CN103980128B - 2,6-dinitrobenzene is to the synthetic method of two benzylalcohol nitric ethers - Google Patents
2,6-dinitrobenzene is to the synthetic method of two benzylalcohol nitric ethers Download PDFInfo
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- CN103980128B CN103980128B CN201410233906.8A CN201410233906A CN103980128B CN 103980128 B CN103980128 B CN 103980128B CN 201410233906 A CN201410233906 A CN 201410233906A CN 103980128 B CN103980128 B CN 103980128B
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- dinitrobenzene
- benzylalcohol
- methylene dichloride
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- benzylalcohols
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Abstract
The present invention relates to energetic plasticiser preparation method, particularly 2,6-dinitrobenzenes are to the method for two benzylalcohol nitric ethers, adopt nitrosonitric acid and 2,6-dinitrobenzene is raw material to two benzylalcohols, obtains 2,6-dinitrobenzene to two benzylalcohol nitric ethers through production technique simple and easy to control synthesis.By designing the structure of energetic plasticiser, change the thinking that traditional itrate group softening agent utilizes inertia polyvalent alcohol to be raw material, use substitutes inertia Organic Alcohol with the aromatic alcohol containing energy group and prepares nitrate esters softening agent, the structure introduced in plasticizer molecule structure contains phenyl ring and nitro, this structure and 2,4,6-trotyl (TNT) structure is close, the interaction between softening agent and explosive molecules can be strengthened, thermally-stabilised increase and reduce the sensitivity of softening agent, thus increase the security of energetic material system.
Description
Technical field
The present invention relates to energetic plasticiser preparation method, particularly 2,6-dinitrobenzenes are to the method for two benzylalcohol nitric ethers.
Background technology
Energetic plasticiser improves explosive wastewater system mechanical property, to adapt to weapon technologies development, to meet the important channel that new weapon uses needs.Energetic plasticiser is as the important component part of propelling charge, propelling agent and explosive, and it affects the mechanical property of system to a great extent, and softening agent determines corresponding complete processing simultaneously.The domestic and international preparation research for energetic plasticiser is more at present, mainly concentrates in different molecular structures and introduces containing energy group, as itrate group (-ONO
2), nitro (-NO
2), nitramino (-NNO
2) and azido-(-N
3) etc.Which not only adds energy, and improve the oxygen balance containing energy system.
The Typical Representative of the nitrate esters energetic plasticiser containing single itrate group is nitroglycerine (NG), it is a kind of conventional high energy, high-density softening agent, still occupies certain status at present in development high-energy propellant, smokeless propellant and nitramine gun propelllant.But NG zero pour is higher, and sensitivity is high, vapour pressure is also high, can make propelling agent generation embrittlement, there is migration problem again in storage under low temperature, makes it there is certain danger in use.
Nitro (-NO
2) be a kind of containing energy group in explosive molecules, Polynitroaramatics is widely used energetic material, as 2，4，6-trinitrotoluene.
2,2-dinitrobenzene-1,3-dinitro oxygen base propane and 2,2,2-trinitro--2-nitre oxygen base ether is had containing energy group softening agent at present containing itrate group and the two of nitro.Wherein, the thermostability of 2,2-dinitrobenzene-1,3-dinitro oxygen base propane is poor, keeps 65 DEG C, within 24 hours, will decompose.Need Silver Nitrate to participate in reaction in the building-up process of 2,2,2-trinitro--2-nitre oxygen base ether, add production cost.And then report is had no to the research that two benzylalcohol nitric ethers synthesize for 2,6-dinitrobenzenes.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of 2,6-dinitrobenzene is to the method for two benzylalcohol nitric ethers, by designing the structure of softening agent thus increasing the kind containing energy group, improve the stability of itrate group softening agent, with containing can the consistency of system, simultaneously for synthesis containing two kinds containing the softening agent of group providing new approaches.
