An azide polyether, a method for preparing the same and use thereof
By controlling the molecular weight distribution of azide polyether through anionic polymerization, the problem of wide molecular weight distribution in existing technologies is solved, and the mechanical properties of azide polyether are improved.
Patent Information
- Application Number
- CN202211598758.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-12-12
- Publication Date
- 2025-12-19
- Estimated Expiration
- 2042-12-12
AI Technical Summary
The wide molecular weight distribution of existing azide polyethers affects their mechanical properties.
Azide polyethers were prepared by anionic polymerization. By controlling the feed ratio of benzyl alcohol to 5-azido-1-pentanol glycidyl ether and optimizing the reaction conditions, azide polyethers with a molecular weight distribution index ≤1.1 were obtained.
The number-average molecular weight of azide polyether was achieved in the range of 4380–7340 g/mol, with uniform molecular weight distribution, which significantly improved its mechanical properties.
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Figure CN116003772B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of energetic binder technology, in particular to an azide polyether and a preparation method and application thereof. BACKGROUND
[0002] The development of solid propellant technology often depends on the development of polymer technology, especially energetic polymer technology. In solid propellants, although the amount of binder is small, it has a crucial influence on the mechanical properties of solid propellants. Generally speaking, the mechanical properties of pure polymers are excellent, and the mechanical properties of the corresponding solid propellants are also ideal. For polymers, the molecular weight and molecular weight distribution are crucial points affecting the mechanical properties.
[0003] Zhang et al. (Zhang, Luo, Li. Synthesis, characterization and thermal decomposition kinetics of BAMO / AMMO triblock copolymer. Chinese Journal of Explosives and Propellants, 2010, 33(6): 11-15.) introduced the preparation of poly(3-azidomethyl-3-methyl oxetane) (PAMMO) and 3,3-bisazidomethyl oxetane (PBAMO) by homopolymerization and copolymerization. Studies have shown that through cationic ring-opening reaction, the molecular weight of the homopolymer is relatively low, and the number average molecular weight of 3400-6300 is regulated. The molecular weight of the AMMO / BAMO triblock copolymer is larger, and the number average molecular weight of 7900-14700 is regulated. However, the molecular weight distribution of the azide polyether polymerized by cationic polymerization is wide, all above 1.8, and even the molecular weight distribution of some samples reaches 2, which greatly affects the mechanical properties. SUMMARY
[0004] Therefore, the purpose of the present application is to provide an azide polyether and a preparation method and application thereof. The azide polyether provided by the present application has excellent mechanical properties.
[0005] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:
[0006] The present application provides an azide polyether having the structure shown in formula I:
[0007]
[0008] In formula I, n is 23-39.
[0009] Preferably, the molecular weight distribution index of the azide polyether is ≤1.1.
[0010] Preferably, the molecular weight of the azide polyether is 4380-7340 g / mol.
[0011] The present application also provides a preparation method of the azide polyether according to the above technical solutions, comprising the following steps:
[0012] mixing benzyl alcohol, an organic superbase phosphazene base having a structure shown in Formula 1, 5-azido-1-pentanol glycidyl ether having a structure shown in Formula 2, and a polar organic solvent, performing an anionic polymerization reaction, thereby obtaining the azide polyether;
[0013]
[0014]
[0015] Preferably, the method for preparing the 5-azido-1-pentanol glycidyl ether comprises the following steps:
[0016] mixing Product 1 having a structure shown in Formula 3, tetrabutylammonium hydrogen sulfate having a structure shown in Formula 4, Raw Material 2 having a structure shown in Formula 5, and KOH solution, performing a nucleophilic substitution reaction, thereby obtaining the 5-azido-1-pentanol glycidyl ether;
[0017]
[0018]
[0019]
[0020] In Formula 5, X includes -F, -Cl, -Br, or -I.
[0021] Preferably, the method for preparing the Product 1 comprises the following steps:
[0022] mixing Raw Material 1 having a structure shown in Formula 6, an alkali metal azide salt, and deionized water, performing an azidation reaction, thereby obtaining the Product 1;
[0023]
[0024] In Formula 6, X is -F, -Cl, -Br, or -I.
