CN104650338A - Preparation method of 3,3-bi(nitrine methyl) epoxybutane and tetrahydrofuran copolymer - Google Patents
Preparation method of 3,3-bi(nitrine methyl) epoxybutane and tetrahydrofuran copolymer Download PDFInfo
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- CN104650338A CN104650338A CN201410767555.9A CN201410767555A CN104650338A CN 104650338 A CN104650338 A CN 104650338A CN 201410767555 A CN201410767555 A CN 201410767555A CN 104650338 A CN104650338 A CN 104650338A
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Abstract
The invention discloses a preparation method of a 3,3-bi(nitrine methyl) epoxybutane and tetrahydrofuran copolymer, relates to a preparation method of the 3,3-bi(nitrine methyl) epoxybutane and tetrahydrofuran copolymer, and in particular relates to a method for preparing the 3,3-bi(nitrine methyl) epoxybutane and tetrahydrofuran copolymer by performing ring opening copolymerization and catalytic nitrogenization on 3,3-bi(chloromethyl) epoxybutane. The method is simple and easy to carry out. Because a method for preparing bi(chloromethyl) polyether at first and nitriding at last to obtain a nitrine rubber product is adopted, a high-sensitivity nitrine monomer purification step is avoided, the safety hidden troubles of operation site are eliminated, and the problem of an existing production method is solved. In a process for preparing the nitrine rubber by nitrogenization of the bi(chloromethyl) polyether, a method of addition of sodium iodide is adopted, and double-decomposition exchange reaction on iodine atoms of halogen elements and chloride atoms in the bi(chloromethyl) polyether is utilized, so that a nitrogenization reaction process is accelerated, and the complete nitrogenization reaction is carried out; and therefore, the reaction effect is achieved and the product quality is greatly improved.
Description
Technical field
The present invention relates to a kind of 3, the preparation method of two (azido-methyl) butylene oxide ring of 3-and tetrahydrofuran copolymer, specifically with cyclisation thing monomer 3, two (chloromethyl) butylene oxide ring of 3-, the preparation method of two (azido-methyl) butylene oxide ring of 3,3-and tetrahydrofuran copolymer is prepared through ring opening copolymer, catalysis azido reaction.
Background technology:
Since 19th-century hydrazoic acid is found, triazo-compound causes the great interest of region of chemistry, and people are to synthetic method, the structure determination of triazo-compound and should be used as the wide research sent out.Azide polyethers can give the energy characteristics of propelling agent excellence and good mechanical property, propelling agent detectable signal can be reduced, and PBT azide propellant sensitivity is low, this nitrine glue is adopted to be one of important channel of new generation high energy, insensitiveness and low signature solid propellant.
Domestic conventional fabrication techniques is high temperature system pure 3, two (azido-methyl) butylene oxide ring of 3-, then by 1,4-butyleneglycol and boron trifluoride. etherate is added in tetrahydrofuran (THF), obtained initiator under whipped state, then by cyclisation monomer 3, two (azido-methyl) butylene oxide ring of 3-adds in initiator, react certain hour at a lower temperature, again through two (azido-methyl) butylene oxide ring of the operations such as extraction, washing, distillation obtained 3,3-and tetrahydrofuran copolymer.Manufacturing nitrine glue is adopt two (azido-methyl) oxetane monomer of first preparation, then nitrine glue product is prepared in ring-opening polymerization.Because two (azido-methyl) oxetane monomer sensitivity is high, therefore pure processed time pyrogenic distillation operation in there is very large danger, for operation field bring safety on hidden danger.
Summary of the invention
For above-mentioned situation, the object of this invention is to provide one and first prepare two (chloromethyl) polyethers, last azide obtains the method for nitrine glue product.So avoid the pure step processed of nitrine monomer of hypersensitivity, the potential safety hazard at cancel job scene.Solve existing production method Problems existing.