The method is that Material synthesis 2,6-dinitrobenzene is to two benzylalcohol nitric ethers with 2,6-dinitrobenzene to two benzylalcohols and nitrosonitric acid.Specifically, comprise the following steps:
(1) 2,6-dinitrobenzene is joined in dichloromethane solvent to two benzylalcohols, stir and form mixture, 0-30 DEG C of constant temperature;
(2) nitrosonitric acid is added drop-wise to 2,6-dinitrobenzene in the mixture of two benzylalcohols and methylene dichloride, 2,6-dinitrobenzene is 1:2 ~ 1:10 to two benzylalcohols and nitrosonitric acid mol ratio, dropwise rear continuation reaction 0.5 ~ 2h, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ether mixed solutions;
(3) 2,6-dinitrobenzene is transferred to separatory in separating funnel to two benzylalcohol nitric ether mixed solutions, discard upper water solution;
(4) methylene dichloride in lower floor's mixture is 5% sodium hydroxide solution washing by mass concentration mutually, and washing to pH value is 5 ~ 6, then carries out washing 3 times with the deionized water with methylene dichloride equal quantities, discards upper water solution;
(5) methylene dichloride phase underpressure distillation, utilizes Rotary Evaporators to reduce pressure at 35-45 DEG C and removes methylene dichloride, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ethers.
Continuation reaction conditions described in step (2) is react 0.5 ~ 2h under 5 DEG C of constant temperature.
Step (2) described reaction process provides temperature of reaction and stirring by heat-collecting magnetic stirring device, in glass three-necked bottle, complete reaction.
2,6-dinitrobenzenes provided by the invention, to the method for two benzylalcohol nitric ethers, adopt nitrosonitric acid and 2,6-dinitrobenzene to be raw material to two benzylalcohols, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ethers through production technique simple and easy to control synthesis.By designing the structure of energetic plasticiser, change the thinking that traditional itrate group softening agent utilizes inertia polyvalent alcohol to be raw material, use substitutes inertia Organic Alcohol with the aromatic alcohol containing energy group and prepares nitrate esters softening agent, the structure introduced in plasticizer molecule structure contains phenyl ring and nitro, this structure and 2,4,6-trotyl (TNT) structure is close, the interaction between softening agent and explosive molecules can be strengthened, thermally-stabilised increase and reduce the sensitivity of softening agent, thus increase the security of energetic material system.
Accompanying drawing explanation
Fig. 1 is that obtained 2, the 6-dinitrobenzenes of embodiment 1 are to the infrared figure of two benzylalcohol nitric ethers;
Fig. 2 is that 2, the 6-dinitrobenzenes that embodiment 1 obtains are composed two benzylalcohol nitric ether nuclear magnetic resonance spectrum hydrogen;
Fig. 3 is that 2, the 6-dinitrobenzenes that embodiment 1 obtains are composed two benzylalcohol nitric ether nuclear magnetic resonance spectrum carbon.
Embodiment
The specific embodiment of the present invention is described in conjunction with the embodiments.
Embodiment 1
2,6-dinitrobenzene, to the mol ratio 1:4 of two benzylalcohols and nitrosonitric acid, joins in methylene dichloride to two benzylalcohols by 2,6-dinitrobenzene, stirs, and keeps 5 DEG C of constant temperature in ice-water bath.
The nitrosonitric acid of metering is added drop-wise to 2,6-dinitrobenzene in the mixture of two benzylalcohols and methylene dichloride, dropwises rear reaction 1h, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ether mixed solutions.
By 2,6-dinitrobenzene transfers to separatory in separating funnel to two benzylalcohol nitric ether mixed solutions, discards upper water solution, and lower floor's methylene dichloride washs until pH value is 5 ~ 6 with 5% sodium hydroxide solution mutually, continue to carry out washing 3 times with the deionized water with methylene dichloride equal quantities, discard upper water solution.At 35 DEG C, utilize the underpressure distillation of Rotary Evaporators methylene dichloride phase, the methylene dichloride that reduces pressure away had both obtained 2,6-dinitrobenzene to two benzylalcohol nitric ethers.
Fig. 1 is that the present embodiment 2,6-dinitrobenzene is to two benzylalcohol nitric ether infrared spectra spectrograms.3091.24cm
-1for c h bond stretching vibration peak in phenyl ring, 2911.29cm
-1for-CH
2antisymmetric stretching vibration peak, 1647.59cm
-1, 1280.71cm
-1, 847.35cm
-1itrate group charateristic avsorption band, 1544.29cm
-1nitro antisymmetric stretching vibration peak, 1348.36cm
-1nitro symmetrical stretching vibration peak.