[0025] Preferably, the molar ratio of the benzyl alcohol, the organic superbase phosphazene base, and the 5-azido-1-pentanol glycidyl ether is 1:1:(10-80).
[0026] The temperature of the anionic polymerization reaction is 0-50℃, and the time is 24-90h.
[0027] Preferably, the molar ratio of the Product 1, the tetrabutylammonium hydrogen sulfate, and the Raw Material 2 is (10-30):1:100.
[0028] The temperature of the nucleophilic substitution reaction is 0-30℃, and the time is 12-36h.
[0029] Preferably, the molar ratio of the raw material 1 and the alkali metal azide salt is 1:1.2-1.5.
[0030] The temperature of the azide reaction is 110-120 DEG C, and the time is 5-24h.
[0031] The application further provides the application of the azide polyether or the azide polyether prepared by the preparation method as an energetic binder.
[0032] The application provides an azide polyether having a structure shown in formula I.
[0033]
[0034] In formula I, n is 23-39.
[0035] The azide polyether provided by the application has a molecular weight distribution index of less than or equal to 1.1 and a number average molecular weight in a range of 4380-7340 g / mol, so that the azide polyether has excellent mechanical properties.
[0036] The application further provides the preparation method of the azide polyether, which comprises the following steps: mixing benzyl alcohol, an organic super strong base phosphine oxide base having a structure shown in formula 1, 5-azido-1-pentanol glycidyl ether having a structure shown in formula 2 and a polar organic solvent, performing an anionic polymerization reaction to obtain the azide polyether.
[0037]
[0038]
[0039] The preparation method provided by the application can control the number average molecular weight of the finally obtained azide polyether by controlling the molar ratio of the benzyl alcohol and the 5-azido-1-pentanol glycidyl ether, and specifically, when the molar ratio of the benzyl alcohol and the 5-azido-1-pentanol glycidyl ether is 1:20, the number average molecular weight of the obtained azide polyether is 4380 g / mol; when the molar ratio of the benzyl alcohol and the 5-azido-1-pentanol glycidyl ether is 1:30, the number average molecular weight of the obtained azide polyether is 5260 g / mol; and when the molar ratio of the benzyl alcohol and the 5-azido-1-pentanol glycidyl ether is 1:40, the number average molecular weight of the obtained azide polyether is 7340 g / mol. BRIEF DESCRIPTION OF DRAWINGS
[0040] Figure 1 It is the nuclear magnetic spectrum of the raw material 1, the product 1 and the product 2 in Example 1.
[0041] Figure 2 It is the nuclear magnetic spectrum of the azide polyether obtained in Examples 1-3.
[0042] Figure 3 GPC elution curve of the azide polyether obtained in Example 1-3;
[0043] Figure 4 MALDI-TOF MS curve of the azide polyether obtained in Example 1;
[0044] Figure 5 Enlarged view of the MALDI-TOF MS curve of the azide polyether obtained in Example 1;
[0045] Figure 6 SEC elution curve of the azide polyether obtained in Example 2;
[0046] Figure 7 SEC elution curve of the anionically polymerized azide polyether obtained in Example 3.
[0047] Figure 8 Tensile curve of the film prepared from the azide polyether obtained in Example 1-3. DETAILED DESCRIPTION
[0048] The present application provides an azide polyether having the structure shown in Formula I:
[0049]
[0050] In the present application, in Formula I, n is 23-39.
[0051] In the present application, the molecular weight distribution index of the azide polyether is preferably ≤1.1, and further preferably 1-1.05.
[0052] In the present application, the molecular weight of the azide polyether is preferably 4380-7340 g / mol.
[0053] In the present application, the molar percentage content of in the azide polyether is preferably ≤20%, and further preferably 2.5-4%.