Technical scheme of the present invention is as follows;
1, technical formula
Above-mentioned methylene dichloride (solvent) also can be ethylene dichloride or trichloromethane
2, preparation method:
In proportion by methylene dichloride, 1,4-butyleneglycol, boron trifluoride. etherate is added in tetrahydrofuran (THF), obtained initiator, then by cyclisation monomer 3, two (chloromethyl) butylene oxide ring of 3-is added dropwise in initiator, be cooled to 0 degree Celsius, dripping 3,3-two (chloromethyl) butylene oxide ring time is 1 ~ 2 hour.Reaction times remains on 10 ~ 20 hours.Add extraction agent, stir 0.5 hour, then wash 0.5 hour, two (chloromethyl) butylene oxide ring tetrahydrofuran copolymer of obtained 3,3-.And then adding sodium iodide, temperature of reaction rises to room temperature.Add sodiumazide again, carry out azido reaction, the reaction times is 10 ~ 15 hours.Again through washing 0.5 hour, steam solvent, two (azido-methyl) butylene oxide ring of obtained 3,3-and tetrahydrofuran copolymer.
Reaction equation is as follows:
The inventive method is simple, easy to implement.Due to employing is first prepare two (chloromethyl) polyethers, and last azide obtains the method for nitrine glue product.Avoid the pure step processed of nitrine monomer of hypersensitivity, the potential safety hazard at cancel job scene.Solve existing production method Problems existing.Preparing in the technique of nitrine glue by two (chloromethyl) polyethers azide, the present invention adopts the method adding sodium iodide, utilize the chlorine atom generation metathesis exchange reaction in the atomic iodine and two (chloromethyl) polyethers being all halogen element, thus promote azido reaction process, and make azido reaction complete.Reaction effect and quality product are increased substantially.
The present invention is without accompanying drawing
Embodiment
Example 1
Get 500ml four-hole boiling flask, be equipped with mechanical stirring, constant pressure funnel, water at low temperature bath, thermometer, add 26g methylene dichloride, add 1.5g1,4-butyleneglycol, 3.08g boron trifluoride ethyl ether complex, 13.6g tetrahydrofuran (THF), initiator is prepared under room temperature state, be cooled to 0 DEG C, 3 are dripped in 1 ~ 2 hour, two (chloromethyl) butylene oxide ring 24g of 3-, temperature 0 ± 2 DEG C reaction 12 hours, then adds 50g dichloromethane extraction, add two (azido-methyl) butylene oxide ring of obtained 3, the 3-of 200g water washing and tetrahydrofuran copolymer.
Take 0.5g sodium iodide, add 3, in two (azido-methyl) butylene oxide ring of 3-and tetrahydrofuran copolymer solution, at ambient temperature, add sodiumazide 20g, react 10 hours, add 200g water and wash 0.5 hour, steam solvent, obtain two (azido-methyl) butylene oxide ring of 3,3-and tetrahydrofuran copolymer.
Example 2
Get: 1000ml four-hole boiling flask, be equipped with mechanical stirring, constant pressure funnel, water at low temperature bath, thermometer, add 52g ethylene dichloride, add 2.6g1,4-butyleneglycol, 6.1g boron trifluoride ethyl ether complex, 27.2g tetrahydrofuran (THF), initiator is prepared under room temperature state, be cooled to-2 DEG C, 3 are dripped in 1 ~ 2 hour, two (chloromethyl) butylene oxide ring 48g of 3-, temperature 0 ± 2 DEG C reaction 18 hours, then through extraction, two (chloromethyl) butylene oxide ring tetrahydrofuran copolymer of obtained 3, the 3-of neutralization;
Take 1.5g sodium iodide, add 3, in two (chloromethyl) butylene oxide ring tetrahydrofuran copolymer solution of 3-, at ambient temperature, add sodiumazide 40g, react 12 hours, add 200g water and wash 0.5 hour, steam solvent, obtain two (azido-methyl) butylene oxide ring tetrahydrofuran copolymer of 3,3-.