Fig. 2 is that 2,6-dinitrobenzenes prepared by the present embodiment are composed two benzylalcohol nitric ether nuclear magnetic resonance spectrum hydrogen.
1hNMR (600M, CD
3cOCD
3) δ 5.91 (2H, s, O-CH
2), 6.10 (2H, s, O-CH
2), 8.53 (2H, s, Ar-CH), solvent acetone peak is 2.0 peaks, place.
Fig. 3 is that 2,6-dinitrobenzenes prepared by the present embodiment are composed two benzylalcohol nitric ether nuclear magnetic resonance spectrum carbon.
13cNMR (150M, CD
3cOCD
3) δ 65.32 (CH
2-O), 71.69 (CH
2-O), 122.01 (Ar-C-3), 128.60,128.91 (Ar-C-5,7), 138.49 (Ar-C-6), 151.06 (Ar-C-4,8), solvent acetone peak is 28.9 place's multiplets and 205.52 peaks, place.
Show that the material synthesized is that 2,6-dinitrobenzene is to two benzylalcohol nitric ethers by infrared spectrum and nmr analysis.
Embodiment 2
2,6-dinitrobenzene, to the mol ratio 1:2 of two benzylalcohols and nitrosonitric acid, joins in methylene dichloride to two benzylalcohols by 2,6-dinitrobenzene, stirs, 0 DEG C of constant temperature in ice-water bath.
The nitrosonitric acid of metering is added drop-wise to 2,6-dinitrobenzene in the mixture of two benzylalcohols and methylene dichloride, dropwises rear reaction 1h, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ether mixed solutions.
By 2,6-dinitrobenzene transfers to separatory in separating funnel to two benzylalcohol nitric ether mixed solutions, discards upper water solution, and lower floor's methylene dichloride washs until pH value is 5 ~ 6 with 5% sodium hydroxide solution mutually, continue to carry out washing 3 times with the deionized water with methylene dichloride equal quantities, discard upper water solution.At 35 DEG C, utilize the underpressure distillation of Rotary Evaporators methylene dichloride phase, the methylene dichloride that reduces pressure away had both obtained 2,6-dinitrobenzene to two benzylalcohol nitric ethers.
Embodiment 3
2,6-dinitrobenzene, to the mol ratio 1:6 of two benzylalcohols and nitrosonitric acid, joins in methylene dichloride to two benzylalcohols by 2,6-dinitrobenzene, stirs, 10 DEG C of constant temperature.
The nitrosonitric acid of metering is added drop-wise to 2,6-dinitrobenzene in the mixture of two benzylalcohols and methylene dichloride, dropwises rear reaction 0.5h, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ether mixed solutions.
By 2,6-dinitrobenzene transfers to separatory in separating funnel to two benzylalcohol nitric ether mixed solutions, discards upper water solution, and lower floor's methylene dichloride washs until pH value is 5 ~ 6 with 5% sodium hydroxide solution mutually, continue to carry out washing 3 times with the deionized water with methylene dichloride equal quantities, discard upper water solution.At 45 DEG C, utilize the underpressure distillation of Rotary Evaporators methylene dichloride phase, the methylene dichloride that reduces pressure away had both obtained 2,6-dinitrobenzene to two benzylalcohol nitric ethers.
Embodiment 4
2,6-dinitrobenzene, to the mol ratio 1:8 of two benzylalcohols and nitrosonitric acid, joins in methylene dichloride to two benzylalcohols by 2,6-dinitrobenzene, stirs, 15 DEG C of constant temperature in ice-water bath.
The nitrosonitric acid of metering is added drop-wise to 2,6-dinitrobenzene in the mixture of two benzylalcohols and methylene dichloride, dropwises rear reaction 2h, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ether mixed solutions.
By 2,6-dinitrobenzene transfers to separatory in separating funnel to two benzylalcohol nitric ether mixed solutions, discards upper water solution, and lower floor's methylene dichloride washs until pH value is 6 ~ 7 with 5% sodium hydroxide solution mutually, continue to carry out washing 3 times with the deionized water with methylene dichloride equal quantities, discard upper water solution.At 40 DEG C, utilize the underpressure distillation of Rotary Evaporators methylene dichloride phase, the methylene dichloride that reduces pressure away had both obtained 2,6-dinitrobenzene to two benzylalcohol nitric ethers.