[0054] The present application also provides a preparation method of the azide polyether according to the above technical solution, comprising the following steps:
[0055] mixing benzyl alcohol, an organic superbase phosphazene base having the structure shown in Formula 1, 5-azido-1-pentanol glycidyl ether having the structure shown in Formula 2, and a polar organic solvent to perform an anionic polymerization reaction, to obtain the azide polyether;
[0056]
[0057]
[0058] In the present application, the raw materials used in the present application are preferably commercially available products, unless otherwise specified.
[0059] In the present application, the preparation of the 5-azido-1-pentanol glycidyl ether is preferably introduced later.
[0060] In the present application, the polar organic solvent preferably includes toluene. In the present application, the water content of the polar organic solvent is preferably <50 ppm.
[0061] In the present application, the molar ratio of the benzyl alcohol, the organic superbase phosphazene base, and the 5-azido-1-pentanol glycidyl ether is preferably 1:1:(10-80). The present application does not make specific limitations on the amount of the polar organic solvent, as long as it can sufficiently dissolve and mix other raw materials.
[0062] In the present application, the mixing of the benzyl alcohol, the organic superbase phosphazene base having the structure shown in Formula 2, the 5-azido-1-pentanol glycidyl ether, and the polar organic solvent preferably includes the following steps:
[0063] Mixing the benzyl alcohol and the polar organic solvent to obtain a benzyl alcohol solution;
[0064] Sequentially adding the organic superbase phosphazene base and the 5-azido-1-pentanol glycidyl ether to the benzyl alcohol solution.
[0065] In the present application, the addition of the organic superbase phosphazene base is preferably dropwise, and the dropwise addition rate is preferably 0.01-0.1 mL / min, and further preferably 0.05 mL / min. After the addition of the organic superbase phosphazene base, the present application preferably further includes stirring and mixing; the stirring and mixing time is preferably 0.5 h.
[0066] In the present application, the addition of the 5-azido-1-pentanol glycidyl ether is preferably dropwise, and the dropwise addition rate is preferably 0.01-0.1 mL / min, and further preferably 0.05 mL / min. After the addition of the 5-azido-1-pentanol glycidyl ether, the present application preferably further includes stirring and mixing.
[0067] In the present application, the anionic polymerization temperature is preferably 0-50°C, and further preferably 25°C; the anionic polymerization time is preferably 24-90 h, and further preferably 30-72 h.
[0068] After the anionic polymerization reaction, the present application preferably further includes sequentially performing a quenching reaction, an alumina basic column separation, and removing the solvent from the obtained eluent.
[0069] In the present application, the reagent for the quenching reaction preferably includes benzoic acid.
[0070] In the present application, the solvent for the separation of the basic alumina chromatographic column preferably comprises tetrahydrofuran.
[0071] In the present application, the method for removing the solvent in the obtained eluent preferably comprises reduced pressure distillation.
[0072] In the present application, the method for preparing the 5-azido-1-pentanol glycidyl ether preferably comprises the following steps:
[0073] The product 1 having the structure shown in formula 3, the tetrabutylammonium hydrogen sulfate having the structure shown in formula 4, the raw material 2 having the structure shown in formula 5 and a KOH solution are mixed to perform a nucleophilic substitution reaction, so as to obtain the 5-azido-1-pentanol glycidyl ether.
[0074]
[0075]
[0076]
[0077] In formula 5, X comprises -F, -Cl, -Br or -I.
[0078] In the present application, the preparation of the product 1 is preferably introduced subsequently.
[0079] In the present application, the molar ratio of the product 1, the tetrabutylammonium hydrogen sulfate and the raw material 2 is preferably (10-30):1:100, and further preferably (15-25):1:100.
[0080] In the present application, the mass concentration of the KOH solution is preferably 20-60%, and further preferably 40%. In the present application, the ratio of the amount of the KOH solution to the raw material 2 is preferably (30-80)mL:0.34mol.