Claims (1)
- The preparation method of two (azido-methyl) butylene oxide ring of 1.3,3-and tetrahydrofuran copolymer, is characterized in that;(1), technical formulaAbove-mentioned methylene dichloride (solvent) also can be ethylene dichloride or trichloromethane(2), preparation method:In proportion by methylene dichloride, 1, 4-butyleneglycol, boron trifluoride. etherate is added in tetrahydrofuran (THF), obtained initiator, then by cyclisation monomer 3, two (chloromethyl) butylene oxide ring of 3-is added dropwise in initiator, be cooled to 0 degree Celsius, drip 3, 3-two (chloromethyl) butylene oxide ring time is 1 ~ 2 hour, reaction times remains on 10 ~ 20 hours, add extraction agent, stir 0.5 hour, then wash 0.5 hour, obtained 3, two (chloromethyl) butylene oxide ring tetrahydrofuran copolymer of 3-, and then add sodium iodide, temperature of reaction rises to room temperature, add sodiumazide again, carry out azido reaction, reaction times is 10 ~ 15 hours, again through washing 0.5 hour, steam solvent, obtained 3, two (azido-methyl) butylene oxide ring of 3-and tetrahydrofuran copolymer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410767555.9A CN104650338A (en) | 2014-12-03 | 2014-12-03 | Preparation method of 3,3-bi(nitrine methyl) epoxybutane and tetrahydrofuran copolymer |
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| CN201410767555.9A CN104650338A (en) | 2014-12-03 | 2014-12-03 | Preparation method of 3,3-bi(nitrine methyl) epoxybutane and tetrahydrofuran copolymer |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713192A (en) * | 2016-02-01 | 2016-06-29 | 营口天元化工研究所股份有限公司 | 3,3-bis (azidoferrocene) epoxybutane/tetrahydrofuran polyether and synthetic method |
| CN105753909A (en) * | 2016-02-01 | 2016-07-13 | 营口天元化工研究所股份有限公司 | 3, 3-bis(azido ferrocene) epoxy butane polyether and synthetic method |
| CN110018267A (en) * | 2019-04-16 | 2019-07-16 | 中国人民解放军国防科技大学 | Low-temperature mechanical property estimation method for PBT propellant based on reversed-phase gas chromatography data and formula |
| CN110059296A (en) * | 2019-04-16 | 2019-07-26 | 中国人民解放军国防科技大学 | High-temperature mechanical property estimation method for PBT propellant based on reversed-phase gas chromatography data and formula |
| CN111440307A (en) * | 2020-04-09 | 2020-07-24 | 苏州大学 | High-functionality azide glue and preparation method thereof |
| CN114558530A (en) * | 2022-01-28 | 2022-05-31 | 杭州三隆新材料有限公司 | Method and device for decomposing tetrahydrofuran and neopentyl glycol copolymer and separating and recycling tetrahydrofuran and neopentyl glycol in decomposition product |
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2014
- 2014-12-03 CN CN201410767555.9A patent/CN104650338A/en active Pending
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713192A (en) * | 2016-02-01 | 2016-06-29 | 营口天元化工研究所股份有限公司 | 3,3-bis (azidoferrocene) epoxybutane/tetrahydrofuran polyether and synthetic method |
| CN105753909A (en) * | 2016-02-01 | 2016-07-13 | 营口天元化工研究所股份有限公司 | 3, 3-bis(azido ferrocene) epoxy butane polyether and synthetic method |
| CN105753909B (en) * | 2016-02-01 | 2018-02-13 | 营口天元化工研究所股份有限公司 | 3,3 pairs of (nitrine ferrocene) epoxy butane polyethers and synthetic method |
| CN110018267A (en) * | 2019-04-16 | 2019-07-16 | 中国人民解放军国防科技大学 | Low-temperature mechanical property estimation method for PBT propellant based on reversed-phase gas chromatography data and formula |
| CN110059296A (en) * | 2019-04-16 | 2019-07-26 | 中国人民解放军国防科技大学 | High-temperature mechanical property estimation method for PBT propellant based on reversed-phase gas chromatography data and formula |
| CN110059296B (en) * | 2019-04-16 | 2021-04-16 | 中国人民解放军国防科技大学 | High-temperature mechanical property estimation method for PBT propellant based on reversed-phase gas chromatography data and formula |
| CN111440307A (en) * | 2020-04-09 | 2020-07-24 | 苏州大学 | High-functionality azide glue and preparation method thereof |
| CN111440307B (en) * | 2020-04-09 | 2022-06-07 | 苏州大学 | High-functionality azide adhesive and preparation method thereof |
| CN114558530A (en) * | 2022-01-28 | 2022-05-31 | 杭州三隆新材料有限公司 | Method and device for decomposing tetrahydrofuran and neopentyl glycol copolymer and separating and recycling tetrahydrofuran and neopentyl glycol in decomposition product |
| CN114558530B (en) * | 2022-01-28 | 2023-09-26 | 杭州三隆新材料有限公司 | Tetrahydrofuran and neopentyl glycol copolymer decomposition and tetrahydrofuran and neopentyl glycol separation and recovery method and device thereof |
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