Embodiment 5
2,6-dinitrobenzene, to the mol ratio 1:10 of two benzylalcohols and nitrosonitric acid, joins in methylene dichloride to two benzylalcohols by 2,6-dinitrobenzene, stirs, 20 DEG C of constant temperature.
The nitrosonitric acid of metering is added drop-wise to 2,6-dinitrobenzene in the mixture of two benzylalcohols and methylene dichloride, dropwises rear reaction 2h, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ether mixed solutions.
By 2,6-dinitrobenzene transfers to separatory in separating funnel to two benzylalcohol nitric ether mixed solutions, discards upper water solution, and lower floor's methylene dichloride washs until pH value is 4 ~ 5 with 5% sodium hydroxide solution mutually, continue to carry out washing 3 times with the deionized water with methylene dichloride equal quantities, discard upper water solution.At 40 DEG C, utilize the underpressure distillation of Rotary Evaporators methylene dichloride phase, the methylene dichloride that reduces pressure away had both obtained 2,6-dinitrobenzene to two benzylalcohol nitric ethers.
Embodiment 6
2,6-dinitrobenzene, to the mol ratio 1:10 of two benzylalcohols and nitrosonitric acid, joins in methylene dichloride to two benzylalcohols by 2,6-dinitrobenzene, stirs, 30 DEG C of constant temperature.
The nitrosonitric acid of metering is added drop-wise to 2,6-dinitrobenzene in the mixture of two benzylalcohols and methylene dichloride, dropwises rear reaction 1h, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ether mixed solutions.
By 2,6-dinitrobenzene transfers to separatory in separating funnel to two benzylalcohol nitric ether mixed solutions, discards upper water solution, and lower floor's methylene dichloride washs until pH value is 6 ~ 7 with 5% sodium hydroxide solution mutually, continue to carry out washing 3 times with the deionized water with methylene dichloride equal quantities, discard upper water solution.At 40 DEG C, utilize the underpressure distillation of Rotary Evaporators methylene dichloride phase, the methylene dichloride that reduces pressure away had both obtained 2,6-dinitrobenzene to two benzylalcohol nitric ethers.
Claims (2)
1.2,6-dinitrobenzene, to the synthetic method of two benzylalcohol nitric ethers, is characterized in that: be that Material synthesis 2,6-dinitrobenzene is to two benzylalcohol nitric ethers with 2,6-dinitrobenzene to two benzylalcohols and nitrosonitric acid; 2,6-described dinitrobenzenes, to the synthetic method of two benzylalcohol nitric ethers, comprise the following steps:
(1) 2,6-dinitrobenzene is joined in dichloromethane solvent to two benzylalcohols, stir and form mixture, 0-30 DEG C of constant temperature;
(2) nitrosonitric acid is added drop-wise to 2,6-dinitrobenzene in the mixture of two benzylalcohols and methylene dichloride, 2,6-dinitrobenzene is 1:2 ~ 1:10 to two benzylalcohols and nitrosonitric acid mol ratio, dropwise rear continuation reaction 0.5 ~ 2h, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ether mixed solutions;
(3) 2,6-dinitrobenzene is transferred to separatory in separating funnel to two benzylalcohol nitric ether mixed solutions, discard upper water solution;
(4) methylene dichloride in lower floor's mixture is 5% sodium hydroxide solution washing by mass concentration mutually, and washing to pH value is 5 ~ 6, then carries out washing 3 times with the deionized water with methylene dichloride equal quantities, discards upper water solution;
(5) methylene dichloride phase underpressure distillation, utilizes Rotary Evaporators to reduce pressure at 35-45 DEG C and removes methylene dichloride, obtain 2,6-dinitrobenzene to two benzylalcohol nitric ethers.
2. 2,6-dinitrobenzenes according to claim 1 are to the synthetic method of two benzylalcohol nitric ethers, it is characterized in that: the continuation reaction conditions described in step (2) is react 0.5 ~ 2h under 5 DEG C of constant temperature.
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