[0081] In the present application, mixing the product 1 having the structure shown in formula 3, the tetrabutylammonium hydrogen sulfate having the structure shown in formula 4, the raw material 2 having the structure shown in formula 5 and the KOH solution preferably comprises the following steps: sequentially adding the tetrabutylammonium hydrogen sulfate, the raw material 2 and the product 1 into the KOH solution. In the present application, the adding mode of the tetrabutylammonium hydrogen sulfate is preferably direct adding. In the present application, the adding mode of the raw material 2 is preferably direct adding. In the present application, after adding the tetrabutylammonium hydrogen sulfate and the raw material 2, the present application preferably further comprises stirring and mixing; the stirring and mixing speed is preferably 500-800 rpm, and the time is preferably 0.5 h. In the present application, the adding mode of the product 1 is preferably dropwise adding, and the dropwise adding rate is preferably 0.01-0.1 mL / min, and further preferably 0.05 mL / min. In the present application, after adding the product 1, the present application preferably further comprises stirring and mixing, and the stirring and mixing speed is preferably 500-800 rpm, and the time is preferably 0.5 h; the stirring and mixing time is preferably counted from the completion of adding the product 1.
[0082] In the present application, the temperature of the nucleophilic substitution reaction is preferably 0-30℃, and further preferably 25℃; the time is preferably 12-36 h, and further preferably 24 h.
[0083] After the nucleophilic substitution reaction, the present application preferably further comprises post-treatment, and the post-treatment preferably comprises sequentially performing ethyl acetate extraction, washing the ethyl acetate extraction phase, drying the ethyl acetate extraction phase, removing ethyl acetate and column chromatography separation and purification.
[0084] In the present application, the washing of the ethyl acetate extraction phase preferably comprises sequentially performing deionized water washing and saturated sodium chloride washing.
[0085] In the present application, the reagent for drying the ethyl acetate extraction phase preferably comprises anhydrous sodium sulfate.
[0086] In the present application, the method for removing ethyl acetate is preferably reduced pressure distillation.
[0087] In the present application, the solvent for column chromatography separation and purification preferably comprises ethyl acetate and petroleum ether; the volume ratio of the ethyl acetate and the petroleum ether is preferably 1:(1-10), and further preferably 1:5.
[0088] In the present application, the preparation method of the product 1 preferably comprises the following steps:
[0089] Mixing the raw material 1 having the structure shown in formula 6, an alkali metal azide salt and deionized water to perform azidation reaction to obtain the product 1;
[0090]
[0091] In the formula 6, X is preferably -F, -Cl, -Br or -I, and more preferably -Cl.
[0092] In the present application, the alkali metal azide salt preferably includes sodium azide.
[0093] In the present application, the deionized water is preferably secondary RO effluent, and the conductivity of the deionized water is preferably 1-1.5 μS / cm, and more preferably 1 μS / cm.
[0094] In the present application, the molar ratio of the raw material 1 to the alkali metal azide salt is preferably 1:1.2-1.5. In the present application, the ratio of the amount of the deionized water to the raw material 1 is (20-50) mL:0.22 mol.
[0095] In the present application, mixing the raw material 1 having the structure shown in the formula 6, the alkali metal azide salt and the deionized water preferably includes the following steps:
[0096] Mixing the deionized water and sodium azide to obtain a sodium azide solution;
[0097] Adding the raw material 1 to the sodium azide solution and mixing.
[0098] In the present application, the temperature of the deionized water is preferably 0-30°C, and more preferably 25°C. In the present application, mixing the deionized water and sodium azide is preferably performed under stirring, and the stirring speed is preferably 500-800 rpm.
[0099] In the present application, the temperature of the sodium azide solution is preferably 30-80°C, and more preferably 60°C.
[0100] In the present application, the adding method of the raw material 1 is preferably dropwise adding, and the dropwise adding rate is preferably 1-10 mL / min, and more preferably 5 mL / min.
[0101] In the present application, when the raw material 1 is added to the sodium azide solution, the sodium azide solution is preferably stirred, and the stirring speed is preferably 500-800 rpm.
[0102] In the present application, adding the raw material 1 to the sodium azide solution and mixing is preferably performed under stirring.
[0103] In the present application, after adding the raw material 1 to the sodium azide solution and mixing, the mixture is preferably incubated at 80-130°C, and more preferably at 110°C.
