tetrahydrofuran solution containing P-toluene sulfonylated poly-3-methyltetrahydrofuran (P3-MeTHF-OTS) into a potassium end alkoxide 3, 3-bis-azidomethyloxetane oligomer or a sodium end alkoxide 3, 3-bis-azidomethyloxetane oligomer, carrying out reflux stirring reaction, and filtering after the reaction is finished to obtain a white liquid;
and 3, removing the tetrahydrofuran solvent in the white liquid by rotary evaporation, dissolving the tetrahydrofuran solvent in dichloromethane, adjusting the pH value to be neutral by using alkene hydrochloric acid and saturated aqueous solution of sodium chloride, separating an organic phase, drying the organic phase by using anhydrous sodium sulfate, filtering, carrying out rotary evaporation, and then extracting by using methanol and mixed solution of petroleum ether and dichloromethane to remove cyclic ether compounds and low molecular oligomers to obtain the BAMO-3-MeTHF energy-containing copolyether with an alternating multi-block structure.
3. The method as claimed in claim 2, wherein the molecular weight of the 3, 3-bis-azidomethyloxetane-3-methyltetrahydrofuran energetic copolyether in step 1 is Mn = 186-930.
4. The method of claim 2, wherein in step 1, the volume ratio of 3, 3-bis-azidomethyloxetane oligomer to tetrahydrofuran is 1: 1-4.
5. The method of claim 2, wherein in step 1, the catalyst is potassium hydroxide, sodium hydride, sodium methoxide, or sodium hydroxide.
6. The method of claim 2, wherein the molar ratio of the potassium/sodium alkoxide 3, 3-bis-azidomethyloxetane oligomer to the p-toluenesulfonylated poly-3-methyltetrahydrofuran in step 1 and step 2 is 1-3: 1.
7. The method of claim 2, wherein the volume ratio of poly (3-methyltetrahydrofuran) to tetrahydrofuran which is p-toluenesulfonylated in step 2 is 1: 1-4.
8. The method of claim 2, wherein the reflux-stirring reaction time in step 2 is 12-72 h.
9. The method of claim 2, wherein the concentration of the hydrochloric acid solution in step 3 is not higher than 2 mol.L -1 。
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| CN113501963A (en) * | 2021-08-04 | 2021-10-15 | 南京理工大学 | 3-azidomethyl-3-methyloxetane-tetrahydrofuran energetic copolyether with alternating multi-block structure and synthesis method thereof |
| CN113621134A (en) * | 2021-08-04 | 2021-11-09 | 南京理工大学 | 3, 3-bis-azidomethyloxetane-tetrahydrofuran energetic copolyether with alternating multi-block structure and synthesis method thereof |
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| CN113621134A (en) * | 2021-08-04 | 2021-11-09 | 南京理工大学 | 3, 3-bis-azidomethyloxetane-tetrahydrofuran energetic copolyether with alternating multi-block structure and synthesis method thereof |
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