[0104] In the present application, the temperature of the azidation reaction is preferably 100-120°C, and more preferably 110°C; the time is preferably 5-24h, and more preferably 12h. In the present application, the azidation reaction is preferably refluxed with condensed water.
[0105] After the azidation reaction, the present application preferably further comprises: cooling to room temperature, then extracting, and then washing, drying and removing the organic solvent from the obtained extraction phase. In the present application, the extraction reagent preferably comprises ethyl acetate. In the present application, the washing preferably comprises sequentially washing with deionized water and saturated sodium chloride solution. In the present application, the drying is preferably desiccant drying; the desiccant used in the desiccant drying is preferably anhydrous sodium sulfate. In the present application, the method for removing the organic solvent is preferably reduced pressure distillation.
[0106] The present application also provides the use of the azide polyether described in the above technical solution or the azide polyether obtained by the preparation method described in the above technical solution as an energetic binder.
[0107] When the azide polyether is used as an energetic binder, the present application does not specifically limit the amount of the azide polyether, which can be set by those skilled in the art according to actual needs.
[0108] The azide polyether, the preparation method and the use thereof provided by the present application will be described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.
[0109] Example 1
[0110] In a single-necked flask, 44mL of deionized water was added, and 20g of sodium azide (0.307mol) was added in batches, and was dissolved under stirring at 500rpm. After the sodium azide was completely dissolved, a sodium azide solution was obtained. The temperature of the oil bath was adjusted to 60°C, and 26.8g of 5-chloro-1-pentanol (0.22mol) was added at a rate of 5mL / min. After the addition of 5-chloro-1-pentanol was completed, the temperature of the oil bath was adjusted to 110°C, and condensed reflux water was passed, and the azidation reaction was carried out for 12h. After the reaction system was cooled to room temperature, the organic phase was extracted with ethyl acetate, and then washed with deionized water and saturated sodium chloride solution, respectively. After drying with anhydrous sodium sulfate, the organic solvent was removed by reduced pressure distillation to obtain 5-azido-1-pentanol.
[0111] In a clean round bottom flask, 57 mL of deionized water was added, 38.18 g of potassium hydroxide was added in batches, and after stirring and uniformity, a 40% mass concentration of potassium hydroide solution was obtained; the potassium hydroxide solution was placed in a low-temperature constant-temperature reaction tank, the reaction temperature was adjusted to 0°C, and after the system was stable, 1.17 g of tetrabutylammonium hydrogen sulfate (0.0034 mol) and 31.8 g of epichlorohydrin (0.34 mol) were added, and after stirring at 0°C for 0.5 h, 9.85 g of 5-azido-1-pentanol (0.08 mol) was added at a rate of 0.05 mL / min, and after continuing to incubate at 0°C for 0.5 h, the reaction system was placed at room temperature for 24 h. The organic phase was extracted with ethyl acetate, washed with deionized water and saturated sodium chloride solution respectively, dried with anhydrous sodium sulfate, and then the organic solvent was removed by distillation under reduced pressure to obtain the crude product of 5-azido-1-pentanol glycidyl ether.
[0112] The crude product of 5-azido-1-pentanol glycidyl ether was loaded into a silica gel chromatography column, purified and separated with ethyl acetate: petroleum ether = 1:5 as the developing agent, the solvent was collected, and the organic solvent was removed by distillation under reduced pressure to obtain high-purity 5-azido-1-pentanol glycidyl ether.
[0113] A previously dried Schlenk flask was subjected to three-cycle water and oxygen removal operation, 3 mL of ultra-dry toluene was added to the reactor, then 12.8 μL of benzyl alcohol (0.000012 mol) was added, and mixed uniformly. 146 μL of phosphine base (0.000012 mol) was added to the reaction system at a rate of 0.05 mL / min, and after stirring for 0.5 h, 0.94 mL of 5-azido-1-pentanol glycidyl ether (0.00025 mol) was added to the reaction container at a rate of 0.05 mL / min, and stirred uniformly, and reacted at room temperature for 30 h. After the reaction was completed, benzoic acid was added to quench the reaction, and then the reaction liquid was passed through an alkaline alumina chromatography column with tetrahydrofuran as the solvent. The organic solvent was removed by distillation under reduced pressure to obtain an anionic polymeric azide polyether with a molecular weight of 4380 g / mol and a molecular weight distribution of 1.12.
[0114] Example 2
[0115] In a single-neck flask, 44 mL of deionized water was added, 20 g of sodium azide (0.307 mol) was added in batches, and dissolved under stirring at 500 rpm. After the sodium azide was completely dissolved, a sodium azide solution was obtained. The temperature of the oil bath was adjusted to 60°C, and 26.8 g of 5-chloro-1-pentanol (0.22 mol) was added at a rate of 5 mL / min. After the 5-chloro-1-pentanol was completely added, the temperature of the oil bath was adjusted to 110°C, and the condensation reflux water was passed. After the azidation reaction was carried out for 12 h, the reaction system was cooled to room temperature, and the organic phase was extracted with ethyl acetate, washed with deionized water and saturated sodium chloride solution, respectively, dried with anhydrous sodium sulfate, and then the organic solvent was removed by distillation under reduced pressure to obtain 5-azido-1-pentanol.
[0116] In a clean round-bottom flask, 57 mL of deionized water was added, and 38.18 g of potassium hydroxide was added in batches. After stirring uniformly, a potassium hydroxide solution with a mass concentration of 40% was obtained. The potassium hydroxide solution was placed in a low-temperature constant-temperature reaction tank, the reaction temperature was adjusted to 0°C, and after the system was stable, 1.17 g of tetrabutylammonium hydrogen sulfate (0.0034 mol) and 31.8 g of epichlorohydrin (0.34 mol) were added. After stirring at 0°C for 0.5 h, 9.85 g of 5-azido-1-pentanol (0.08 mol) was added at a rate of 0.05 mL / min. After continuing to incubate at 0°C for 0.5 h, the reaction system was placed at room temperature for 24 h. The organic phase was extracted with ethyl acetate, washed with deionized water and saturated sodium chloride solution, respectively, dried with anhydrous sodium sulfate, and then the organic solvent was removed by distillation under reduced pressure to obtain 5-azido-1-pentanol glycidyl ether crude product.
[0117] The 5-azido-1-pentanol glycidyl ether crude product obtained was loaded into a silica gel chromatographic column, purified and separated with ethyl acetate: petroleum ether = 1:5 as the developing agent, the solvent was collected, and the organic solvent was removed by distillation under reduced pressure to obtain high-purity 5-azido-1-pentanol glycidyl ether.
[0118] A previously dried Schlenk flask was subjected to three-cycle water and oxygen removal operation, 3 mL of ultradry toluene was added to the reactor, followed by the addition of 12.8 μL of benzyl alcohol (0.000012 mol), and mixed uniformly. 146 μL of phosphine base (0.000012 mol) was added to the reaction system at a rate of 0.05 mL / min, stirred for 0.5 h, and then 1.4 mL of 5-azido-1-pentanol glycidyl ether (0.00037 mol) was added to the reaction container at a rate of 0.05 mL / min, stirred uniformly, and reacted at room temperature for 30 h. After the reaction was completed, benzoic acid was added to quench the reaction, and then the reaction liquid was passed through an alkaline alumina chromatographic column with tetrahydrofuran as the solvent. The organic solvent was removed by distillation under reduced pressure to obtain an anionic polyazide polyether with a molecular weight of 5260 g / mol and a molecular weight distribution of 1.10.
[0119] Example 3
[0120] In a single-necked flask, 44 mL of deionized water was added, 20 g of sodium azide (0.307 mol) was added in batches, and the solution was stirred at 500 rpm until the sodium azide was completely dissolved to obtain a sodium azide solution; the temperature of the oil bath was adjusted to 60°C, and 26.8 g of 5-chloro-1-pentanol (0.22 mol) was added at a rate of 5 mL / min; after the 5-chloro-1-pentanol was completely added, the temperature of the oil bath was adjusted to 110°C, and the solution was mixed uniformly; then, the reaction was carried out for 12 h under reflux with water; after the reaction system was cooled to room temperature, the organic phase was extracted with ethyl acetate, and then washed with deionized water and saturated sodium chloride solution, respectively; after drying with anhydrous sodium sulfate, the organic solvent was removed by distillation under reduced pressure to obtain 5-azido-1-pentanol.
[0121] In a clean round-bottom flask, 57 mL of deionized water was added, and 38.18 g of potassium hydroxide was added in batches; after stirring uniformly, a potassium hydroxide solution with a mass concentration of 40% was obtained; the potassium hydroxide solution was placed in a low-temperature constant-temperature reaction tank, and the reaction temperature was adjusted to 0°C; after the system was stabilized, 1.17 g of tetrabutylammonium hydrogen sulfate (0.0034 mol) and 31.8 g of epichlorohydrin (0.34 mol) were added; after stirring at 0°C for 0.5 h, 9.85 g of 5-azido-1-pentanol (0.08 mol) was added at a rate of 0.05 mL / min; after continuing to incubate at 0°C for 0.5 h, the reaction system was placed at room temperature for 24 h; the organic phase was extracted with ethyl acetate, and then washed with deionized water and saturated sodium chloride solution, respectively; after drying with anhydrous sodium sulfate, the organic solvent was removed by distillation under reduced pressure to obtain 5-azido-1-pentanol glycidyl ether crude product.
[0122] The 5-azido-1-pentanol glycidyl ether crude product was loaded into a silica gel chromatography column, and purified and separated with ethyl acetate: petroleum ether = 1:5 as the developing agent; after the solvent was collected, the organic solvent was removed by distillation under reduced pressure to obtain high-purity 5-azido-1-pentanol glycidyl ether.
[0123] A previously oven-dried Schlenk flask was subjected to three cycles of water and oxygen removal, 3 mL of super-dry toluene was added into the reactor, followed by 12.8 μL of benzyl alcohol (0.000012 mol), mixed well. 146 μL of phosphine base (0.000012 mol) was added dropwise into the reaction system at a rate of 0.05 mL / min, after stirring for 0.5 h, 1.90 mL of 5-azido-1-pentanol glycidyl ether (0.0005 mol) was slowly added into the reaction vessel at a rate of 0.05 mL / min, stirred well, and reacted at room temperature for 30 h. After the reaction was completed, benzoic acid was added to quench the reaction, followed by passing the reaction solution through an alkaline alumina chromatographic column with tetrahydrofuran as the solvent. The organic solvent was removed by distillation under reduced pressure to obtain an anionic polymeric azide polyether with a molecular weight of 7340 g / mol and a molecular weight distribution of 1.08.
[0124] Figure 1 NMR spectra of raw material 1, product 1 and product 2 in Example 1.
[0125] Figure 2 NMR spectra of azide polyethers obtained in Examples 1-3, from Figure 2 It can be seen that the NMR peak position and integration correspond to the structure of the substance, indicating that the corresponding substance is successfully synthesized.
[0126] Figure 3 GPC elution curves of azide polyethers obtained in Examples 1-3, from Figure 3 It can be seen that the number average molecular weight of the azide polyether obtained in Example 1 is 4380 g / mol, the number average molecular weight of the azide polyether obtained in Example 2 is 5240 g / mol, and the number average molecular weight of the azide polyether obtained in Example 3 is 7420 g / mol.
[0127] Figure 4 MALDI-TOF MS curve of azide polyether obtained in Example 1, from Figure 4 It can be seen that the number average molecular weight of the azide polyether obtained in Example 1 is 4368 g / mol, the weight average molecular weight is 4892 g / mol, and the molecular weight distribution coefficient is 1.12.
[0128] Figure 5 Enlarged view of the MALDI-TOF MS curve of the azide polyether obtained in Example 1, from Figure 5 It can be seen that the relative mass of each repeating unit in the azide polyether obtained in Example 1 is 82.
[0129] Figure 6 SEC elution curve of azide polyether obtained in Example 2, from Figure 6It can be seen that the number average molecular weight of the azide polyether obtained in Example 2 is 5246 g / mol, the weight average molecular weight is 5770 g / mol, and the molecular weight distribution coefficient is 1.10.
[0130] Figure 7 The SEC elution curve of the anionic polymerization azide polyether obtained in Example 3 is shown in Figure 3. Figure 7 It can be seen that the number average molecular weight of the azide polyether obtained in Example 3 is 7431 g / mol, the weight average molecular weight is 8025 g / mol, and the molecular weight distribution coefficient is 1.08.
[0131] Figure 8 The tensile curve of the film prepared from the azide polyether obtained in Examples 1-3 is shown in Figure 4. Figure 8 It can be seen that the tensile strength of the azide polyether obtained in Example 1 is 337.5 kPa, the elongation at break is 1125%, the tensile strength of the azide polyether obtained in Example 2 is 58.2 kPa, the elongation at break is 915%, and the tensile strength of the azide polyether obtained in Example 3 is 13.6 kPa, the elongation at break is 675%.
[0132] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.
Claims
1. An azide polyether, characterized in that, It has the structure shown in Equation I: Formula I; In Equation I, n is 23~39; The preparation method of the aforementioned azide polyether includes the following steps: Benzyl alcohol, an organic superbase phosphononitrile having the structure shown in Formula 1, 5-azido-1-pentanol glycidyl ether having the structure shown in Formula 2, and a polar organic solvent are mixed and subjected to anionic polymerization to obtain the azide polyether. Formula 1; Formula 2; The molar ratio of benzyl alcohol, organic superbase phosphononitrile base, and 5-azido-1-pentanol glycidyl ether is 1:1:
20.
2. The azide polyether according to claim 1, characterized in that, The number-average molecular weight of the azide polyether is 4380~7340 g / mol.
3. The method for preparing the azide polyether according to claim 1 or 2, characterized in that, Includes the following steps: Benzyl alcohol, an organic superbase phosphononitrile having the structure shown in Formula 1, 5-azido-1-pentanol glycidyl ether having the structure shown in Formula 2, and a polar organic solvent are mixed and subjected to anionic polymerization to obtain the azide polyether. Formula 1; Formula 2; The molar ratio of benzyl alcohol, organic superbase phosphononitrile base, and 5-azido-1-pentanol glycidyl ether is 1:1:
20.
4. The preparation method according to claim 3, characterized in that, The preparation method of the 5-azido-1-pentanol glycidyl ether includes the following steps: The product 1 having the structure shown in Formula 3, the tetrabutylammonium hydrogen sulfate having the structure shown in Formula 4, the raw material 2 having the structure shown in Formula 5, and KOH solution were mixed and subjected to a nucleophilic substitution reaction to obtain the 5-azido-1-pentanol glycidyl ether. Formula 3; Equation 4; Formula 5; In Formula 5, X is -F, -Cl, -Br, or -I.
5. The preparation method according to claim 4, characterized in that, The preparation method of product 1 includes the following steps: Raw material 1, which has the structure shown in Formula 6, alkali metal azide salt, and deionized water are mixed and azide reaction is carried out to obtain product 1. Formula 6; In Formula 6, X is -F, -Cl, -Br, or -I.
6. The preparation method according to claim 3, characterized in that, The anionic polymerization reaction is carried out at a temperature of 0~50℃ for a time of 24~90h.
7. The preparation method according to claim 4, characterized in that, The molar ratio of product 1, tetrabutylammonium hydrogen sulfate and raw material 2 is (10~30):1:100; The nucleophilic substitution reaction is carried out at a temperature of 0-30°C for a time of 12-36 hours.
8. The preparation method according to claim 5, characterized in that, The molar ratio of raw material 1 to alkali metal azide salt is 1:1.2~1.5; The azide reaction is carried out at a temperature of 100-120°C for 5-24 hours.
9. The application of the azide polyether according to claim 1 or 2 or the azide polyether prepared by the preparation method according to any one of claims 3 to 8 as an energetic binder.